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Journal of Cultural Heritage xxx (2017) xxx–xxx

Available online at

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Original article

Conservation of acidic papers using a dispersion of oleic

acid-modified MgO nanoparticles in a non-polar solvent
Jie Huang a , Guozhou Liang a , Gang Lu a,∗ , Jinping Zhang b
a
College of Material Science and Engineering, Nanjing Tech University, 210009 Nanjing, PR China
b
Research Institute of Cultural Heritage, Nanjing Museum, 210016 Nanjing, PR China

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

Article history: In this study, a new method was developed for the deacidification of acidic papers, by using a deacidify-
Received 14 December 2017 ing dispersion of oleic acid-modified magnesium oxide (MgO) nanoparticles in cyclohexane. We reported
Accepted 19 April 2018 that oleic acid-modified MgO nanoparticles were prepared by using a surface modification method. The
Available online xxx
results showed that the carboxylic group of oleic acid could react with the hydroxyl group on the sur-
face of nanoparticles and the reaction was esterification. MgO nanoparticles were transformed from
Keywords: hydrophilic to lipophilic, with well dispersibility in cyclohexane for 6 h. Pure MgO nanoparticles all sank
Acidic paper
in cyclohexane after 30 s, so the deacidifying agents of pure MgO nanoparticles in cyclohexane could not
Oleic acid-modified MgO nanoparticles
Deacidification
be prepared for the deacidification of papers. The stable dispersion of oleic acid-modified MgO nanopar-
Dispersibility ticles in cyclohexane then was used for the deacidification of papers. The accelerated aging tests were
also used to evaluate the effect of the new method. Results showed that the surface pH of all types of
papers were alkaline after the deacidification treatment and tensile strength values of those remained
stable after accelerated aging. The deacidification treatment had ignorable influence on the appearance of
papers, as well as inks and pigments on the paper surface. As the use of hydrophobic oleic acid-modified
MgO nanoparticles, hydrophobicity of papers changed from hydrophilic to hydrophobic.
© 2018 Elsevier Masson SAS. All rights reserved.

1. Introduction and Magnesium hydroxide in water or short-chain alcohols, was

As carriers of precious cultural information and materials, paper
relics based on cellulose are the important part of cultural her-
itages [1]. However, paper relics are now suffering from a series of
erosion such as acidification, oxidation, photo-degradation and air
pollution [2]. Acidification is the main factor leading to depolymer-
ization of cellulose [3]. It has been reported that acidity catalyzes
could increase the rate of the hydrolysis of cellulose [4]. Water in
the air and inside papers could also speed up the hydrolysis of cel-
lulose by providing H+ as the catalyst [5]. The depolymerization of
cellulose could also play a leading role in the decrease of mechani-
cal properties and surface color changes of paper relics [6]. By the
time, acidic papers may turn brittle and darken.
Fortunately, a variety of methods have been prepared for the
deacidification and pH control of paper relics. The dispersion of
alkaline nanoparticles in water or organic solvents has been widely
used to neutralize the acidic substances in papers. For example,
the use of a dispersion of alkaline nanoparticles such as Calcium
∗ Corresponding author.
E-mail address: lugang@njtech.edu.cn (G. Lu).
reported as an effective method of the neutralization of paper relics
[7–11]. However, the major drawback of these methods is that they
may not be suitable for the inks, dyes and pigments, which are
sensitive to water or polar solvents. A stabilizer-free non-polar dis-
persion of magnesium hydroxide in cyclohexane was applied to the
deacidification of contemporary art on paper by spraying, creating
a neutral or weakly alkaline environment in papers because of the
conversion of hydroxides and carbonates [12]. A dispersion of MgO
particles in perfluo-roheptane (C7 F16 ) was widely used in paper
®
deacidification by the Bookkeeper process [13,14]. This method
has several advantages such as its general ease of application, no
need for preconditioning of papers and its non-swelling action.
However, a great deal of fluorinated dispersants, surfactants used
to prevent the aggregation of MgO particles in perfluoroheptane
(C7 F16 ), are high priced. And it has been shown that the use of sur-
factants and other stabilizers could reduce the reactivity of particles
or nanoparticles, creating a too alkaline environment in papers
that could resulting in the occurrence of alkaline depolymerization
[15]. In addition, the interaction and degradation of surfactant were
not completely clear [12]. Therefore, a deacidifying agent without
surfactants for the deacidification of acidic paper relics should be
studied and prepared.

https://doi.org/10.1016/j.culher.2018.04.018
1296-2074/© 2018 Elsevier Masson SAS. All rights reserved.

Please cite this article in press as: J. Huang, et al., Conservation of acidic papers using a dispersion of oleic acid-modified MgO nanopar-
ticles in a non-polar solvent, Journal of Cultural Heritage (2017), https://doi.org/10.1016/j.culher.2018.04.018
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In this study, Magnesium oxide nanoparticles were applied to
paper deacidification owing to their outstanding advantages such
as high reaction activity, minor side effect and economic bene-
fits. However, many studies showed that nanoparticles are easily
to agglomerate in non-polar solvents due to their large surface
area and poor compatibility between their hydrophilic surface
of nanoparticle and hydrophobic non-polar solvents. Therefore,
the applications of nanoparticles were seriously limited. Thus in
order to improve their dispersion capacity in non-polar solvents
and gain stable deacidifying agents, the surface of nanoparticles
should change from hydrophilicity to hydrophobicity by surface-
modification agents. These surface-modification agents should
have a hydrophobic long alkyl chain that provides steric stabiliza-
tion in non-polar solvents and a hydrophilic functional group that
reacts with the nanoparticle surface [16]. Cis-9-octadecenoic acid
(oleic acid) has been widely used for the surface modification of
inorganic nanoparticles, because the carboxylic group of oleic acid
interacts with the nanoparticle surface and the long alkyl chain
acts as a dispersion agent to form steric hindrance. For example,
it has been reported that ZnO, CuO, SiO2 and Mg(OH)2 nanopar-
ticles modified with oleic acid have been prepared to enhance
their dispersion stability in non-polar organic solvents [17–19].
In their studies, a covalent bond was formed by the esterifica-
tion reaction between the carboxylic group of oleic acid and the
hydroxyl groups on the surface of nanoparticles. However, little
work reported the oleic acid-modified MgO nanoparticles and their
dispersion performance in non-polar solvents. And few studies
have been reported that oleic acid-modified MgO nanoparticles
were used for paper deacidification. The chemical reaction among
MgO nanoparticles, acidic substances and carbon dioxide could cre-
ate a neutral or weakly alkaline environment in papers by means
of the conversion of magnesium oxide into hydroxides and carbon-
ates [20]. Cyclohexane, a non-polar and volatile solvent, was used
in this study to minimize the risk of color changes of inks, dyes and
pigments.
In this work, a dispersion of oleic acid-modified MgO nanopar-
ticles in cyclohexane was utilized for the deacidification of acidic
papers. Herein, we reported that oleic acid-modified MgO nanopar-
ticles were prepared by using a surface modification method.
The chemical reaction between oleic acid and MgO nanoparti-
cles was investigated with Fourier transform infrared (FT-IR). The
absorption of oleic acid was also measured by Thermo gravimetric
analysis (TGA) and X-ray diffraction (XRD). The dispersion stabi-
lization of oleic acid-modified MgO nanoparticles in cyclohexane
was assessed by sedimentation tests. Also, the micro-structure
of the nanoparticles was investigated with transmission elec-
tron microscopy (TEM). The efficacy of oleic acid-modified MgO
nanoparticles was investigated by accelerated aging tests. The sur-
face pH, tensile strength and colorimetric measurements of paper
samples were tested in each case. Scanning electron microscope
(SEM) was used to analyze the micro morphologies of the paper
surfaces. Moreover, the surface properties of paper sample were
also assessed by using water contact angle test.
Table 1
Parameters of the paper samples.
Machine-made paper of 50
Components Groundwood pulp (c. 50%) and
chemical pulp (c. 50%)
2
Grammage (g/m ) 70–75
pH 4.25–4.45
Tensile strength (kN/m) 1.28–1.41
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ticles in a non-polar solvent, Journal of Cultural Heritage (2017), https://doi.org/10.1016/j.culher.2018.04.018
2. Experimental
2.1. Materials
Cyclohexane (AR), oleic acid (AR), MgO nanoparticles (AR) and
acetone (AR) were purchased from Lingfeng Chemical Reagent Co.,
Shanghai, Ltd. and used without further purification.
2.2. Oleic acid-modified MgO nanoparticles preparation and
characterization
At first, the cyclohexane solution (0.07 w/v% oleic acid) was
prepared by dissolving 0.07 gram of oleic acid to 100 ml of cyclo-
hexane in a flask, then 1 gram of pure MgO nanoparticles was
added into them. The mixture was heated by using oil bath heating
under vigorous stirring at 40 ◦ C for 60 min. The nanoparticles were
vacuum-filtered and washed with acetone for three times. Then the
white powders were dried under vacuum at 50 ◦ C for 24 h to obtain
the oleic acid-modified MgO nanoparticles.
Fourier transform infrared (FT-IR) analysis was performed using
iN10 (Nicolet, USA) with KBr method. X-ray diffraction (XRD)
analysis for powders was performed using D/Max-IIIC (Rigaku,
Japan) with Cu K␣ radiation (40 kV, 100 mA). The shape and size
of nanoparticles were observed by using a transmission electron
microscope (TEM, Tecnai G2 T20). Thermogravimetric analysis
(TGA) was performed by using a Netzsch Sta 449 C thermo gravi-
metric analyzer and the powder samples were heated in N2 up to
600 ◦ C and the heating rate was 10 ◦ C/min.
The stability of oleic acid-modified MgO nanoparticles in
cyclohexane/water was assessed by the sedimentation tests. In
sedimentation tests, 0.1 gram of pure or oleic acid-modified MgO
nanoparticles was dispersed in 10 ml of cyclohexane/water under
vigorous stirring for 30 minutes. Then the suspensions were placed
statically at room temperature and the dispersion capacity of
nanoparticles was observed.
2.3. Paper samples preparation
Three kinds of paper samples were selected for the experimen-
tal and Table 1 showed the parameters of paper samples. Chinese
art paper of 50 , known as an Xuan paper, was a type of Chinese
traditional hand-made papers. Compared with the Machine-made
papers and newspapers of 50 , they had higher pH values and were
under the weakly acidic or nearly neutral condition. However, they
should be treated by deacidifying agents in order to change their
pH from weakly acid to above neutral and form enough alkaline
reservoir for enhancing their durability. These paper samples were
stored at 50% RH and 23 ◦ C (ISO 187-1990).
2.4. Dispersions preparation and paper deacidification
An amount of 0.7 g of oleic acid-modified MgO nanoparticles
was re-dispersed in 100 ml of cyclohexane via ultrasonic treatment
Newspaper of 50 Chinese art paper of 50
Chemical pulp (c. 70%) with Blue sandalwood bark fibers (c.
massive lignin and other additives 30–40) mixed with rice straw
49–52 24–26
5.22–5.42 6.86–6.98
1.34–1.46 0.82–0.98
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at 100 W for 10 minutes to obtain the dispersion. The dispersion of

oleic acid-modified MgO nanoparticles in cyclohexane was applied
to the acidic paper samples by impregnation by immersion for
10 minutes. Then the treated paper samples were dried rapidly
in the natural environment. Afterwards, the untreated and treated
samples, stored at 23 ◦ C and 50% RH for 24 hours, were investigated.

2.5. Accelerated aging tests

Following the standard ISO 5630-1:1991, the samples were

exposed to 105 ± 2 ◦ C and relative humidity of 65% in an aging oven
for 72 hours, which corresponds to about 25 years of natural aging.
Previous to and after the tests, paper samples were stored at 23 ◦ C
and 50% RH for at least 24 hours (ISO 187-1990).

2.6. Paper characterization

The characteristics of paper samples (surface pH, tensile

strength, scanning electron microscope and water contact angle) Fig. 1. FT-IR spectrum of (a) pure oleic acid, (b) pure MgO nanoparticles and (c) oleic
acid-modified MgO nanoparticles.
were measured to investigate the efficacy of the oleic acid-modified
MgO nanoparticles in the deacidification of papers by using stan-
dard technique.
Following the standard TAPPIT 529 OM-2004, the surface pH
values of paper samples were measured using Orion 3 STAR pH
Benchtop (Thermo).
Tensile strength tests on paper samples were performed on an
electron tensile testing machine (Drick DRK101B), according to the
standard ISO 1924-2:1994. At least 10 specimens, with 180 mm
long and 15 mm wide, were tested in order to check for repeatabil-
ity.
Colorimetric measurements CIE (L* a* b* ) were performed by
using the colorimeter DRK 103B (Drick), in the D65/10 mode. The
parameter of L* represents the lightness (the smallest value being
black), the parameter of a* represents the position between red
and green (the smallest value being green), and the parameter of
b* represents the position between yellow and blue (the smallest
value being blue) [21]. The total color difference (E* ) was calcu-
lated using the equation of E* = (L*2 + a*2 + b*2 )1/2 . For each
Fig. 2. TGA curves of (a) the pure and (b) oleic acid-modified MgO nanoparticles.
colorimetric value, an average of ten specimens was calculated.
A scanning electron microscope (JEOL JSM-5900) was used to
evaluate the distribution and sizes of pure and oleic acid-modified at 1710 cm−1 in the spectrum of pure oleic acid, replaced by a
MgO nanoparticles on paper sample surfaces. new band at 1574 cm−1 which was in the spectrum of oleic acid-
The water contact angles were measured by using dynamic con- modified MgO nanoparticles. And this new band was attributed to
tact angle and absorption tester (DTA1100). The acidic papers were the stretching vibration of carboxylate, representing that the car-
cut into pieces of dimensions 200 mm × 15 mm. boxyl group of pure oleic acid reacted with the hydroxyl groups on
the surface of pure MgO nanoparticles and the product was car-
3. Results and discussion boxylate ( C(=O) OMg). Thus, the chemical reaction could take
place through esterification process of:
3.1. Preparation of oleic acid-modified MgO nanoparticles MgO(OH)n + yHOOCC17 H33 → MgO(OH)n−y [OOCC17 H33 ]y + yH2 O

3.1.1. FT-IR analysis
Fourier transform infrared measurements were carried out to
understand the adsorption behaviors of the oleic acid on MgO
nanoparticle surface. Fig. 1 shows the typical FT-IR spectra of pure
oleic acid (a), pure MgO nanoparticles (b) and oleic acid-modified
MgO nanoparticles(c), respectively. In the curve (a), the peaks
located at 2924 and 2854 cm−1 were derived from the existence
of the asymmetric CH2 stretch and the symmetric CH2 stretch,
respectively. The strong adsorption at 1710 cm−1 was attributed to
the stretching vibration of carbonyl group ( C = O) in the oleic acid.
In the curve (b), the spectrum of pure MgO nanoparticles showed a
broad peak at 3440 cm−1 , which was assigned to the characteristic
absorption of hydroxyl groups. However, in the curve(c), peaks at
2924 and 2852 cm−1 corresponded to the alkyl chain, which were
not observed in the spectrum of pure MgO nanoparticles. Further-
more, the C = O stretch band of carbonyl group, which was present
It was concluded that the long alkyl chain of oleic acid was
chemically absorbed onto the surface of MgO nanoparticles.
3.1.2. TGA analysis of oleic acid-modified MgO nanoparticles
In order to verify and further investigate the chemical bond-
ing between MgO nanoparticles and oleic acid, TGA curves of the
pure and oleic acid-modified MgO nanoparticles were recorded in
Fig. 2. The TGA curves revealed that the weight loss occurred in the
temperature range from 50 to 600 ◦ C. From Fig. 2(a), one can find
that about 3.21% of total weight of pure MgO nanoparticles was
lost which may be due to the evaporation of adsorbed water. From
Fig. 2(b), it was clear that about 7.02% of the total weight of the
oleic acid-modified MgO nanoparticles was lost. The weight loss of
these modified nanoparticles could be attributed to the desorption
of water and the decomposition of oleic acid. Therefore, com-
pared the two TGA curves, about 3.81% of the weight loss of oleic

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Fig. 3. X-ray diffraction patterns of (a) the pure and (b) oleic acid-modified MgO
nanoparticles.
acid-modified MgO nanoparticles corresponded to the chemisorp-
tion of oleic acid. The results also suggested that there was an
effective chemical bonding between MgO nanoparticles and oleic
acid.
3.1.3. X-ray diffraction patterns
To further investigate the influence of the chemical reaction
between oleic acid and the surface of MgO nanoparticles on the
crystalline structure of MgO nanoparticles, X-ray diffraction pat-
terns of the pure MgO nanoparticles and oleic acid-modified MgO
nanoparticles were shown in Fig. 3. The positions and relative inten-
sities of all characteristic peaks at Fig. 3b were well in accordance
with the phase structure of magnesium oxide (International Cen-
ter for Diffraction Data, JCPDS 4-829). The XRD patterns of the oleic
acid-modified MgO nanoparticles (Fig. 3a) were almost the same
as those of the pure MgO nanoparticles (Fig. 3b), implying that the
oleic acid only modified the surface properties of MgO nanoparti-
cles and did not influence the internal crystalline structure of MgO
nanoparticles.
3.1.4. Morphology of nanoparticles
The TEM images of the pure and oleic acid-modified MgO
nanoparticles in cyclohexane solution were shown in Fig. 4a, b. As
shown in Fig. 4, the main sizes of nanoparticles were between 50
and 100 nm, as calculated statistically in the visual field. The pure
MgO nanoparticles easily aggregated to bigger ones in cyclohexane
(Fig. 4a), while oleic acid-modified ones showed good dispersion
(Fig. 4b). This phenomenon indicated that the long alkyl chain of
oleic acid on the surface of MgO nanoparticle can effectively hin-
der the agglomeration of oleic acid-modified MgO nanoparticles in
cyclohexane.
3.1.5. Dispersion capacity of nanoparticles in water or
cyclohexane
In order to evaluate the compatibility and dispersion stability
of pure and oleic acid-modified MgO nanoparticles with water and
non-polar solvents, the sedimentation photographs of the nanopar-
ticles in cyclohexane and water for time periods of 30 s (left) and 6 h
(right) were respectively observed in Fig. 5. After 30 s, most of the
pure MgO nanoparticles sank in cyclohexane, while they had good
dispersion capacity in water. These results suggested that pure
MgO nanoparticles dispersed in cyclohexane could not be well pre-
pared, therefore the deacidifying agents of pure MgO nanoparticles
in cyclohexane could be ineffective. Compared with the pure MgO
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ticles in a non-polar solvent, Journal of Cultural Heritage (2017), https://doi.org/10.1016/j.culher.2018.04.018
nanoparticles in water and cyclohexane, the oleic acid-modified
MgO nanoparticles can stably suspend in cyclohexane for 6 h and
no obvious sedimentation was observed. However, these nanopar-
ticles were observed to float on the surface of water for 10 days
or even longer. The above phenomenons illustrated that the pure
MgO nanoparticles had transformed from hydrophilic to lipophilic
owing to the presence of the hydrophobic long alkyl chain of oleic
acid on the surface of MgO nanoparticles. And this hydrophobic
long alkyl chain on the MgO nanoparticle surface can improve the
compatibility and dispersibility of nanoparticles in non-polar sol-
vents.
3.2. Deacidification and protection of acidic papers
3.2.1. Surface pH variation
In Table 2, after the deacidification treatment, the surface pH
values of all types of paper samples increased considerably. The pH
values achieved after deacidification should keep from 7.0 to 8.5
but not high enough to result in alkaline depolymerization [22].
The optimal pH values of three types of paper samples were in
the 8.0 range. The pH values of both treated and untreated paper
samples were shown to decrease after the accelerated aging tests.
However, the untreated samples showed a higher decrease in the
pH compared with the treated ones, probably because oleic acid-
modified MgO nanoparticles could react with acidic substances and
carbon dioxide by means of the conversion of magnesium oxide
into hydroxides and carbonates. The neutralization reaction can
effectively inhibit the acid hydrolysis of cellulose fibers. In addition,
the remaining alkaline reserve in papers could play an important
role in neutralizing with the later accumulation of acidic substances
in order to achieve long-term deacidification of papers during the
natural aging process.
3.2.2. Tensile strength variation
Tensile strength was measured to characterize the mechanical
properties of the paper samples (Fig. 6). After the accelerated aging
tests, the tensile strength of untreated paper samples was reduced
sharply to approximately 80%, which could be caused by the hydrol-
ysis of cellulose under the acidic condition. However, after the
deacidification treatment, the tensile strength of paper samples
remained substantially unchanged. And after accelerated aging,
the treated paper samples still retained good resistance to tensile
strength, which was due to the present of alkaline nanoparticles.
Therefore, the above results confirmed that the oleic acid-modified
MgO nanoparticles could improve the mechanical properties of
acidic papers, along with deacidification.
3.2.3. Surface morphology of paper relics
We also investigated the micro morphologies of surfaces of
paper samples. Fig. 7 respectively showed the SEM images of
untreated and treated paper samples before and after accelerated
aging tests. The micrographs in Fig. 7(a) and Fig. 7(b) revealed that
the densely packed cellulose fibers, within the acidic papers, pre-
sented a net structure and appeared to be random in orientation. It
was clearly found from Fig. 7(c) that plenty of white particles, pos-
sibly related to the oleic acid-modified MgO nanoparticles, were
filled into the inter-layer crevice and covered on the surface of cel-
lulose fibers after deacidification treatment. It was also seen from
Fig. 7(d) that the net structured cellulose fibers, after the acceler-
ated aging test, were not damaged compared with the untreated
ones. The above results confirmed that oleic acid-modified MgO
nanoparticles deposited on the fibers can effectively retard the
aging of papers and inhibit the damage to cellulose fibers.
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Fig. 4. TEM images of (a) the pure and (b) oleic acid-modified MgO nanoparticles in cyclohexane solution.

Fig. 5. Sedimentation photographs of pure MgO nanoparticles in water (a) and cyclohexane (b), oleic acid-modified MgO nanoparticles in water (c) and cyclohexane (d).

Table 2
Surface pH variation before and after accelerated aging tests for the treated and untreated paper samples.

Measured after treatment Measured after accelerated aging tests

Untreated Treated Untreated Treated


50 machine-made paper 4.35 8.50 3.46 8.05
50 newspaper 5.32 8.23 4.48 7.67
50 Chinese art paper 6.95 8.45 6.10 8.12

3.2.4. Chromatic changes

Fig. 6. Results of tensile strength of the treated and untreated paper samples before
and after accelerated aging tests.
The colorimetric coordinates of the three paper samples before
and after deacidification were presented in Table 3. All of the paper
samples showed no obvious color changes after the deacidification
treatment. Therefore, this phenomenon suggested that oleic acid-
modified MgO nanoparticles have no influence on the appearance
of paper matrix.
In Fig. 10, an ancient Chinese painting from the Qing dynasty
(about 1890 A.D.) was chosen as the test subject for the deacid-
ification experimental. This painting was sourced from Nanjing
Museum. The CIE L* a* b* system was also used to investigate the
influence of the dispersion of oleic acid-modified MgO nanoparti-
cles in cyclohexane on the inks and pigments of papers. The color
changes before and after the deacidification treatment were shown
in Table 4, and 4 sites which were related to various inks and
pigments were chosen on the painting. The results showed that
the color changes of the inks and pigments on the painting were
around 1.0, illustrating that the dispersion of oleic acid-modified

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Fig. 7. SEM images of the surface of untreated paper sample (a) before and (b) after accelerated aging test; treated paper sample (c) before and (d) after accelerated aging
test.

deacidification treatment. Meanwhile, a drop of water was lowered

on the surface of the untreated and treated papers respectively, as
shown in Fig. 9. Compared with the untreated papers, it was obvi-
ous that the drop of water on the treated ones kept a spherical shape
rather than spreading on the surface or penetrating into the paper
fibers. The above results confirmed that the oleic acid-modified
MgO nanoparticles which were deposited on the papers increased
the hydrophobicity of the acidic paper because the hydrophobic
carbon-hydrogen long chains of oleic acid were grafted onto the
surface of MgO nanoparticles by ester reaction.

4. Conclusion

This study presented that hydrophobic oleic acid-modified MgO

Fig. 8. Water contact angles of machine-made paper of 50 before and after deacid-
ification treatment.
MgO nanoparticles in cyclohexane did not affect the inks and pig-
ments on papers.
3.2.5. Water contact angle test
Contact angle is a qualitative measure of the wetting of a solid
by a liquid. It is defined as the angle formed by a liquid at the three
phase boundary where a liquid, gas and solid intersect [23,24]. The
hydrophobic properties of the surface of the treated and untreated
paper samples were studied through contact angle measurements.
Fig. 8 showed the results of water contact angle of paper sam-
ples before and after deacidification treatment. The contact angle
of untreated machine-made papers sharply decreased from initial
116◦ to 50◦ in 20 s. However, the contact angle of the paper sam-
ple, which had an initial value of 120◦ , remained constant after the
nanoparticles with good compatibility and dispersibility in cyclo-
hexane were utilized for the deacidification of acidic papers. The
oleic acid-modified MgO nanoparticles were prepared by a surface
modification method. FT-IR and TGA results confirmed that there
was an effective chemical bonding between MgO nanoparticles
and oleic acid. This ester reaction did not change the crys-
talline structure of MgO nanoparticles. The reaction can effectively
avoid the agglomeration of oleic acid-modified MgO nanoparti-
cles in cyclohexane. In addition, this reaction between OH on the
nanoparticles and COOH of the oleic acid can promote the dis-
persion stability of a magnesium oxide suspension in non-polar
solvent of cyclohexane. Then the oleic acid-modified MgO nanopar-
ticles dispersion in cyclohexane were applied to the conservation
of acidic paper. After deacidification treatment, the surface pH of
all types of acidic papers was in the 8.0 range, which can effectively
eliminate the acidic substances in papers to inhibit the degradation
of paper and avoid alkaline depolymerization. In addition, the ten-
sile strengths of the three kinds of papers were almost constant.
After accelerated aging tests, the surface pH and tensile strength

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Table 3
Colorimetric coordinates of paper samples before and after deacidification.

Machine-made paper of 50 Newspaper of 50 Chinese art paper of 50

Before L* = 72.23 ± 0.23 L* = 67.26 ± 0.46 L* = 92.40 ± 0.28

a* = 1.79 ± 0.13 a* = 4.26 ± 0.17 a* = −0.52 ± 0.07
b* = 18.96 ± 0.78 b* = 22.31 ± 0.14 b* = 8.61 ± 0.19
After L’ = 72.42 ± 0.14 L* = 67.52 ± 0.04 L* = 92.92 ± 0.10
a’ = 1.64 ± 0.35 a* = 4.10 ± 0.56 a* = −0.70 ± 0.05
b’ = 18.39 ± 0.80 b* = 22.13 ± 0.40 b* = 8.42 ± 0.38
Variation (after - before) L* = −0.19 ± 0.54 L* = +0.26 ± 0.46 L* = +0.52 ± 0.73
a* = −0.15 ± 0.28 a* = −0.16 ± 0.13 a* = −0.18 ± 0.01
b* = −0.57 ± 0.14 b* = −0.18 ± 0.04 b* = −0.19 ± 0.25

Fig. 9. Water drop on the surfaces of (a) untreated machine-made paper of 50 and (b) treated by dispersions of oleic acid-modified MgO nanoparticles.

Acknowledgment

The authors gratefully acknowledge the financial supports

from National science and technology support program (No.
2014BAK09B00), and from the Cultural Relic Museum of Nanjing.

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Please cite this article in press as: J. Huang, et al., Conservation of acidic papers using a dispersion of oleic acid-modified MgO nanopar-
ticles in a non-polar solvent, Journal of Cultural Heritage (2017), https://doi.org/10.1016/j.culher.2018.04.018