Journal of Cultural Heritage 61 (2023) 65–75

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Journal of Cultural Heritage

journal homepage: www.elsevier.com/locate/culher

Original article

Investigating the moisture sorption behavior of naturally and

artificially aged bamboo paper with multi-analytical techniques
Jing Tan a, Xiaohang Fu a, Yujing Lu a, Biao Chen a,∗, Yanwei Ding b,∗
a
Department of History of Science and Scientific Archaeology, University of Science and Technology of China, Hefei 230026, China
b
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China

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

Article history: Hygroscopicity affects the chemical and physical stabilities of paper-based historical relics. In this re-
Received 28 November 2022 search, the moisture sorption behavior of naturally aged bamboo paper dating from the Qing Dynasty to
Accepted 10 March 2023
the Republic of China, and artificially aged and untreated modern bamboo paper was investigated using
dynamic vapor sorption analysis (DVS). The results were fitted by sorption models to analyze the regulari-
Keywords: ties of changes in the moisture absorption of aged bamboo paper. Fourier transform infrared spectroscopy
Aged bamboo paper (FTIR) and scanning electron microscopy (SEM) were used to characterize the chemical and physical struc-
Isothermal moisture sorption tures of aged bamboo paper. It was found that untreated and aged bamboo paper showed similar mois-
Sorption model ture sorption isotherms at 25 °C, indicating that aging did not alter the sorption mechanism of paper.
Chemical structure
Guggenheim Anderson de Boer (GAB) and Hailwood Horrobin (H–H) models provided good fits to the ex-
Micromorphology
perimental data and meaningful physical parameters regarding the effective sorption surface area (SGAB ),
monolayer water content (W0 ), and multilayer water content (Ws ), showing that the SGAB , W0 , and Ws of
naturally and artificially aged bamboo paper were decreased. Results of FTIR demonstrated that the lev-
els of hydrophilic groups decreased, causing a reduction in the effective adsorption sites of naturally and
artificially aged bamboo paper, which was the principal reason for a decrease in their hygroscopicity. The
fiber structure damage of naturally and artificially aged bamboo paper was observed through microscopic
morphology, which has different influences on the capillary adsorption of paper depending on the extent
of degradation.
© 2023 Consiglio Nazionale delle Ricerche (CNR). Published by Elsevier Masson SAS. All rights reserved.

1. Introduction
As the primary writing medium since papermaking was in-
vented, paper has played an invaluable role in human civilization
[1]. Manuscripts, books, documents, and works of art on paper are
the carriers of a precious heritage with the values of culture, sci-
ence, and art, which are original materials that can be used for
the research of ancient society and historical developments [2]. The
conservation state of paper materials is affected by some degrada-
tion factors due to their organic composition and hygroscopicity,
such as temperature, water, ultraviolet, microorganisms, etc. [3–5].
Especially the paper has a strong affinity for polar solvents such
as water as a result of its abundant hydrophilic groups [6]. Dur-
ing storage, it can continuously interact with moisture in the air,
adversely affecting the life of paper cultural relics. Paper will ab-
sorb water vapor in a high-humidity environment, and its inter-
nal fibers will be hydrolyzed and destroyed [7]. Moreover, it will
∗
Corresponding authors.
E-mail addresses: chenbiao@ustc.edu.cn (B. Chen), ywding@ustc.edu.cn (Y. Ding).
elongate after the hygroscopic swelling. When the ambient humid-
ity decreases, the fiber shrinks after desorption and evaporation of
water in the paper to achieve equilibrium with the atmosphere.
Under the action of cyclic changes in the environment from wet
to dry, the paper repeatedly undergoes expansion and deforma-
tion, resulting in internal stress to cause mechanical damage to
the paper [8]. Therefore, studying the moisture sorption behavior
of paper is essential to find appropriate humidity conditions for
the long-term preservation of paper cultural relics [9].
The paper sheet is a composite structure composed of fibers
and voids. Moisture is absorbed directly by fibers and transported
by diffusion through voids. Depending on the level of interaction
between cellulose fibers and water, water in paper can be classi-
fied as free water, non-freezing water, and freezing water [10,11],
which affects the physical properties as well as the chemical prop-
erties of paper. Researches reveal that the elastic modulus, yield
stress, and the ultimate tensile strength of paper will decrease at
higher moisture contents [12]. Similarly, the electrical properties of
paper are influenced by its moisture level [13,14]. During use and
storage, paper’s structure and properties will change due to aging.
It is found that thermal aging diminishes the paper’s absorption

https://doi.org/10.1016/j.culher.2023.03.004
1296-2074/© 2023 Consiglio Nazionale delle Ricerche (CNR). Published by Elsevier Masson SAS. All rights reserved.
J. Tan, X. Fu, Y. Lu et al.
and swelling capability, resulting in a more compact structure and
promoting hornification [15,16]. Additionally, swelling rate of paper
decreases due to its aging, with the water retention value (WRV)
decreasing as well, which is related to the decrease in the ability
of fiber structure to interact with water [17–19]. In order to better
understand water-cellulose interactions, various theoretical models
have been established. Some models have been applied to paper
and predict the equilibrium moisture content (EMC) of paper with
good precision [20,21].
Although the water sorption of paper has been studied, most
research has focused on chemical woody paper [22–24]. How-
ever, the majority of paper-based relics were made from tradi-
tional handmade papers, which exhibit significant differences in
physicochemical properties from mechanical paper. In addition, re-
searchers have utilized artificially accelerated aging treatments to
study the moisture adsorption of aged paper, but it’s not easy to
interpret the hygroscopic characteristics of naturally aged paper
unambiguously and generally. Due to the paucity of studies on the
moisture sorption of ancient paper, the mechanism of the changes
in water absorption properties has not been conclusively deter-
mined.
In this paper, several naturally aged paper dating from the Qing
Dynasty to the Republic of China will be evaluated for their mois-
ture sorption properties. It is a valuable and rare set of ancient ma-
terials that have the same raw materials and storage conditions,
which are very suitable for studying the natural aging character-
istics of paper. In order to conduct a comprehensive analysis, we
prepared artificially aged modern paper for comparison. The re-
search on the regularity and cause of changes in moisture absorp-
tion behavior of naturally and artificially aged paper in this work
not only compensates for the deficiencies of previous studies, but
also contributes to the preservation of paper cultural relics from
the perspective of scientific theory.
2. Research aims
This study focuses on the moisture sorption behavior of natu-
rally aged bamboo paper dating from the Qing Dynasty to the Re-
public of China as well as artificially aged modern bamboo paper
through DVS analysis. Additionally, six isothermal adsorption mod-
els (Smith, Oswin, Guggenheim Anderson de Boer, Hailwood Hor-
robin, Peleg, and Halsey) are applied for regression analysis, de-
termining the optimal adsorption models to study the regularities
for changes in moisture adsorption characteristics of bamboo pa-
per under different aging modes. Lastly, the chemical and physi-
cal structures of aged bamboo paper are characterized by Fourier
transform infrared spectroscopy (FTIR) and scanning electron mi-
croscopy (SEM). The differences in moisture sorption behavior be-
tween naturally and artificially aged paper, the regularities and
reasons for the changes in hygroscopicity of aged bamboo paper,
and the theoretical references for determining appropriate humid-
ity conditions for preserving paper cultural relics will be presented
in this paper.
3. Materials and methods
3.1. Experimental materials
The naturally aged bamboo paper is four contract documents
dating from the Qing Dynasty to the Republic of China (see Fig.
S1), including the 3rd year of Xianfeng in the Qing Dynasty (AD
1853, No. XF3), the 10th year of Guangxu in the Qing Dynasty (AD
1884, No. GX10), the 17th year of the Republic of China (AD 1928,
No. MG17), and the 28th year of the Republic of China (AD 1939,
No. MG28). All of them are from Mayang Miao autonomous county
in Hunan province and have been stored together in hemp sacks
66
Journal of Cultural Heritage 61 (2023) 65–75
to this day, and made of Moso bamboo by identifying their fibers
via optical microscopy [25]. These are excellent and rare ancient
materials with the same raw materials and storage environment
to study the characteristics of natural aging for paper. Notably, the
samples used to experiment were taken from the corners of the
contract documents to avoid visible damage.
In order to make a more comprehensive analysis, we prepared
artificially aged modern paper for comparison. The modern bam-
boo paper is also made of Moso bamboo, sourced from Longhui
county in the southwestern of Hunan province. The paper was
treated with dry heat at 105 °C for 36 and 90 days according to the
standard ISO 5630-1:1991, and moist heat at 80 °C and 65% rela-
tive humidity (RH) for 12 and 24 days according to the standard
ISO 5630-3:1996, respectively. Modern bamboo paper without any
treatment can be used to compare with aged bamboo paper.
Modern bamboo paper is similar in appearance to the naturally
aged bamboo paper above. By observing the fiber morphology of
ancient and modern samples, it can be concluded that they used
the same raw materials and papermaking technology (see Fig. S2).
In addition, FTIR was used to determine the relative content of
components (hemicellulose and lignin) among samples, indicating
that the difference in component content is minor (see Table S1).
Therefore, it would be reasonable and feasible to study the mois-
ture sorption characteristics of naturally aged and artificially aged
bamboo paper based on these two types of samples.
3.2. Dynamic vapor sorption analysis
An automatic gravimetric vapor sorption analyzer Q50 0 0 SA
(TA Instruments, USA) was used to measure scanning isotherms
of moisture (de)sorption at 25 °C. The balance and humidity were
controlled by high-purity nitrogen flowing at 10 and 200 mL/min,
respectively. About 2.0 mg of sample was used for each analysis.
The samples were exposed to increasing RH in 10% steps from 0 to
98% at 25 °C. Samples were considered in equilibrium with RH if
the weight change was less than 0.1% in 30 min. After reaching a
balance of 98%, the RH was reduced to 0 in 10% steps. The time at
which the sample reached adsorption or desorption saturation at
different RH conditions was also recorded.
The equilibrium moisture content (EMC) and the sorption rate
(R) of samples during the sorption isotherm process were calcu-
lated with Eqs. (1) and (2), respectively.
m − m 
x 0
EMC = × 100% (1)
m0
where m0 (mg) is the mass of sample after drying at 0 RH; mx
(mg) is the mass of sample after moisture absorption or desorption
equilibrium at different RH conditions.
M
R= (2)
t
where M (%) is the saturated adsorption capacity of sample at a
certain RH; t (min) is the time for sample to reach adsorption or
desorption saturation at a certain RH.
3.3. Mathematical models of sorption isotherms
Various models have been developed to mathematically express
the relationship between water activity and moisture content of
various materials, such as nonlinear, linear, and regression mod-
els. In this paper, six commonly-used sorption models as seen
in Eqs. (3)–(8) [26–28] were used to fit the experimental data
of isothermal moisture absorption and desorption for samples via
Origin analysis software (OriginLab Corporation, USA). The good-
ness of fit was evaluated by two indexes that are squared corre-
lations (R2 ) and residual sum of squares (RSS) to determine the
optimal model for moisture sorption of paper.
J. Tan, X. Fu, Y. Lu et al. Journal of Cultural Heritage 61 (2023) 65–75

Smith model:
W = a − b ln(1 − aw ) (3)
Guggenheim Anderson de Boer (GAB) model:
W0CKaw
W = (4)
(1 − Kaw )(1 − K aw +CK aw )
Oswin model:
 a b
w
W =a (5)
1 − aw
Halsey model:
 −a 1/b
W = (6)
ln aw
Hailwood Horrobin (H–H) model:
1800
 K1 K2 H K2 H

W = W0 + Ws = + (7)
Wm 100 + K1 K2 H 100 − K2 H
Peleg model: Fig. 1. Dynamic sorption water content curve of untreated sample.

W = Caaw + Kabw (8)

Here W is the water content; W0 is the monolayer water content;
Ws is the multilayer water content; Wm is the molecular weight
of the cell wall polymer per adsorption site; H is the relative hu-
midity; aW is the water activity; others are the constants of above
models.
3.4. Fourier transform infrared spectroscopy
The chemical structure of sample was characterized with a
Nicolet 8700 FTIR spectrometer (Thermo Nicolet Corporation, USA).
Approximately 1.0 mg of sample was used to prepare the transpar-
ent sheet with KBr. The spectra were measured at room tempera-
ture from 40 0 0 to 40 0 cm−1 with an accumulation of 64 scans and
a resolution of 4 cm−1 . The identification of paper components was
performed by comparing the main features of the obtained spectra
with those of the FTIR collection library, and in their absence, with
published spectra.
3.5. Scanning electron microscopy
The micromorphology of sample was observed by GeminiSEM
500 Schottky field emission scanning electron microscopy (Carl
Zeiss AG, Germany). Mounted on a sample holder with carbon con-
ductive tape and then coated with a thin layer of platinum using
a sputter coater to obtain good conductivity. The instrument was
operated at 2.0 kV with different magnifications.
4. Results and discussion
4.1. Adsorption and desorption isotherms
The dynamic sorption water content curve for the sample can
be determined by DVS. Fig. 1 presents the sorption data for the
untreated sample, showing that the internal water content was re-
moved from the sample firstly at 0 RH, and its equilibrium mois-
ture content (EMC) decreased from 3.01% to 0 (the black curve in
Fig. 1). As RH ascended, the EMC increased gradually. During the
desorption process with 98%∼0 RH, the EMC decreased continu-
ously and finally dropped to 0. Additionally, the time for the sam-
ple reaching saturation at various RH conditions (the length of the
red step-shaped curve in Fig. 1) was extended with an increase in
RH, especially at the high-humidity stage of 80–98%.
Sorption isotherms provide some information about the mech-
anism of materials interacting with water in different humid en-
vironments. As shown in Fig. 2, there are sigmoidal sorption
isotherms that concave upwards for both untreated and aged sam-
ples, belonging to Brunauer’s class II [27], which indicates that
the moisture sorption mechanism of paper was not affected by
aging. As expected, the EMC of all samples was added with in-
creasing RH. Furthermore, the EMC in the desorption was always
higher than that in the absorption, resulting in a retention loop
between the moisture absorption and desorption isotherms. The
difference between these curves is defined as hysteresis, which re-
lates to the nature and state of the components of materials and
reflects their potential for structural and conformational rearrange-
ments. The explanation for the occurrence of moisture sorption
hysteresis comprises the ink bottle theory, the molecular shrink-
age theory, the capillary condensation, and the swelling fatigue
theory [29–31].
As the time of artificial and natural aging was extended, the
moisture sorption isotherms gradually shifted downward (Fig. 2).
That is, aging reduced the moisture absorption capacity of the pa-
per. To analyze the effects of different aging modes on the hy-
groscopic capacity of paper, the EMC decrease rates of aged sam-
ples at 98% RH were calculated. The untreated sample was the
initial reference for artificially aged samples, and the latest sam-
ple, No. MG28 (AD 1939) was the initial reference for naturally
aged samples. The inserts in Fig. 2 illustrate the EMC decrease
rates of different aged samples. Among artificially aged samples,
the EMC decrease rate of 24 days with moist heat (15.49%) is
slightly higher than that of 90 days with dry heat (14.98%). There-
fore, the multiple-effect of water and temperature in moist heat
aging results in destroying the hygroscopicity of paper more in-
tensively than the single effect of temperature in dry heat ag-
ing. A similar conclusion is that the presence of water would
accelerate the hydrolysis of fibers, resulting in a greater degree
of damage to the mechanical and chemical properties of paper
with hydrothermal aging than dry heat aging [32]. By contrast,
there are minor changes in the EMC decrease rates between nat-
urally aged samples. It is possible that the hygroscopic proper-
ties of the paper remain relatively stable after a long period of
storage.
The moisture absorption and desorption rates of samples
during the isotherm sorption process as seen in Fig. 3 show that
both decreased initially, then increased, and the changing trend
resembles the shape of the letter "U’’. This appears that there
may be different acting forms in the moisture sorption process
of paper. It was observed that the absorption rates of all samples
gradually declined with increasing RH until they dropped to the
lowest level at approximately 50% RH. Since then, the rates have

67
J. Tan, X. Fu, Y. Lu et al.
Fig. 2. Moisture sorption isotherms and EMC decrease rates of untreated and aged samples: (a) dry heat aging; (b) moist heat aging; (c) natural aging.
risen incrementally and reached the maximum value at 98% RH.
The desorption rates decreased as RH lowered and reached the
lowest value near 40% RH, after which they gradually increased.
Consequently, the storage humidity for the bamboo paper should
be about 40∼50% RH, which can reduce the degrees of water ex-
change between paper and ambient environment, contributing to
maintaining the stability of paper. In addition, it also can be seen
from Fig. 3 that the moisture absorption and desorption rates of
artificially aged samples show a decreasing trend with extending
the aging time. However, the regularity of that in naturally aged
samples is barely noticeable.
4.2. Moisture sorption models analysis
We selected the untreated sample for fitting analysis to deter-
mine appropriate isothermal sorption models. Using Origin analy-
sis software, a regression analysis was conducted based on exper-
imental data regarding water content (W) and water activity (aw )
68
Journal of Cultural Heritage 61 (2023) 65–75
of the sample and isothermal sorption models from Eqs. (3) to (8).
The results are shown in Table 1.
Among six models, the R2 of Peleg model in adsorption and
desorption are both greater than 0.999, and the RSS are all close
to 0, indicating the best fit. Followed by GAB and H–H models,
whose R2 of moisture absorption and desorption fitting are higher
than 0.99, showing well-fitting. Thus, Peleg, GAB, and H–H models
can be used to describe the isothermal moisture sorption process
of bamboo paper, and their equations are shown in Table S2.
The physical and chemical stabilities of paper are directly in-
fluenced by moisture absorption. Generally, the water content of
monolayer covering the hydrophilic part of paper surface has been
considered to be the moisture content standard for materials to
maintain optimal storage stability [33,34]. It is necessary to study
the monolayer water content and the changes in hygroscopicity
of aged paper for its long-term preservation. The Peleg model,
which has no theoretical basis, is an empirical equation without
the monolayer [35]. In contrast, the GAB and H–H models include
J. Tan, X. Fu, Y. Lu et al. Journal of Cultural Heritage 61 (2023) 65–75

Fig. 3. Moisture absorption and desorption rates of untreated and aged samples: (a) dry heat aging; (b) moist heat aging; (c) natural aging.

Table 1
Fitting parameters and evaluation indexes of sorption models.

Models W0 (Wm , a) b (K1 ) C (K2 ) K R2 RSS

Adsorption Smith 1.63 6.18 0.9914 4.52

GAB 3.65 15.01 0.87 0.9940 3.15
Oswin 6.62 0.35 0.9899 5.31
Halsey 79.56 2.53 0.9713 15.13
H-H 493.78 14.01 0.87 0.9940 3.15
Peleg 0.88 12.94 12.45 17.28 0.9994 0.34
Desorption Smith 3.23 6.36 0.9513 28.37
GAB 6.14 7.66 0.78 0.9996 0.23
Oswin 8.82 0.29 0.9558 25.76
Halsey 501.76 3.05 0.9216 45.65
H–H 293.08 6.66 0.78 0.9996 0.23
Peleg 7.00 0.79 12.66 14.78 0.9999 0.06

the calculation of monolayer water content, and their equation pa-
rameters have a physical meaning. Thus, the GAB and H–H models
were used to analyze the characteristics of moisture adsorption for
aged bamboo paper.
GAB model, developed from Langmuir and BET theories of phys-
ical adsorption, is a multimolecular layer sorption equation that
can explain the sigmoidal sorption isotherms. As shown in Eq. (4),
the W0 is monolayer water content, and the C and K are Guggen-
heim constants corresponding to the energies of interaction be-
tween the first and further sorbed molecules at individual sorption
sites [36]. Water content (W) and water activity (aw ) during mois-
ture absorption process measured by DVS for untreated and aged
samples were fitted with the GAB model. The fitting parameters
are shown in Table 2, and Fig. S3 illustrates the fitting effects.
The R2 of naturally and artificially aged samples are above 0.98
and the RSS are less than 10 (Table 2). The correlations between
the experimental values and predicted values of EMC for most of
the samples are greater than 0.99 (see Fig. S3), indicating the va-
lidity of fitting. Thus, GAB parameters can be used to characterize
the hygroscopic properties of aged bamboo paper.
According to the W0 in Table 2, the effective sorption surface
area (SGAB , m2 ·g−1 ) of samples was calculated by Eqs. (9) [37], and
the results are presented in Fig. S4.
SGAB = W0 NA ρσ /Mwat (9)

69
J. Tan, X. Fu, Y. Lu et al. Journal of Cultural Heritage 61 (2023) 65–75

Table 2 ples, the Wm increased significantly. It will be seen from this that
Fitting parameters of samples in moisture adsorption process based on
aged samples have fewer effective adsorption sites and more ma-
GAB model.
trix mass is required to reach the number of adsorption sites in
Samples W0 (%) C K R2 RSS the untreated sample, which is consistent with the result of SGAB
Untreated 3.65 15.01 0.87 0.9940 3.15 of aged samples being reduced in Fig. S4. The changes in constants
Dry heat-36 days 3.53 14.28 0.87 0.9939 2.77 K1 and K2 correspond to the C and K in GAB model respectively.
Dry heat-90 days 3.09 13.07 0.88 0.9977 0.92 Based on the Eqs. (7) and parameters in Table 3, the mois-
Moist heat-12 days 3.57 13.79 0.87 0.9963 1.69
ture adsorption isotherms of samples were divided into monolayer
Moist heat-24 days 3.16 12.04 0.87 0.9955 1.78
No. MG28 3.24 12.91 0.90 0.9956 2.67 adsorption and multilayer adsorption as shown in Fig. 4. During
No. MG17 3.18 12.73 0.90 0.9943 3.41 moisture absorption process, samples undergo three phases: Phase
No. GX10 3.04 12.25 0.90 0.9850 8.34 I (0∼20% RH), the monolayer water content increased rapidly at
No. XF3 2.91 11.97 0.91 0.9876 6.86
a maximum rate, while multilayer water content remained low,
so the monolayer adsorption was predominant. In Phase II (20–
Table 3 80% RH), the adsorption rate of monolayer became slow as RH
Fitting parameters of samples during moisture adsorption process based on increased and its adsorption capacity tended to be saturated at
H–H model.
about 50% RH, which corresponds to the moisture absorption rates
Samples Wm (g·mol−1 ) K1 K2 R2 RSS of samples reaching the lowest value near 50% RH in Fig. 3. Con-
Untreated 493.78 14.01 0.87 0.9940 3.15 versely, the multilayer water content ascended significantly with
Dry heat-36 days 527.72 13.81 0.87 0.9915 3.89 increasing RH and its adsorption rate also increased synchronously,
Dry heat-90 days 581.97 12.07 0.88 0.9977 0.92 so this phase was dominated by multilayer adsorption. A sharp in-
Moist heat-12 days 507.72 13.79 0.87 0.9963 1.69 crease in the water content of samples occurred in phase III after
Moist heat-24 days 596.95 11.70 0.88 0.9917 3.24
No. MG28 545.51 12.82 0.90 0.9959 2.49
80% RH. There was no limitation for multilayer adsorption when
No. MG17 551.97 12.63 0.90 0.9947 3.12 RH neared 100%, indicating that capillary condensation occurred in
No. GX10 595.61 12.09 0.90 0.9853 8.18 a high-humidity environment.
No. XF3 607.13 11.89 0.91 0.9883 6.47 The three phases above all exist in the isothermal moisture ab-
sorption of untreated and aged samples in Fig. 4, and their re-
spective humidity ranges have no change. It demonstrates that ag-
where NA is the Avogadro number; ρ is the water density; σ is the ing has little effect on the adsorption mechanism of paper, which
average area where water occupies the complete monolayer (0.114 is consistent with the fact that the type of moisture sorption
nm2 ); Mwat is the molar mass of water. isotherms of aged samples did not alter in Fig. 2. However, some
There are many active polar adsorption sites with high inter- changes in capacity at different adsorption phases of naturally and
action energy on the paper surface, which can combine with wa- artificially aged samples were observed. The adsorption capacities
ter molecules through strong microforces such as van der Waals of monolayer, multilayer, and capillary were significantly lower in
and electrostatic forces to form the monolayer. As the monolayer artificially aged samples with greater aging degrees. Similar to ar-
is saturated in moisture adsorption, it becomes the secondary ad- tificially aged samples, naturally aged samples exhibited the same
sorption site that will adsorb more water molecules from the in- change trend before 90% RH while then their capillary adsorp-
side out due to the intermolecular force between water molecules, tion capacity gradually coincided with increasing RH, eventually
and then forms multilayer water [38]. From Table 2, the mono- exceeding that of untreated and artificially aged samples. Accord-
layer water content W0 and the adsorption constant C of naturally ing to above results, we can conclude that aging destroyed the el-
and artificially aged samples gradually decreased with extending ementary adsorption sites of paper resulting in the reduction of
aging time. A similar pattern is also evident in the changes in SGAB monolayer water content, which affects secondary adsorption sites
of aged samples (Fig. S4). This means that aging reduced the ef- causing the decrease of multilayer water content. Capillary adsorp-
fective adsorption sites of paper and weakened their interaction tion is generated from multilayer water, but theoretically, it can be
with water molecules, resulting in the monolayer water content adsorbed water infinitely as long as there is enough space for wa-
decreased. Among all samples, the adsorption constant K is lower ter molecules. Thus, capillary adsorption is related to the adsorp-
than C, and the changes of K during aging are smaller. Accordingly, tion sites, but not the decisive factor, thereby explaining why natu-
the binding strength of water molecules in multilayer adsorption is rally aged samples have lower monolayer adsorption capacity than
weaker than that of monolayer adsorption. Wan et al. studied lig- untreated and artificially aged samples, but their capillary water
nite’s thermodynamic properties during moisture adsorption, and content eventually becomes higher.
the results also showed that the first layer of water molecules has
higher adsorption heat [39]. Besides, we found that the K values of
naturally aged samples are higher than that of untreated and arti- 4.3. FTIR analysis
ficially aged samples, indicating that naturally aged samples have
a stronger multilayer adsorption capacity. Bamboo paper is composed of cellulose, hemicellulose, and
H–H model was proposed by Hailwood and Horrobin in 1946 lignin. The molecular chain of hemicellulose is abundant with hy-
and widely used to explain the moisture adsorption mechanism for droxyl groups, making it the strongest in hygroscopicity. Since
fiber and other materials [26]. According to the sorption theory of the hydroxyl groups in the crystalline regions of cellulose have
this model, the sorption isotherms can be divided into monolayer formed hydrogen bonds, it relies mainly on the free hydroxyl
water (W0 ) and multilayer water (Ws ). Table 3 shows the param- groups in amorphous areas to combine with water molecules.
eters obtained by fitting the H–H model with experimental data Lignin contains large amounts of phenylpropane structures that are
during moisture absorption process for untreated and aged sam- hydrophobic, which plays a minimal role in moisture absorption
ples. for paper [40,41]. In order to study the relationship between the
Like the GAB model, H–H model also performed well fitting changes in chemical constitution and moisture absorption of aged
the aged samples (R2 > 0.98) according to Table 3. The Wm rep- paper, we performed FTIR analysis. The collected infrared spectra
resents the apparent molecular mass of paper per sorption. As the were normalized at 1640 cm−1 (attributed to OH bending of ad-
aging degree aggravated in both naturally and artificially aged sam- sorbed water [42,43]), as shown in Fig. 5.

70
J. Tan, X. Fu, Y. Lu et al.
Fig. 4. The water content of monolayer and multilayer calculated by H–H model for untreated and aged samples: (a) dry heat aging; (b) moist heat aging; (c) natural aging.
Both naturally and artificially aged samples show simi-
lar changes in chemical structure. The absorption intensity at
3420 cm−1 which is characteristic FTIR band of hydroxyl groups
decreased as the aging progressed of paper. This indicates that hy-
droxyl was easily destroyed during aging due to its active chemi-
cal properties, resulting in the dehydroxylation of aged paper and
the relative content of hydroxyl decline. A continuous FTIR band
in the range of 120 0∼10 0 0 cm−1 formed the fingerprint area of
cellulose [44]. Among them, the absorbance at about 1160, 1052,
and 898 cm−1 are characteristic of C–O–C in β -glycoside-bond and
the intensity of aged samples decreased in various degrees at these
wavelengths [45]. The cellulose molecular chain has been degraded
and broken. C–C stretching vibration of saccharide ring in hemicel-
lulose produces a characteristic band at nearly 658 cm−1 . As in-
creasing aging degrees, its absorbance gradually diminished, indi-
cating the hemicellulose was easily degraded during aging. Besides,
the infrared spectrum of naturally aged samples differs markedly
from that of artificially aged samples, with the former showing a
sharp absorption at 1380 cm−1 . It may be related to the difference
in degradation degrees of bamboo paper during natural and arti-
71
Journal of Cultural Heritage 61 (2023) 65–75
ficial aging, new chemical structures were generated in naturally
aged samples.
From a microstructure point of view, crystallinity is a key pa-
rameter to consider as it directly impacts the water absorption ca-
pacity of cellulose. The crystallinity of cellulose indexes of samples
was calculated for lateral order index (LOI, A1422/A896) and to-
tal crystallinity index (TCI, A1369/A2918) [46–48]. As aging time
increased, the LOI in both artificially and naturally aged samples
decreased (Table 4), which indicates that the ordered structure of
cellulose has been degraded to varying degrees. The TCI of arti-
ficially aged samples increased initially and then declined, while
that of naturally aged samples almost rose. Due to the disordered
arrangement of molecular chains in the amorphous region, the in-
termolecular force is weak and easily damaged by temperature and
other factors, whereas the crystalline region is more stable due
to its compact structure [49]. During the early phases of artificial
aging, the cellulose structure of samples degraded largely in the
amorphous area, resulting in an increase in the relative propor-
tion of the crystalline region, similar to what Castro [50] and Mała-
chowska [51] observed. They found an increase in the crystallinity
J. Tan, X. Fu, Y. Lu et al. Journal of Cultural Heritage 61 (2023) 65–75

Fig. 5. FTIR spectra of untreated and aged samples: (a) dry heat aging; (b) moist heat aging; (c) natural aging.

Table 4
Results of crystallinity of cellulose indexes and ratios of change in crystallinity.

Crystallinity of cellulose indexes Ratios of change in crystallinity (%)

Samples LOI TCL RLOI RTCL

Untreated 1.49 0.73 0.00 0.00

Dry heat-36 days 1.46 0.77 −2.01 5.48
Dry heat-90 days 1.35 0.64 −9.40 −12.33
Moist heat-12 days 1.47 0.79 −1.34 8.22
Moist heat-24 days 1.30 0.66 −12.75 −9.59
No. MG28 1.36 0.68 0.00 0.00
No. MG17 1.34 0.67 −1.25 −1.47
No. GX10 1.30 0.69 −4.40 1.47
No. XF3 1.27 0.71 −6.63 4.41

LOI, lateral order index of cellulose; TCI, total crystallinity index of cellulose; RTCL and RLOI , ratio of
change in TCI and LOI of samples, respectively (the untreated sample was the initial reference for
artificially aged samples, and the latest sample, No. MG28 (AD 1939) was the initial reference for
naturally aged samples).

72
J. Tan, X. Fu, Y. Lu et al.
Fig. 6. SEM images of samples: (a) untreated; (b) dry heat-90 days; (c) moist heat-24 days; (d) No. XF3.
index of aged paper and concluded that cellulose degradation hap-
pened primarily in its amorphous area.
Małachowska also noted that when the percentage of the crys-
talline phase decreased, the course of the degradation process be-
came likelier [51]. The TCI of artificially aged samples decreased
with increasing aging time, as shown in Table 4, indicating that the
damage to the cellulose structure at this time is dominated by the
crystalline region, which is consistent with the significant decrease
in RLOI . The RTCL of naturally aged samples continued to rise, infer-
ring that the destruction of amorphous areas still played a major
role. Due to its porous structure and exposed hydroxyl sites, cel-
lulose’s amorphous regions are hydrophilic, while water molecules
cannot penetrate into the crystalline regions [52]. As a result, the
changes in the crystallinity of cellulose during the aging process
will affect the way water interacts with cellulose.
As can be seen from above results, the cellulose and hemicel-
lulose gradually degraded in naturally and artificially aged sam-
ples, causing abundant hydrophilic groups in the fiber chain to be
destroyed, such as hydroxyl. This reduced the effective adsorption
sites and specific surface area for moisture adsorption, resulting in
a diminished monolayer adsorption capacity of aged samples. Ad-
ditionally, the amorphous region of cellulose is vulnerable to de-
terioration during aging. This not only results in the loss of hy-
drophilic components but also increases the difficulty of water en-
tering cellulose due to the retained crystalline structure.
73
Journal of Cultural Heritage 61 (2023) 65–75
4.4. SEM analysis
The physical structure of paper will affect its hygroscopic prop-
erties. Scanning electron microscopy was used to magnify the typ-
ical paper morphology and structure of fibers to better understand
the effects of degradation on the microstructure of aged bamboo
paper. It can be seen from the untreated sample presented in
Fig. 6(a) that the heterogeneous network in the paper is consti-
tuted by the fibrous bundle together randomly, which have differ-
ent shapes and sizes, explaining the presence of many voids re-
lated to the high porosity level for paper. Further, there are many
fine fibers filled between long fibers [53], and the surface of long
fiber appears smooth with pleated structure in the image magni-
fied by 20 0 0. As shown in Fig. 6(b), the distribution of fine fibers in
the aged sample with dry heat for 90 d has become more compact,
and the surface of long fiber was cracked slightly. Fig. 6(c) shows
the structure of the aged sample with moist heat for 24 days, it
appears that the fine fibers have not been significantly altered,
whereas the long fiber surface was peeled off. It can be seen from
the micrographs in Fig. 6(d) that the cellulose structure became
vulnerable under natural aging. The long fiber of No. XF3 was de-
stroyed, broken, and split due to its age, and its fiber surface has
been fragmented.
There are irreversible structural changes that occur in the paper
through the drying process, which results in a reduction in large
J. Tan, X. Fu, Y. Lu et al.
and intermediate-sized pores in the paper and a more compact
structure [15,16]. Therefore, the shrinkage and aggregation of fine
fibers as a result of water evaporation is reflected in the morphol-
ogy of the sample after dry heat aging for 90 days. This is sim-
ilar to our previous research’s observation that fiber shrank and
severely agglomerated in bamboo paper after aging at 150 °C for
24 days [54]. Consequently, the capillary water absorption capa-
bility of the paper was diminished as the original pores were de-
stroyed and the microstructure collapsed. It is consistent with the
current theories that the decrease in wet swelling ability of fiber
materials after drying is due to pore closure and cellulosic fibril
aggregation [55].
In contrast, the naturally aged sample was not affected by the
high temperature that occurs during artificial thermal aging. Thus,
no apparent aggregation was observed in the fine fibers. However,
due to the cumulative influence of temperature, humidity, oxy-
gen, and other environmental conditions on paper during storage,
fiber fragmentation is more severe in naturally aged sample. As
the fibers cracked and peeled, new porous structures were formed
that could accommodate more water molecules during capillary
condensation. This may explain why the constant K value in the
GAB model and the capillary water content calculated by the H–H
model of naturally aged samples are higher than that of untreated
and artificially aged samples.
5. Conclusions
In this research, multi-analytical techniques comprising DVS,
sorption model fitting, FTIR, and SEM were conducted to study
the moisture sorption behavior of naturally and artificially aged
bamboo paper as well as to investigate the regularities and rea-
sons for changes in hygroscopicity of aged paper for the first
time.
DVS was used to study the isothermal moisture absorption
characteristics of bamboo paper under different aging modes, in-
dicating that aging has little effect on the adsorption mechanism
of paper but reduces the equilibrium moisture content. Addition-
ally, the moisture absorption and desorption rates of aged bam-
boo paper reached the minimum at about 40∼50% RH, and the
monolayer adsorption capacity become saturated at nearly 50% RH.
Thus, for bamboo paper cultural relics, the storage humidity at ap-
proximately 50% RH is conducive to maintaining their physical and
chemical stability.
GAB and H–H models can be used to describe the isothermal
moisture sorption process of aged bamboo paper, showing that
there are three phases during the isothermal moisture absorption
process of bamboo paper. A decrease in the effective sorption sur-
face area of naturally and artificially aged bamboo paper reduces
the capacity of monolayer adsorption as well as multilayer adsorp-
tion. Naturally aged bamboo paper exhibit higher capillary adsorp-
tion capacity than untreated and artificially aged bamboo paper,
confirming that the adsorption site is not the decisive factor for
capillary adsorption.
FTIR studies indicate that hemicellulose, and amorphous re-
gions in cellulose degraded in both naturally and artificially aged
bamboo paper, resulting in the destruction of hydrophilic compo-
nents such as hydroxyl. It demonstrates that the reduction in the
number of hydrophilic groups is the primary cause of the decrease
in the monolayer adsorption capacity of aged bamboo paper. Fur-
thermore, the micromorphology shows that the physical structure
of artificially aged bamboo paper has been damaged, which weak-
ens the capillary adsorption capacity of paper. Nevertheless, the
cracking and peeling of fibers in naturally aged bamboo paper cre-
ate new porous structures, which is an important factor contribut-
ing to their stronger capillary adsorption capacity.
74
Journal of Cultural Heritage 61 (2023) 65–75
CRediT authorship contribution statement
Jing Tan: Conceptualization, Writing – original draft, Writing
– review & editing. Xiaohang Fu: Writing – review & editing.
Yujing Lu: Writing – review & editing. Biao Chen: Conceptualiza-
tion, Writing – review & editing, Supervision, Funding acquisition.
Yanwei Ding: Conceptualization, Methodology, Supervision, Fund-
ing acquisition, Writing – review & editing.
Acknowledgments
Funding: This work was supported by the National Natural Sci-
ence Foundation of China [grant number 12027804]; the National
Key R&D Program of China of the Ministry of Science and Tech-
nology [grant number 2022YFF0904501]; and the Provincial Qual-
ity Project of Anhui Higher Education Institution [grant numbers
2020jyxm2275, 2022szsfkc010, 2022jyjxggyj031].
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.culher.2023.03.004.
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