Carbohydrate Polymer Technologies and Applications 2 (2021) 100107

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Carbohydrate Polymer Technologies and Applications

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carbohydrate-polymer-technologies-and-applications

Preparation of cellulose nanocrystals from deinked waste newspaper and

their usage for papermaking
Ying Guan a, Wenqi Li a, Hui Gao a, *, Liping Zhang a, Liang Zhou a, Feng Peng b
a
Forestry and Landscape Architecture, AnHui Agricultural University, Hefei 230036, China
b
Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China

A R T I C L E I N F O A B S T R A C T

Keywords: Cellulose nanocrystals (CNC) were successfully prepared from waste newspapers through a simple pretreatment
Waste newspapers and hydrolysis process. The Fourier transform infrared spectroscopy (FTIR) result for the CNC suggested that no
Deinking new chemical bonds were formed during the preparation of CNC. X-ray diffraction results indicated that the
Cellulose nanocrystals
crystallinities of the deinked and untreated waste newspapers were 66% and 73.8%, respectively. Greater
Papermaking
smoothness of the deinked waste newspapers fibers could be clearly observed by scanning electron microscope
(SEM), which was attributed to the removal of ink from the chemical treatment. The transmission electron
microscopy (TEM) and atomic force microscopy (AFM) results of the CNC revealed a needle-like natural fiber
with a length of 300 nm to 600 nm, a diameter of 10 nm to 30 nm, and an aspect ratio in the 10 to 60 range. The
obtained CNC particles were found to improve the physical properties of paper sheets, specifically that of the
tear, tensile, and burst indices. The maximum increase in the physical properties was achieved with a 5.5% CNC
addition.

1. Introduction
Exhaustion of non-renewable resources has led to an increasing trend
toward enhanced efficiency in the utilization of waste newspapers
(WNPs) as a raw material for various applications. As typical waste
biomass materials, WNPs comprise about 7% of the municipal solid
waste and contain low-cost cellulosic material (Fan et al., 2017). Mil­
lions of tons of WNPs are generated and used in China, resulting in a
considerably large amount of wastepaper. Owing to the cellulosic con­
tent of WNPs, the production of high-value cellulose-based materials
from WNPs can provide an alternative recycling method.
Cellulose is one of the most abundant renewable natural resources,
consisting of linear bonds of glucose as a monosaccharide (C6H10O5)n;
the cellulose polymer includes both crystalline and amorphous regions
(Morais et al., 2013). Additionally, cellulose has been widely used in
various applications, such as paper, clothes, adhesives, textiles, food,
cosmetics, and pharmaceuticals (Kallel et al., 2016). With the advent of
nanotechnology, the isolation of nanocellulose from various renewable
sources and its utilization in technical applications have received
increased attention. The production of CNC from WNPs has recently
drawn increased research interest (Danial et al. 2015; Campano et al.,
2017). Danial et al. (2015) successfully extracted CNC from wastepaper
by alkali and acid treatments. The CNC exhibited the following char­
acteristics: diameter of 3 nm to 10 nm, length of 100 nm to 300 nm, and
crystallinity index of 75.9%. Campano, Miranda, Merayo, Negro and
Blanco (2017) also produced high-quality CNC directly from old news­
papers and recycled newsprint. Several studies using nanocellulose as a
reinforcing phase within biocomposite materials have been published in
recent years; however, its application in pulp and paper has rarely been
reported (Sehaqui, Zhou, Ikkala & Berglund, 2011; Stelte & Sanadi,
2015). There are only a few studies that have produced nanocellulose
from old newspapers or newsprint paper; thus, a deeper knowledge on
this area is of interest. Nanocellulose has drawn considerable attention
for its application as an additive in papermaking to improve mechanical
properties, such as bursting, tearing, and tensile strengths (Afra, Yousefi,
Hadilam & Nishino, 2013; Boufi et al., 2016; González et al., 2012). As
an additive, nanocellulose presents several advantages: a large surface
area, biodegradability, high tensile strength, and a high modulus
(Campano et al., 2017). Therefore, the addition of nanocellulose to pulp
shows a high potential in increasing hydrogen bonding between pulp
fibers and resulting in stronger formed paper (Xu et al., 2013). Nano­
crystalline cellulose was isolated from bleached aspen kraft pulp by Xu

* Corresponding author.
E-mail address: huigaozh@163.com (H. Gao).

https://doi.org/10.1016/j.carpta.2021.100107
Received 2 April 2021; Received in revised form 23 June 2021; Accepted 27 June 2021
Available online 29 June 2021
2666-8939/© 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Y. Guan et al.
et al. (2013), and its application as a pulp-strengthening additive was
investigated. Carboxymethyl cellulose (CMC) was also used as an ad­
ditive to improve the strength of the fiber network (Fatehi, Kititerakun,
Ni & Xiao, 2010).
Strong sulfuric acid hydrolysis is one of the promising preparation
processes that have been extensively studied in the literature (Wang,
Zhao & Zhu, 2014). During acid hydrolysis, the disordered cellulose is
preferentially attacked, leaving the crystalline cellulose as the final CNC
product (Habibi, Lucia & Rojas, 2010). The unique properties associated
with CNC, such as a high elastic modulus, abundant hydroxyl (-OH)
groups (Ng et al., 2015) and chemical reactivity (Sun, Hou, Liu & Ni,
2015), render it highly desirable for value-added applications (Kamal &
Khoshkava, 2015). The cellulose nano-crystals (CNC) have been
emerging as new material in many potential applications, such as food,
medicine, cosmetics, pulp and paper, reinforcing and other special
function additives (Antczak, Kazimierczak & Antczak, 2012; Dong et al.,
2012).
In the current study, a chemical pretreatment with hydrogen
peroxide and sodium hydroxide was used to deink the WNPs. The
chemical composition, fiber morphology, and brightness of the WNP
were analyzed to optimize the technological conditions for deinking.
Controlled sulfuric acid hydrolysis was used to prepare the CNC.
Chemical characterizations were conducted by atomic force microscopy
(AFM), Fourier transform infrared spectroscopy (FTIR), and trans­
mission electron microscopy (TEM). CNC and CMC were also used as dry
strength additives in papermaking. The effects of different additives on
the tensile strength, bursting strength, tearing strength, and elongation
of the paper sheets were also analyzed in this study.
2. Materials and methods
2.1. Materials
WNPs (Anhui Daily Newspaper) were used as raw materials in this
study. Sodium hydroxide (NaOH), sulfuric acid (H2SO4), and hydrogen
peroxide (H2O2) were provided by Xilong Scientific Co., Ltd. (Guang­
dong, China). Microcrystalline cellulose, CMC, NaClO2, and sodium
silicate (Na2SiO3) were purchased from Aladdin (Shanghai, China). All
reagents used were of analytical grade.
2.2. Deinking of WNPs
The WNPs were cut into small pieces (2 cm × 2 cm) and then treated
with 5% (w/v) NaOH, 10% (w/v) H2O2, and 10% (w/v) sodium silicate
at 60 ◦ C for 1.5 h (together in a single stage). The mixture was stirred for
30 min at 1000 r/min and aged for 1 h. Then, the deinked pulps were
filtered and washed with distilled water until neutral pH was achieved.
The sample was dried at 105 ◦ C overnight to obtain the deinked WNPs.
2.3. Preparation of CNC and papermaking
CNC were prepared by acid hydrolysis as described in previous
studies with minor modifications (Danial et al. 2015; Chen, Lee, Juan &
Phang, 2016). The obtained dried deinked WNPs (5 g) was added into
61wt% H2SO4 at 45 ◦ C with constant stirring. The optimum reaction
time was fixed at 1 h, and the fiber–liquor ratio was maintained at 1:20
(w/v). Deionized water was then added into the mixture to terminate the
reaction of H2SO4 with the WNP pulp. The suspension of the mixture was
centrifuged to remove the H2SO4. CNC were subsequently filtered and
washed several times with distilled water, placed in a dialysis bag with
molecular weight cut-off of 12,000–14,000 Da, and dialyzed until
neutral pH was obtained. The obtained CNC was sonicated for 20 min to
disperse it and stored in a refrigerator at 4 ◦ C.
Dried eucalyptus pulp with a beating degree of 45.7 ◦ SR was used as
the primary raw material. Pulp was dispersed at 1 wt% (pulp consistency
of 1 wt%) in water, and the pulp was put in laboratory pulper for 30 min
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Carbohydrate Polymer Technologies and Applications 2 (2021) 100107
at 3000 rpm. Subsequently, the different contents of CNC were added to
the eucalyptus slurry during the disintegration process. After that, the
pulp and CNC mixture were drained by gravity through 80 mesh copper
mesh, and then the paper was dried at 105 ◦ C for 15 min under vacuum.
The obtained paper was then placed in controlled temperature and hu­
midity chamber (HSB-100 L, Anke Instrument, Hefei, China) with a
constant temperature of 25 ◦ C and relative humidity of 60% to balance
the moisture before mechanical test. For comparison, different per­
centages of CMC (0–10%) were added into the pulp slurries in the same
way with the CNC during the disintegration process. And then, following
the same above procedures with the addition of CNC, the CMC-
reinforced paper was obtained.
2.4. Measurements of chemical composition
The holocellulose,α-cellulose and pentosan contents were deter­
mined according to the standard PN-P-50092 (1992). The acid-insoluble
lignin and acid-soluble lignin contents were determined according to the
TAPPI T222 om-02 (2011) standard, and benzene alcohol extractives
were determined according to TAPPI T204 cm-97 (2007).
2.5. Fiber length and width
0.5 g WNP pulp was diluted with constant stirring in 500 Ml
deionized water till the fibers were separated. The fibers were then
placed under an optical microscope (Nikon E200MV) to measure the
length and width of the fibers. The values of about 200 fiber length and
width of WNP pulp were measured with Image J, and the average values
were obtained by the calculation.
2.6. Polymerization degree
0.5 g broken dried pulp was put into a plastic type flask before
dissolution. 2 ~ 3 pieces of copper, 25 mL distilled water were added to
the flask, which was shaken until completely dispersed. Then, 25 mL 1.0
mol/L copper ethylenediamine solution was added to the mixture to
eliminate the residual air. The solution was shoked repeatedly until the
sample was completely dissolved, and the temperature of the solution
was kept to 25 ◦ C. The outflow time of fiber solution was carefully
measured three times at 25 ± 0.1 ◦ C, and the average value was calcu­
lated for use. The Polymerization degree (DP) was obtained according to
the formulas as follows:
ηrel = hn × tn (1)
ηrel = hn × tn (2)
DP0.905 = 0.75[η] (3)
where the hn was viscometer constant, s− 1; tn was outflow time of so­
lution,s; c was the solution concentration,g/mL.
2.7. Optical properties
Brightness was typically used to evaluate the optical properties of the
WNP pulp and was determined by measuring the reflectance of light
from white or nearly white sheets of paper. The ISO brightness of paper
sheets was evaluated using an SBDY-1 brightness tester (Shanghai Yuet
Feng Instrument, Shanghai, China).
2.8. Measurements of the paper sheet
The Tensile index, tear index, and burst index were determined ac­
cording to the standard ISO 1924-1 (1992), ISO 1974 (2012), and ISO
2758 (2014), respectively.
Y. Guan et al.
2.9. Fourier transform infrared spectroscopy
The FTIR spectra of the samples were measured using a Nicolet 6670
spectrometer (Thermo Fisher, Waltham, MA, USA) from 4000 cm− 1 to
400 cm− 1 range with a resolution of 2 cm− 1. The samples (about 5 mg)
were ground into powder and then blended with KBr (1:100, w/w) and
pressed into transparent pellets.
2.10. X-ray diffraction
X-ray diffraction (XRD) measurements were performed using an
XRD-3 diffractometer (PERSEE, Beijing, China) by Cu-Kα radiation and a
X-ray wavelength of 0.154 nm at 36 KV and 20 mA. Samples were
analyzed between 2θ = 10◦ and 40◦ , with the angle size at a 2θ = 0.02◦
speed of 1 o/min at room temperature. The crystallinity index (CrI) of
each sample was calculated using the following empirical equation
(Segal, Creely, Jr & Conrad, 1959),
I002 − Iam
CrI = × 100% (4)
I002
Where I002 is the peak intensity of (002) (2θ = 22.9◦ ), and Iam is the
minimal diffraction intensity (a. u.) of the amorphous region.
2.11. Imaging analysis
The extracted CNC were previously coated with gold by sputtering,
and the morphology of the coated CNC were examined by field emission
scanning electron microscopy (FESEM) (S-4800, Hitachi, Japan). The
diameter and size distribution of the CNC were further estimated by an
AFM using a Vescon nanoscope IV. Several drops of the diluted sus­
pension were deposited onto a freshly cleaved mica substrate and
allowed to dry. The dispersibility of CNC were investigated by TEM
using an HT7700 (Hitachi, Japan) instrument.
3. Results and discussion
3.1. Deinking optimization of WNPs
The deinking optimum condition was conducted using doses of
H2O2, NaOH, and Na2SiO3, and the three optimum parameters were
determined by the final brightness of the pulp. Single factor analysis was
used to explore the optimal conditions in this experiment. In order to
study the effect of the amount of NaOH on deinking, the other two
factors were all in optimal conditions (10% Na2SiO3 and H2O2). The
effects of H2O2, Na2SiO3, and NaOH doses on the brightness of the WNP
deinking pulp are presented in Fig. 1. The brightness of the deinked
WNPs gradually increased initially and then stabilized with an increase
in the H2O2/Na2SiO3/NaOH dosage. The results indicated that the
highest brightness of the deinked WNPs was obtained while the amounts
of H2O2, NaOH, and Na2SiO3 were 10%, 5%, and 10%, respectively. The
brightness was increased by 32.3% ISO, 30.3% ISO, and 28.2% ISO with
10% H2O2, 10% Na2SiO3, and 5% NaOH, respectively.
3.2. Chemical composition analysis
The chemical compositions of the deinked and untreated WNPs were
presented in Fig. 2. Relative to the untreated WNPs (Fig. 2b), the
extractive, lignin, and pentosan contents of the deinked WNPs (Fig. 2a)
were decreased by 0.34%, 2.83%, and 1.47%, respectively. The initial
extractive content of the untreated WNPs was about 0.85% and
decreased to 0.51% after the chemical pretreatment. This reduction was
probably caused by the removal of ink during deinking. Owing to the
degradation of lignin during the bleaching stage, the lignin content
decreased from 19.44% to 16.01%. The contents of the chemical com­
positions of the WNPs were completely changed after deinking,
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Carbohydrate Polymer Technologies and Applications 2 (2021) 100107
Fig. 1. Effects of H2O2, NaOH, and Na2SiO3 doses on the brightness of the
deinked WNP pulp.
indicating that there was a high effective removal of the components,
such as lignin, extractives, and hemicelluloses during the alkali and
bleach treatment stages. The deinked WNPs were enriched with 60.14%
α-cellulose, resulting in highly purified cellulose suitable for the pro­
duction of CNC.
3.3. Polymerization degree
The fiber length, fiber width, and polymerization degree (PD) from
before and after treatment of WNPs were compared in Table 1. No sig­
nificant change in fiber length and width was observed between the
deinked and untreated WNPs, indicating that the fiber was not damaged
during the chemical treatment. A non-uniform frequency distribution
was commonly used to analyze the distribution of fiber length. The
length distributions of the fibers were presented in Fig. 3a and 3b. As
shown in Fig. 3a, 65% of the fiber lengths were in the range from 200 μm
to 800 μm; 25.5% of the fiber lengths ranged from 800 μm to 1000 μm;
and 9.5% of the fiber lengths were longer than 1000 μm. Fig. 3b showed
that 60.5% of the fiber lengths were ranged from 200 μm to 800 μm, and
26% of the fiber lengths were ranged from 800 μm to 1000 μm. The PDs
of the untreated and deinked WNPs are 654 and 768, respectively, as
listed in Table 1. The average PDs of the deinked WNP fiber lengths were
remarkable increased. This finding indicated that the short fibers were
washed away during with the increase of average PD, resulting in the
remaining long fibers. This observation was also consistent with the
reduction in the proportion of short fibers (Fig. 5b). A greater length
promoted crosslinking with the remaining fibers, thereby improving the
physical properties of paper sheets.
3.4. X-ray diffraction analysis
The XRD spectra of the untreated and deinked WNPs were illustrated
in Fig. 4. Fig. 4 showed diffraction peaks of the deinked WNPs at 2θ =
16.1◦ and 22.9◦ , which were basically consistent with the untreated
WNPs. In addition to the main diffraction peaks at 2θ = 16.1◦ and 22.9◦ ,
the untreated WNPs exhibited two small peaks at 12.5◦ and 29.80◦ ,
which might be related to the presence of kaolin and calcium carbonate.
The most intense peak for kaolin was usually found at 12.3◦ , while the
most intense peak for CaCO3 was typically found at 2θ = 29.80◦ These
peaks indicated that the crystallinity of deinked WNPs was 66%, which
was 7.8% lower than that of the untreated WNPs; the crystallization area
of the cellulose was damaged by NaOH during deinking (Campano et al.,
2017 and Segal et al., 1959). The crystallinity index (CrI) of CNC was
70.21%. The CrI of CNC was higher than deinked WNPs but lower than
Y. Guan et al. Carbohydrate Polymer Technologies and Applications 2 (2021) 100107

Fig. 2. Proportions of lignin, α-cellulose, pentosan, and extractive in deinked (a) and untreated (b) WNPs.

Thus, the CNC had a high crystallinity, and this property could be
Table 1
important for papermaking.
The Fiber Length, Width, and Degree of Polymerization of the Untreated and
Deinked WNPs.
Fiber Length Fiber Width Degree of
3.5. FTIR analysis
(µm) (µm) Polymerization
The infrared spectra of the untreated WNPs (a), deinked WNPs (b),
Untreated 763 21.97 654
WNPs CNC (c), and microcrystalline cellulose (d) were presented in Fig. 5. The
Deinked WNPs 760 21.61 768 absorption peak at 1165 cm− 1 was in accordance with the glycosidic
bond (C–O–C) stretching of the cellulose (Danial et al. 2015). The FTIR
spectra in Fig. 5b (deinked WNPs) showed the stretching vibration ab­
that of untreated WNPs, which was due to the higher proportion of sorption peak of -OH at about 3200 cm− 1 to 3600 cm− 1, which was
cellulose I crystallites existed in the untreated WNPs. Amorphous region significantly stronger than that of the untreated WNPs (Fig. 5a). Ferrer
of cellulose was removed during the hydrolysis process, which and Vila (2006) reported that the ink had an absorption band at 3380
contributed to the low yield (34.54%) and higher crystallinity of CNC. cm− 1, which reduced the concentration of hydroxyl groups from the

Fig. 3. Fiber length distribution diagrams of the untreated (a) and deinked (b) WNPs; the fiber picture under the optical microscope (c).

4
Y. Guan et al.
Fig. 4. X-ray diffraction patterns of untreated (a) and the deinked (b) WNPs.
Fig. 5. FTIR spectra of the untreated WNPs (a), deinked WNPs (b), CNC (c),
and microcrystalline cellulose (d).
untreated pulp. In the spectrum of the untreated (a) WNPs, a charac­
teristic peak at 1733 cm− 1 was corresponds to the C– – O stretching fre­
quency of carboxyl groups in their acidic forms. (Filpponen, Sadeghifar
& Argyropoulos, 2011). Moreover, the absorption peak at 1733 cm− 1
might be attributable to the C–– O stretching of hemicelluloses (Alemdar
& Sain, 2008; Mandal and Chakrabarty 2011; Danial et al. 2015). The
peak intensity at 1733 cm− 1 of the deinked WNPs (spectrum b) was
lower than that of the untreated WNPs (spectrum a), which might have
resulted from the degradation of hemicelluloses by the pretreatment
with NaOH. In Fig. 5a (untreated WNPs), the band at 1505 cm− 1
ascribed to C in-plane aromatic vibrations indicated the presence of
lignin (Danial et al. 2015). The peak at 1505 cm− 1 of the deinked WNPs
(Fig. 5a) was significantly weaker than that of the untreated WNPs
(Fig. 5b), indicating the effectiveness of using a chemical treatment to
remove lignin. The peak at 1263 cm− 1 presented in the spectra of WNPs
was also weak intensity, which was ascribed to lignin (Xia et al., 2016).
In comparison to the starting material, changes showed in the peak at
1733, 1505, and 1263 cm− 1 indicated that the chemical treatment
partially removed the hemicelluloses and lignin from the fiber surface.
These results were consistent with those of chemical composition
analysis.
The spectrum of the CNC (Fig. 5c) contains bands similar to that of
the microcrystalline cellulose (Fig. 5d). The peak near 1635 cm− 1 was
attributable to the absorbed water in Fig. 5c (Jiang & Hsieh, 2013;
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Carbohydrate Polymer Technologies and Applications 2 (2021) 100107
Kallel et al., 2016). The specific bands of the β-(1–4) glycoside bridge at
896 cm− 1, as well as the C–O-C stretching vibration of the pyranose at
1165 cm− 1, were also clearly presented in the spectra, which were the
salient features of the cellulose structure. Accordingly, the intensity of
C–H stretching peak at 2900 cm− 1 for deinked WNPs was lower than
that of untreated WNPs, indicating that the broken of hydrogen-bonding
structure and crystal form were occurred during the deinked process
(Cao, Li, Zhang, Zhang & He, 2010). This result was consistent with the
XRD result. Overall, these results indicated that the molecular structure
of the cellulose was not destroyed after pretreatment with H2SO4, and
the CNC still showed the basic chemical structure of the cellulose.
3.6. Morphological characteristics of CNC
The FE-SEM images of the untreated and deinked WNPs were pre­
sented in Fig. 6a and 6b. In Fig. 6a, the ink particles were attached to the
fiber surface of the WNPs. Contrastingly, the ink particles on the deinked
WNP pulp almost disappear in Fig. 6b at 1.5k. The fibers were more even
and workable after than that before the alkali and bleaching treatment.
The TEM images in Fig. 7 confirmed the dispersibility of the CNC. A
smooth surface with fibrillar orientation and uniform shape was clearly
exhibited in the TEM of CNC image, which possessed a high aspect ratio
in the 10 to 60 range. The aspect ratio of the CNC was higher than that of
CNC (20 to 50) in the study by Campano (Cristina Campano et al., 2017).
The aspect ratio of the CNC was a significant parameter for exerting a
substantial influence on the reinforcing capacity of the nanofiller. The
aspect ratio of the CNC, which was higher than 30, could provide a
higher increment in the strength of the material (Ng et al., 2015). In
addition, the diameter of the CNC ranged from 10 nm to 30 nm, while
the length ranged from 300 nm to 600 nm. A fraction of particle-like
items were presented in TEM image of CNC, which was probably the
residual ink and additives. Although the deinking process was operated
before the preparation of CNC, the fractions of ink and other additives
were still existed among the fibres. The obtained CNC with a high aspect
ratio was successfully prepared from WNPs by simple pretreatment and
hydrolysis, and accordingly could provide reinforcement for paper
sheets.
The surface structures and morphologies of the CNC were further
elucidated by AFM (Fig. 8). The AFM micrographs provided documen­
tation for the preparation of CNC from WNPs. The diameters of the CNC
were ranged from 20 nm to 40 nm, the lengths were ranged from 400 nm
to 800 nm, and the aspect ratios were ranged from 10 to 40. However,
larger dimensions were observed in the AFM studies in contrast to the
TEM results, which might be attributable to the needle tip used during
the ATM. As shown in Fig. 8, the CNC had the shape of a relatively
regular whisker. From the Cristina et al. (2017), lower physical prop­
erties of the paper sheets were observed when the CNC exhibited
agglomeration by hydrogen bonding. A higher dispersion of both CNC
could reduce the dose needed to gain the same increment in tensile
strength, as well as reduce material costs.
3.7. Effect of CNC on the physical properties of paper sheets
With an abundance of surface hydroxyl groups, a large specific sur­
face area, a high aspect ratio, excellent mechanical properties, and a
high thermal resistance, the CNC have showcased its potential for
application as a reinforcement in papermaking and increasing the
strength of paper sheets (Abdullah-Al-Mamun et al., 2016). Nano­
cellulose and CMC were used in papermaking to improve the physical
performance of paper sheets without causing structural damage to the
fibers (Tarrés et al., 2018). In the current study, CNC and CMC were
added to the eucalyptus pulp for papermaking. Moreover, the effects of
additive agents with varying measures on the tensile strength, tear
index, burst index, and elongation of the paper sheets were evaluated
with the results shown in Fig. 9.
The tensile strengths of the paper sheets were increased by the
Y. Guan et al.
Fig. 6. FE-SEM images of untreated (a) and deinked (b) WNPs.
Fig. 7. TEM images of CNC prepared by the sulfuric acid hydrolysis method.
Fig. 8. AFM images of CNC prepared by the sulfuric acid hydrolysis method.
addition of CNC, which was prompted by the creation of a bond among
the fibers. More specifically, the tensile index was increased to its
maximum value at 5.5% CNC, which was 32.74% higher than that of
6
Carbohydrate Polymer Technologies and Applications 2 (2021) 100107
paper sheets without CNC. The maximum values of burst index, tear
index, and elongation of the paper sheets were obtained at a CNC dose of
5.5% wt. These measures were increased 41.4%, 11.0%, and 12.2%,
respectively. The increases in various physical properties were obtained
by the addition of CNC, which was attributable to the adhesion among
the fibers. In addition, the physical properties of the paper sheets were
enhanced by the combination of hydrogen bonds. Further, the relative
bond area might be increased by the higher specific surface of the CNC to
improve its physical properties (Espinosa, Domínguez-Robles, Sánchez,
Tarrés & Rodríguez, 2017). At a 5.5% CNC addition, the maximum in­
crease in physical properties was achieved. Regardless, when CNC
addition exceeded 5.5%, the physical properties exhibited a downward
trend because of the aggregation of nanofiber particles. The results lead
to the conclusion that the CNC exhibited the capacity to improve the
physical properties of the paper sheets.
The effects of CMC as an additive in papermaking were also
measured in this study. Fig. 9 presents a comparison of the effects of
additives at varying amounts on the physical properties. The tensile
index reached the maximum values of 40.54% and 37.52% with the
addition of 5.5% CNC and 5.5% CMC, respectively. The burst index
initially increased and then decreased with the increase in CMC dosage.
This behavior might be attributed to the increase in maximum pressure
caused by the appropriate addition of CMC before the paper is broken.
However, a greater addition would cause more negative charges in the
system, which increased the electrostatic repulsion between the CMC
and fibers (Liu, Wu, Cao, Xue & Yao, 2011). Therefore, the burst index of
the paper sheet was decreased. The burst index was increased gradually
by 17.6% with the addition of 5.5% CMC. The tear index and elongation
were increased by 12.8% and 7.9%, respectively, with the addition of
5.5% CMC.
This study clearly demonstrated that the physical properties were
related to the additives of CNC and CMC. The most apparent finding of
this study was that the greatest reinforcement capacity of the paper
sheets was obtained with the addition of CNC rather than the addition of
CMC. To illustrate, compared with CMC, CNC as the additive further
improved the physical properties of the paper sheets. Therefore, CNC are
a good candidate as an industrial-scale reinforcement to improve the
physical properties of paper sheets.
4. Conclusions
The best deinking conditions for waste newsprint (WNP) were
identified as follows: H2O2 of 10%, NaOH of 5%, and Na2SiO3 of 10%.
The degree of brightness was improved by 32.5% ISO on the optimal
conditions. Relative to the extractive, lignin, and pentosan contents of
the untreated WNPs, those of the deinked WNPs were decreased by
0.34%, 2.83%, and 1.47%, respectively. The XRD patterns showed the
Y. Guan et al.
Fig. 9. Effect of CNC and CMC dosage on the elongation, tensile, burst, and tear indexes of paper sheets.
crystallinity index of CNC were higher than deinked WNPs but lower
than that of untreated WNPs. The FTIR spectra indicated that hemi­
celluloses and lignin were removed after the chemical treatment. And
the thermal stability of the CNC was lower than that of untreated WNPs.
The TEM showed that the CNC had a length of 300 nm to 600 nm and a
width of 10 nm to 30 nm. AFM studies confirmed the isolation of CNC
from WNPs. CNC improved the physical properties of the paper sheets.
These physical properties reached their maximum values with the
addition of 5.5% CNC.
Conflicts of Interest
The funders had no role in the design of the study; in the collection,
analyses, or interpretation of data; in the writing of the manuscript; or in
the decision to publish the results.
Author statements
Conceptualization was done by Ying Guan and Hui Gao; methodol­
ogy by Wenbin Luo; formal analysis by Wenqi Li and Liping Zhang;
writing original draft preparation by Ying Guan and Wenqi Li; v su­
pervision by Liang Zhou and Feng Peng; project administration by Ying
Guan, Hui Gao, Liang Zhou and Feng Peng. All authors have read and
agreed to the published version of the manuscript.
Acknowledgments
This work was supported by the Anhui Provincial Natural Science
Foundation of China (1808085MC68), Anhui Science Foundation Grant
(2008085MC99), National Natural Science Foundation of China (No.
31770596).
7
Carbohydrate Polymer Technologies and Applications 2 (2021) 100107
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