Article

Critical Role of Degree of Polymerization of

Cellulose in Super-Strong Nanocellulose Films
Zhiqiang Fang, Bo Li, Yu Liu, ...,
Gaoyuan Hou, Jie Zhou,
Xueqing Qiu
lygy0527@126.com (Y.L.)
cexqqiu@scut.edu.cn (X.Q.)

HIGHLIGHTS
Super-strong nanocellulose film is
presented by a cellulose DP
protection strategy

ASAM pulping enables rapid

lignin removal and cellulose DP
protection of wood block

The as-prepared anisotropic

nanocellulose film has a tensile
strength up to 1.13 GPa

Cellulose DP has a positive effect

on the mechanical properties of
nanocellulose film

Growing environmental awareness and depleting fossil resources pose an

emerging quest for lightweight materials with outstanding mechanical properties
and economic production from sustainable resources that are biodegradable,
carbon neutral, and safe. Super-strong yet lightweight anisotropic nanocellulose
films are demonstrated by a cellulose DP protection strategy, exhibiting a tensile
strength up to 1.13GPa. The high strength and low density of the nanocellulose
films renders the highest specific strength of 820 MPa cm3 g 1 among any known
natural polymers and some strong metals.

Fang et al., Matter 2, 1000–1014

April 1, 2020 ª 2020 Elsevier Inc.
https://doi.org/10.1016/j.matt.2020.01.016
Article
Critical Role of Degree of Polymerization
of Cellulose in Super-Strong
Nanocellulose Films
Zhiqiang Fang,1,3,4 Bo Li,1 Yu Liu,1,5,* Jiatian Zhu,1 Guanhui Li,1 Gaoyuan Hou,1 Jie Zhou,2
and Xueqing Qiu1,2,*

SUMMARY Progress and Potential

Translation of the outstanding mechanical performance of individual nanocellu- Many efforts have been devoted
lose to macroscopic nanocellulose films can be achieved by various alignment to translating the superb
techniques. However, attention has seldom been paid to the degree of polymer- mechanical properties of
ization (DP) of cellulose that plays a pivotal role in increasing the mechanical individual nanocellulose to
strength of nanocellulose films. In this work, nanocellulose film with superior macroscopic film by diverse
tensile strength (1,014.7 G 69.1 MPa) is presented by a cellulose DP protection alignment techniques. However,
strategy. An alkaline sulfite-anthraquinone-methanol pulping is applied to not sparse works focus on the critical
only rapidly remove most of lignin and hemicellulose from wood blocks, which role of cellulose DP in the
facilitates the formation of hydrogen bonds among neighboring fiber cell walls mechanical properties of
in subsequent mechanical pressing, but also to significantly suppress the nanocellulose films. We
decomposition of cellulose DP. Such strong nanocellulose film sheds light on un- demonstrate super-strong yet
locking the exceptional mechanical potential of cellulose and has the potential lightweight anisotropic
for use in advanced applications traditionally dominated by nonrenewable ma- nanocellulose films with strength
terials such as plastics, glass, and metals. of up to 1.13 GPa by combining an
alkaline sulfite-anthraquinone-
methanol pulping with
INTRODUCTION
mechanical pressing. This pulping
Growing environmental awareness and depleting fossil resources have posed an
can not only rapidly remove most
emerging quest for lightweight materials with superb mechanical properties and
of lignin from wood blocks,
economic production from sustainable resources that are biodegradable, carbon
facilitating the formation of
neutral, safe, and natural.1–4 Natural cellulose materials (e.g., wood, paper,
hydrogen bonds among
clothing), one of oldest materials widely used by human for thousands of years,
neighboring fiber cell walls in
have long been recognized as inexhaustible, renewable, and sustainable polymers
subsequent pressing, but also
for building, textiles, tools, writing, and reading.1,3,5–15 However, with the increasing
remarkably suppress the
demands of modern society for high-performance materials, their functions have
decomposition of cellulose DP
been gradually replaced by metals and/or petroleum-based synthetic polymers.
that retains the outstanding
intrinsic properties of
As material innovation enters a new era of experiencing an unprecedented pace of
nanocellulose to a large extent.
progress, natural cellulose materials would have much more to offer us as high-per-
Such super-strong nanocellulose
formance materials for diverse high-strength yet lightweight applications such as
film has the potential for use as
electronics, building, and automobiles, with a view to the fascinating hierarchical
high-performance materials in the
structure and exceptional mechanical performance of cellulose.7,16–18 Anisotropic
areas traditionally dominated by
nanocellulose films, fabricated by diverse bottom-up nanofibril alignment tech-
nonrenewable materials such as
niques (e.g., wet stretching, wet extrusion, cold drawing, electric field-assisted align-
plastics and metals.
ment),19–27 have triggered increasing interest due to their exceptional mechanical
properties and environmental friendliness. For example, ribbons of oriented nano-
cellulose bearing polyethylene glycol were achieved by stretching the nanocellulose
networks in hydrogel state, simultaneously showing ultra-high tensile strength

1000 Matter 2, 1000–1014, April 1, 2020 ª 2020 Elsevier Inc.

(576 G 54 MPa) and modulus (32.3 G 5.7 GPa).27 Wang and coworkers presented an
ultra-strong biofilm with aligned bacterial cellulose (BC) by wet stretching.28 The as-
prepared BC film exhibited extraordinary tensile strength (1,005.3 MPa) and Young’s
modulus (48.1 GPa).

Although progress has been made to translate the exceptional mechanical proper-
ties to macroscopic nanocellulose films by different alignment methods, these
methods have disadvantages of complexity and being difficult to scale up. In the
wood industry, pretreatment with steam, heat, ammonia, or cold rolling followed
by mechanical compression is an effective way to enhance the mechanical properties
of natural wood.29–32 In 2018, Hu’s group proposed a facile and economic top-down
approach to fabricate strong anisotropic nanocellulose films (350 MPa tensile
strength) directly from natural longitudinal wood blocks by combining delignifica-
tion with mechanical pressing.25 A similar manufacturing procedure was also em-
ployed to process bulk natural wood into a high-performance structural material
with an average strength of 548.8.3 G 47.2 MPa.33 This top-down method avoids
the sophisticated yet complicated procedure of nanocellulose alignment by directly
utilizing the hierarchical structure of natural wood, shedding light on the facile, inex-
pensive, and scalable fabrication of anisotropic nanocellulose films with exceptional
mechanical properties.

Nevertheless, the anisotropic nanocellulose films fabricated by the top-down

method are still far inferior to individual natural nanocellulose or BC nanofiber films
obtained from nanofibril alignment techniques in terms of mechanical properties,
which is ascribed to the deterioration of the intrinsic properties of cellulose or incom-
plete delignification during the delignification procedure. Therefore, in this work we
proposed a cellulose DP protection strategy to prepare nanocellulose films with
exceptional mechanical properties. Wood blocks were first treated with an aqueous
alkaline sulfite-anthraquinone-methanol (ASAM) cooking liquor to quickly remove
lignin and hemicellulose while achieving a high degree of polymerization (DP) of cel-
lulose. The delignified wood blocks were then mechanically pressed with a presser
to obtain anisotropic nanocellulose films with outstanding mechanical properties by
increasing the number of hydrogen bonds between neighboring fiber cell walls.
Moreover, the relationship between the cellulose DP and the mechanical properties
of as-prepared nanocellulose films was elucidated in detail.

RESULTS AND DISCUSSION

Nature has developed the ability to obtain superior mechanical properties by 1StateKey Laboratory of Pulp and Paper
rational self-assembly of ordered structure at the nano level and molecular Engineering, South China University of
level.34–36 Therefore, to fully exploit the mechanical potential of cellulose, it is neces- Technology, Guangzhou 510640, China
2Schoolof Chemistry and Chemical Engineering,
sary to understand the structural hierarchy and mechanical properties of cellulose
South China University of Technology,
spanning from the molecular to the nano, micro, and macroscopic levels. Guangzhou, Guangdong 510640, PR China
3South China Institute of Collaborative
Cellulose generated from repeating b-D-glucopyranose molecules is the most Innovation, South China University of
crucial skeletal component in trees and plants and exhibits fascinating hierarchical Technology, Dongguan 523808, China
4Key Laboratory of Pulp and Paper Science &
structure. From the structural viewpoint, individual cellulose chains pack side by
Technology of Ministry of Education/Shandong
side via inter- and intrachain hydrogen bonding to form elementary fibrils (3–4 nm Province, Qilu University of Technology
in width) that possess both crystalline and amorphous regions alternating in the axial (Shandong Academy of Sciences), Jinan 250353,
China
direction.37 The crystalline cellulose possesses remarkable mechanical properties,
5Lead Contact
e.g., 7.5–7.7 GPa tensile strength and 110–220 GPa Young’s modulus, exceeding
*Correspondence: lygy0527@126.com (Y.L.),
those of glass, Kevlar, and steel fibers. The elementary fibrils are further assembled cexqqiu@scut.edu.cn (X.Q.)
into microfibrils that mainly constitute the cell wall of wood fiber with a tensile https://doi.org/10.1016/j.matt.2020.01.016

Matter 2, 1000–1014, April 1, 2020 1001

strength of about 0.3–1.4 GPa and a Young’s modulus of 14–27 GPa.3 The wood fi-
bers run parallel to the axis of the trunk and bind together by a matrix of hemicellu-
lose and lignin to form natural wood with a tensile strength of 50–140 MPa.4,38

There is a remarkable loss in mechanical properties in transition from nanoscale to

macroscale owing to poor adhesion and a large amount of nano- and microscale de-
fects that restricts the ideal stress transfer (Figure S1). This phenomenon is ubiqui-
tous across the nanomaterials such as graphene and carbon nanotubes.39,40 Various
sophisticated but complex alignment techniques were employed to transfer the
exceptional mechanical performance of nanocellulose to macroscopic nanocellu-
lose films through promoting ideal stress transfer and mitigating stochastic defects
emerging at larger scales.9,12,41–43 For example, a biofilm obtained by aligning the
BC had a record high tensile strength of 1 GPa and a Young’s modulus of 48.1 GPa.
Attaining such high mechanical properties for the films of nanocellulose isolated
from trees is, however, still a vital hurdle. This is probably attributed to the deterio-
ration of the intrinsic properties of nanocelluloses during their disintegration and to
the defects (such as boundaries and voids) within nanocellulose films.

To conquer the aforementioned obstacle, we used a combination of an aqueous

ASAM pulping approach and mechanical pressing to fabricate nanocellulose films
with exceptional mechanical properties. The aqueous ASAM pulping of wood blocks
can not only remove the lignin and hemicellulose quickly but also gain a high DP of
cellulose resulting from the synergistic effect of the rapid lignin removal and the
stopping reaction of cellulose chains (Figure 1A). The subsequent mechanical press-
ing renders the remarkably increased formation of hydrogen bonding among adja-
cent fiber cell walls while significantly reducing the defects within nanocellulose
films, thus contributing to the transformation of the exceptional mechanical proper-
ties of nanocellulose to the macroscopic nanocellulose films.

Rapid lignin fragmentation is able to mitigate the cellulose degradation induced by

peeling reaction and alkaline hydrolysis through reducing the reaction time. During
the ASAM pulping, hydrophobic lignin macromolecules quickly break down into
dissolvable molecular fragments by the action of sulfite ions and anthrahydroqui-
none dianion (AHQ2 ) under high-temperature and high-pressure conditions.44
The cleavage reactions take place in the predominant b-aryl ether that is mainly
responsible for the lignin removal.45 Figure S2 shows the cleavage of b-aryl ethers
to a large extent in the presence of sulfite ions. A sulfite ion first gives an electron
to quinone methide that results in the sulfonation of lignin at the a position. After
that, a new sulfite ion attacks the b-carbon atom in the sulfonated lignin to rupture
the b-aryl ethers. Nucleophile AHQ2 significantly contributes to the cleavage of
b-aryl ethers as well by transferring electrons to lignin quinone methide (Fig-
ure 1B).44,46 Furthermore, methanol in cooking liquor not only accelerates the pene-
tration of chemicals in wood blocks but also blocks the lignin condensation during
the cooking, which promotes the rapid removal of lignin.

In addition to the rapid lignin removal, the alkaline degradation of cellulose macromol-
ecules, which arises mainly from the peeling reaction and partly from the alkaline hydro-
lysis, is restricted dramatically by using anthraquinone as an oxidant. The reducing end
group in the cellulose chain is prone to be eliminated under alkaline conditions, and a
new reducing group is exposed (Figure S3A). The generation of new reductive ends will
render the repeated removal of reductive ends from the cellulose macromolecules,
leading to the continuous depolymerization of the cellulose that inevitably deteriorates
the intrinsic properties of nanocellulose. Moreover, cellulose macromolecules are

1002 Matter 2, 1000–1014, April 1, 2020

Figure 1. Schematic Diagram
(A) Schematic illustration of the ASAM pulping of wood blocks that degrades the lignin rapidly while achieving a high DP of cellulose.
(B) Lignin macromolecules are quickly fractured into small molecules under high temperature and pressure condition of ASAM pulping, which facilitates
the protection of cellulose DP.
(C) The stopping reaction between reducing end units in the cellulose chains and anthraquinone under alkaline conditions. The peeling reaction
is terminated by converting the reducing end groups into stable carboxylate groups, which also contributes to the protection of cellulose DP.
The cellulose DP degrades remarkably without using anthraquinone under alkaline conditions. Note that n represents the numbers of glucose units,
and n 1 > n 2 .

inclined to break into two or more short cellulose chains through the alkaline hydrolysis
of cellulose as the cooking approaches the maximum temperature, thus creating two or
more reductive ends that further promote the peeling reaction (Figure S3B). The occur-
rence of anthraquinone (AQ) ensures the conversion of the reducing aldehyde ends into

Matter 2, 1000–1014, April 1, 2020 1003

stable carboxyl groups (Figure S3C), thereby protecting cellulose DP from degradation
(Figures 1C and S3C).

To confirm the effect of AQ on the cellulose DP, we further cooked the wood blocks
with an aqueous alkaline sulfite-methanol cooking liquor (ASM). As shown in Fig-
ure S4, the cellulose DP of the wood blocks cooked by ASM is 1,639 G 17, which
is lower than the cellulose DP of the wood blocks cooked by ASAM (1,944 G 44).
The reduced cellulose DP is mainly due to the excessive peeling reaction of cellulose
under high temperature.

The entire procedure for the fabrication of nanocellulose film with exceptional mechan-
ical properties is as follows (as shown in Figure S5A): Wood blocks obtained by longitu-
dinally cutting the wood trunk were first treated with an aqueous ASAM cooking liquid
to obtain delignified wood blocks with high cellulose DP. Removing lignin in the middle
lamella promotes the subsequent formation of hydrogen bonding among aligned fiber
cells in the subsequent mechanical hot pressing. Furthermore, the delignified wood
block with well-preserved aligned wood fibers was mechanically pressed to prepare
nanocellulose films. The contents of cellulose, lignin, and hemicellulose in wood block
and the as-prepared nanocellulose film are shown in Figure S5B.

Figure 2A schematically shows the changes in lignin and hemicellulose contents, cel-
lulose DP, and hydrogen bonds among neighboring fiber cell walls during the whole
fabrication process. During ASAM pulping, the covalent linkages between lignin and
polysaccharides broke down at high temperature and high pressure, thereby
enabling the dissolution of lignin fragments and hemicellulose in the water/meth-
anol solution. As a consequence, the rigid and tight cellular structure of wood blocks
become soft and loose, and simultaneously numerous hydroxyls are exposed on the
surface of wood fibers that facilitates the formation of hydrogen bonds among the
adjacent fiber cells during the subsequent mechanical pressing. The cellulose DP
reaches 1,994 after cooking for 3 h, resulting from the peeling reaction and alkaline
hydrolysis of cellulose. Despite the cellulose DP of the delignified wood blocks
dramatically decreasing from 10,000 to 1,994 after ASAM pulping, it is still superior
to the commercial pulp (DP % 1,200). In the mechanical pressing procedure, the
loose macroscopic configuration tends to densify while numerous hydrogen bonds
are formed among neighboring fiber cell walls, which makes a significant contribu-
tion to the efficient transformation of the exceptional mechanical properties of nano-
cellulose to the resulting nanocellulose film.

The microscopic structures of the natural wood block, the delignified wood block,
and the as-prepared nanocellulose films were investigated by a scanning electron
microscopy (SEM) analysis. SEM images in Figure S6A demonstrate the ordered
orientation of wood lumina parallel to the growth direction of the tree. The cell walls
adhere to each other by a mixture of lignin and hemicellulose. The tight adhesion
between neighboring fiber cells becomes loose after delignification because of
the lignin removal in the middle lamella (Figure 2B). Figure 2C shows the well-
defined lumina of wood and delignified wood. The magnified SEM image in Fig-
ure S6B indicates that there are many rectangle-like pores (cell lumina) with a diam-
eter of 20–25 mm, and the boundaries between adjacent cell walls are fuzzy owing to
the existence of the heavily lignified middle lamella. After delignification, visible
gaps between adjacent cell walls appear due to the removal of the middle lamella
(Figure 2B). Meanwhile, as shown in Figures 2C and S7, the well-aligned configura-
tion of fiber cells in the delignified wood block is maintained, and the length of the
cellulose fibers is about 3 mm (Figures S7 and S8). Figure 2D shows the S1 and S2

1004 Matter 2, 1000–1014, April 1, 2020

Figure 2. Characterization of Chemical Composition and Structure of the Delignified Wood Block and Nanocellulose Film
(A) Schematic representation of the changes in the lignin and hemicellulose contents, DP of cellulose, and hydrogen bonds among neighboring fiber
cell walls during the whole fabrication process for super-strong nanocellulose film with a maximal tensile strength of 1.13 GPa (cooking time is 3 h).
(B and C) SEM images indicating the well-defined lumina in the radial direction (B) and the good alignment of fiber cells in the longitudinal direction (C)
of the delignified wood block.
(D) The nanocellulose orientation in S2 layer of fiber cell, suggesting a nanofibril angle of approximately 25  .
(E) Cross-sectional SEM images showing the densely packed structure of the as-prepared nanocellulose film.
(F) The parallelizable fiber cells along the growth direction of the tree in the as-prepared super-strong nanocellulose film.
(G) XRD pattern of the as-prepared nanocellulose film in the surface plane (beam perpendicular to the surface).

layers of the cell wall. The S2 layer, consisting of helically wound semicrystalline
nanocelluloses (inset in Figure 2D) bound together by a matrix of hemicellulose
and lignin via an abundance of carboxyl groups, possesses the highest strength
and stiffness among all layers.

Mechanical pressing along the radial direction was applied to compress the loose
configuration of delignified wood into a dense structure with approximately a 6-
fold reduction in thickness by the formation of hydrogen bonds among neighboring
fiber cell walls. No conspicuous lumen is observed from the SEM images in Figure 2E,
suggesting the highly dense structure of the as-prepared nanocellulose film that
promotes efficient stress transfer and mitigates the stochastic defects. The axial fiber
cells are running vertically through the growth direction of the wood even after high-
pressure pressing (Figure 2F), which suggests the perfect preservation of the

Matter 2, 1000–1014, April 1, 2020 1005

Figure 3. Mechanical Properties and the Operative Failure Modes of Nanocellulose Films
(A) Stress-strain curves of natural wood, anisotropic nanocellulose film, and isotropic paper made of randomly distributed wood fibers extracted from
the same natural wood.
(B) Tensile strength and modulus of natural wood, anisotropic nanocellulose films, and isotropic paper.
(C) Tensile strength and Young’s modulus of anisotropic nanocellulose film compared with other nanocellulose films.
(D–F) Proposed fracture mechanism of (D) natural wood, (E) isotropic paper, and (F) anisotropic nanocellulose film.
(G–I) SEM images showing the tensile-broken surfaces of (G) natural wood, (H) isotropic paper, and (I) anisotropic nanocellulose film; insets are zoomed-
in SEM images of corresponding tensile-broken surfaces.

alignment feature of fiber cells. X-ray diffraction (XRD) analysis in Figure 2G displays
the highly anisotropic distribution of scattering intensity, indicating the preferred
alignment of nanocelluloses in the cell wall, especially for the S2 layer.

In summary, a combination of the ASAM pulping of wood blocks and subsequent

mechanical pressing not only achieves a high DP of cellulose and preserves the or-
dered arrangement of fiber cells and nanocelluloses in the cell walls, but also in-
creases the numbers of hydrogen bonds among neighboring fiber cells. The high
DP of cellulose and the oriented arrangement of micro- and nanostructures along
with the increased numbers of hydrogen bonds among neighboring fiber cells
ensure the efficient translation of the outstanding mechanical properties of nanocel-
lulose to the as-prepared nanocellulose films.

Figure 3A displays the stress-strain curves of the natural wood, the anisotropic nano-
cellulose film, and the paper made of wood fibers extracted from the natural wood.

1006 Matter 2, 1000–1014, April 1, 2020

The tensile strength and toughness of the as-prepared nanocellulose film is as high
as 1.13 GPa and 19.7 MJ m 3, which is approximately 9-fold stronger than that of
natural wood (130 MPa and 2 MJ m 3).

To further verify the correlation between the highly aligned fibers and the excep-
tional mechanical properties, we prepared both anisotropic nanocellulose film
and isotropic paper. Anisotropic nanocellulose films were prepared through me-
chanically pressing the delignified wood blocks, while the isotropic paper was fabri-
cated by vacuum filtration of wood fibers disintegrated from the delignified wood
blocks, followed by the same mechanical pressing. The maximum tensile strength
of the anisotropic nanocellulose film is about 28-fold stronger than that of the
isotropic paper (only 40 MPa). This result indicates that the good alignment of fibers
is primarily favorable to transferring the exceptional mechanical properties of micro-
and nanofibers to the nanocellulose films. In addition, its maximum Young’s
modulus (57.8 GPa) is nearly 15-fold that of the original wood (3.9 GPa) and 55-
fold that of the isotropic paper (1.1 GPa), as shown in Figure 3B.

We compared the tensile strength and modulus of our nanocellulose film with pre-
viously reported cellulose-based films and materials, including all-cellulose films,
polyethylene glycol-grafted cellulose nanofibrils ribbon, nanofibrillar cellulose
(NFC) film, self-reinforced cellulose films, stretched BC arrays, wood fiber/NFC bio-
composites, and oriented nanofibrous BC film (Figure 3C).7,12,20,27,41,47–52 Notably,
the value for our nanocellulose films is much higher than those of previously reported
nanocellulose films.

The nanocellulose films also presented a low density (1.37 g cm 3). Strong and
lightweight materials are highly desired for modern applications ranging from build-
ing and transportation to automobiles and electronics. In the next experiments, we
compared our nanocellulose film with several strong metals (aluminum, cast iron,
carbon steel, Mg2Zn, Monel, and GrNbTiVZr)53–55 and other nanocellulose films
by normalizing their tensile strength and Young’s modulus by weight, respec-
tively.56–59 The high tensile strength and low density of our nanocellulose films led
to the highest specific strength (up to 820 MPa cm3 g 1) among any known natural
polymers and some strong metals (as shown in Figures S9A and S9B). Besides, our
nanocellulose film indicates a lowest specific Young’s modulus (up to 7.7 GPa cm3
g 1). Moreover, Figure S9C displays the toughness versus strength of our nanocel-
lulose film and other nanocellulose films,12,20,25,27,47,49,50 whereby our nanocellulose
films have the highest toughness and tensile strength.

The tensile strength of the nanocellulose films depends on the operative failure
modes including fiber fracture mode (Figures 3C and 3D) and fiber pull-out mode
(Figure 3E), which in turn is determined by whether advantage is taken of the excep-
tional mechanical properties of nanocellulose. To explore the difference in mechan-
ical properties of our anisotropic nanocellulose film and the paper made of randomly
distributed wood fibers, we carried out an SEM analysis to examine their fracture
morphology. According to the SEM images of the fracture morphology of paper
(Figure 3H), many pull-out fibers are observed due to the slippage of individual
wood fiber in the network, indicating that the paper fails under fiber pull-out
mode. Consequently, the paper exhibits a much lower tensile strength (40 MPa)
than the anisotropic nanocellulose films. The SEM images of the tensile-broken sur-
faces in Figure 3I show the fracture of the anisotropic nanocellulose film, suggesting
that it ruptures under fiber fracture mode. The strong hydrogen bonding among the
neighboring fiber cells enables the effective utilization of the ultra-strength of

Matter 2, 1000–1014, April 1, 2020 1007

nanocellulose. Consequently, the anisotropic nanocellulose film demonstrates su-
per-strong mechanical properties.

Table S1 illustrates the chemical components and mechanical properties of the nat-
ural wood and the as-fabricated anisotropic nanocellulose films with varying cooking
times. It can be seen that the cellulose DP and lignin content do correlate with the
mechanical properties (e.g., tensile strength, toughness, strain-to-failure) of the
nanocellulose films. Figure 4A displays the changes in lignin content and DP of cel-
lulose as the cooking time increases (1, 2, 3, 4, 5, 6, and 7 h) at intervals of 1 h. When
the cooking time increases to 2 h, the lignin content rapidly decreases from 26.5% to
4.5%. With the extension of cooking time, the delignification efficiency becomes
quite low. The removal of lignin is beneficial to the formation of hydrogen bonds
among adjacent fiber cells in the subsequent hot mechanical pressing, which leads
to the exceptional mechanical properties of the nanocellulose films.

Cellulose in natural wood has a DP of approximately 10,000.6,59 The average DP of

cellulose dramatically decreases to 2,538 G 34.2 after cooking the wood for 1 h. As
the cooking time increases from 1 h to 7 h, the average DP of cellulose gradually re-
duces from 2,538 G 34.2 to 1,448 G 46.4 because of the peeling reaction and alka-
line hydrolysis of cellulose under alkaline environment. XRD analysis was used to
investigate the crystallinity and polymorphy of cellulose for the natural wood and
the nanocellulose film from the wood blocks cooked for 3 h. Peaks at 2q = 16.8 ,
22.7 , and 34.6 assign to the (110), (200), and (004) lattice planes, respectively, sug-
gesting a typical cellulose crystal I organization (Figure S10A). The thermal degrada-
tion behavior of natural wood and the as-prepared nanocellulose films with varying
cooking times is shown in Figure S10B and Table S2. It is obvious that the nanocel-
lulose films have higher degradation temperature compared with the natural wood,
which is ascribed to the removal of hemicellulose. It is well known that hemicellulose
is amorphous with various branches and decomposes before lignin and cellulose as
the presence of acetyl groups inside the macromolecule.60 While most of the lignin
and hemicellulose are removed after cooking for 2 h, the thermal stability of the as-
prepared nanocellulose films decreases gradually, mainly due to the degradation of
cellulose DP.

A comparison of tensile strength of the as-prepared nanocellulose films with varying

cooking times is shown in Figure S11. The tensile strength shows a gradually growing
trend initially, and reaches a maximum value when the cooking time is 3 h. There-
after, a declining tendency is observed. When the cooking time is shorter than
3 h, the lignin content plays a predominant role in the mechanical properties of
the nanocellulose films (Table S1). Taking the tensile strength of the as-prepared
nanocellulose films as an example, the cellulose DP of the delignified wood blocks
cooking for 1 h has a highest average value of 2,538 G 34.2 but shows a
lowest average tensile strength of 766.7 G 63.1 MPa (Figure S12A). As the
delignification continues, the average strength increases to a maximum value of
1,014.7 G 69.1 MPa (Figure S12B), albeit with a remarkable decrease in the DP of
cellulose (from 2,538 to 1,944). This result indicates that the increased numbers of
hydrogen bonds among adjacent fiber cells after lignin removal primarily contrib-
uted to the utilization of the exceptional mechanical properties of nanocellulose
because the cooking time was shorter than 3 h.

When the cooking time is in the range of 3–7 h, the lignin content changes slightly
while the cellulose DP decreases continuously. Notably, the mechanical properties
of the as-prepared nanocellulose films begin to decline (Table S1). For example,

1008 Matter 2, 1000–1014, April 1, 2020

Figure 4. Relationship between Mechanical Properties of Nanocellulose Film and Cellulose DP and Lignin Content
(A) Lignin content and DP of cellulose as a function of cooking time. Note that the DP of cellulose in natural wood is unreachable.
(B) Tensile strength and DP of cellulose as a function of cooking time ranging from 3 h to 7 h. When the cooking time is in the range of 3–7 h, the DP of
cellulose dominates the mechanical properties of the as-prepared nanocellulose film.
(C and D) Tensile strength (C) and toughness (D) of the as-prepared nanocellulose film is almost linearly proportional to the DP of cellulose.
(E) The tensile strength and the DP of cellulose as a function of cooking time. The darker rectangular area indicates the ideal cooking time for the
delignification of wood blocks.

Matter 2, 1000–1014, April 1, 2020 1009

the average tensile strength decreases from 1,014.7 G 69.1 MPa to 718.1 G 73.3
MPa (Figure 4B). As shown in Figures 4C and 4D, cellulose DP has a linear relation-
ship with the average strength and toughness: the increased average DP of cellulose
leads to higher ultimate tensile strength and toughness. There is a turning point be-
tween the cellulose DP and the lignin content, which primarily determines the me-
chanical properties of the as-prepared nanocellulose films. As the cooking time is
lower than 3 h, the lignin content mainly determines the mechanical properties:
once the lignin content approaches a critical point at which the hydrogen bonding
among neighboring fiber cells is enough to prevent the slippage of neighboring fi-
bers during mechanical testing, the change in lignin content has a negligible impact
on the mechanical properties. In contrast, cellulose DP becomes a crucial parameter
that decides the mechanical properties of the resultant nanocellulose film.

Figure 4E shows the strength and cellulose DP as a function of cooking time. Accord-
ing to this figure, the ideal cooking time is in the range of 2–4 h (the darker rectan-
gular area). In this area, most of the lignin in wood blocks has been removed, which
facilitates the formation of hydrogen bonds among neighboring fiber cell walls that
ensures the ideal stress transfer. Once in a while, a high DP of cellulose leads to
excellent mechanical properties of the nanocellulose. Both the increased number
of hydrogen bonds among adjacent fiber cell walls and the high cellulose DP
contribute to the exceptional mechanical properties of the resulting nanocellulose
film.

Once most of lignin is removed, the DP of cellulose plays a predominant role in the
mechanical properties of the nanocellulose films. To further verify this viewpoint, we
utilized ASAM and sodium hypochlorite pulping to prepare delignified wood blocks
with similar lignin content, followed by the same mechanical hot pressing. As shown
in Figure S13A, an obvious variation in tensile strength is observed. The tensile
strength of the nanocellulose film obtained from ASAM pulping is 1,014.7 G 69.1
MPa, which is about 3-fold stronger than that of the anisotropic nanocellulose film
(325 MPa) prepared from sodium hypochlorite pulping. This is mainly due to the
serious deterioration of cellulose DP during the sodium hypochlorite pulping. Fig-
ure S13B shows the cellulose DP of nanocellulose films obtained from two different
pulping methods. The cellulose DP of the delignified wood blocks produced from
ASAM pulping (1,944 G 44.2) is much higher than that of the delignified wood
blocks prepared from sodium hypochlorite pulping (400).

Conclusion
We demonstrate super-strong yet lightweight anisotropic nanocellulose films by a
cellulose DP protection strategy. ASAM pulping ensures the rapid removal of lignin
from wood blocks while attaining a high DP of cellulose, thus facilitating the efficient
transformation of the extraordinary mechanical properties of nanocellulose to the
macroscopic nanocellulose films. As a result, the as-prepared nanocellulose film
not only presents maximal mechanical properties (1,014.7 G 69.1 MPa tensile
strength, 60.2 G 0.8 GPa modulus, and 15.2 G 1.9 MJ m 3 toughness), but also ex-
hibits a highest specific tensile strength (820 MPa cm3 g 1) among current natural
polymers that are superior to novel lightweight Mg2Zn (433 MPa cm3 g 1). The DP
of cellulose plays a pivotal role in increasing the mechanical properties of the ob-
tained nanocellulose films when the lignin content is lower than or equal to
3.3% G 0.14%: the higher the DP of cellulose, the better the mechanical properties
of the nanocellulose films. A high cellulose DP along with the increased numbers of
hydrogen bonds among neighboring fiber cell walls during mechanical hot pressing
promotes the ideal stress transfer and inhibits the occurrence of stochastic defects.

1010 Matter 2, 1000–1014, April 1, 2020

Such super-strong yet lightweight anisotropic nanocellulose films have the potential
for use as high-performance materials in areas traditionally dominated by nonrenew-
able materials such as plastics, glass, and metals, and give a critical clue to novel ma-
terial design from natural resources.

EXPERIMENTAL PROCEDURES
Materials
Pinewood blocks were used in this work. Their dimensions are 100 mm 3 35 mm,
with a thickness of 3 G 0.2 mm. Sodium hydroxide (>96%), sodium sulfite (>97%),
methanol (>99.5%), and anthraquinone (>98%) were all purchased from Guangzhou
Jinhuada Chemical Reagent.

Fabrication of Nanocellulose Film

The delignification of wood blocks was performed in a 1-L stainless steel autoclave
reactor (Parr 4523, USA). The delignification solution was prepared by dissolving so-
dium hydroxide (5 g), sodium sulfite (15 g), and anthraquinone (0.03 g) in 600 mL of
20 wt % methanol solution (methanol/water = 1:4). The wood blocks and the deligni-
fication solution (wood/solution = 1:20) were added into the reactor and kept for 1 h,
2 h, 3 h, 4 h, 5 h, 6 h, and 7 h, respectively at 170 C. After the reaction, the reactor
was first cooled down to 100 C and then quickly quenched to room temperature
with a water bath. The samples were immersed in 20 wt % methanol solution for
24 h to remove the residual black liquor. The delignified wood blocks were pre-
served in deionized (DI) water.

The delignified samples were covered with filter paper and pressed with a hydraulic
press under pressure of 8 MPa for 3 h. During this process, the filter paper should be
replaced at intervals to ensure the removal of water in wood chips. Finally, the de-
lignified samples were pressed at 90 C for 3 min under 8 MPa to obtain nanocellu-
lose films.

Individual wood fibers were isolated from the delignified wood blocks in water by
mechanical stirring and were then utilized to prepare wet isotropic paper of
randomly distributed wood fibers by vacuum filtration. The wet isotropic paper
was dried with the same mechanical hot process of the anisotropic nanocellulose
films.

Measurements and Characterizations

The microstructure of nanocellulose films and wood blocks were characterized by a
scanning electron microscope (Hitachi SU-70). The mechanical properties were carried
out on an Instron 5565 universal tester using a 2 KN load cell, and nanocellulose films
were dried at 105 C for 40 min prior to the test. The dimension of the nanocellulose
film for tensile testing was 100 mm 3 2 mm. The tensile curves were measured at a ten-
sile speed of 5 mm min 1 in a standard environment (T = 23 C, relative humidity = 50%),
as shown in Video S1. At least ten strips were tested for each sample to obtain average
tensile strength, and five points of a strip were measured by a micrometer to obtain the
average thickness of nanocellulose film. Thermogravimetric analysis was determined by
using a Q500 TGA (TA, USA). For X-ray single crystal diffractometer experiments, Mo X-
ray radiation with a wavelength of 0.07107 nm (R-AXIS SPIDER, Japan) was used.

The lignin contents were measured according to Technical Association of Pulp and
Paper Industry Standard Method T 222-om-83. In brief, 1 g of dry wood (m0) was ex-
tracted with ethanol alcohol for 4 h, which was then treated with cold H2SO4 (72%,
15 mL) for 2 h with vigorous stirring at 20 C. The mixtures were transferred to a

Matter 2, 1000–1014, April 1, 2020 1011

beaker and diluted to 3 wt H2SO4 by adding 560 mL of DI water and boiling for 4 h.
Finally, they were filtered and washed with DI water. The insoluble materials were
dried and weighed (m1). The lignin content was calculated as [m1/m0] 3 100%.

The DP was measured by the standard methods for cellulose (Pulps-determination of

viscosity National standard T1548-1989). In brief, dried wood cellulose (0.15 g) was
dissolved in 0.5 M copper ethylenediamine (20 mL) for 30 min. Intrinsic viscosities of
the solutions were obtained by using a Cannon-Fenske capillary viscometer, and
these values were converted to [h]∙r values by using the Mark-Houwink-Sakurada
equation, DP0.905 = 0.75 [h]. However, for the wood slices softened for 1 h and 2 h
with high lignin content, this method was not suitable for measuring viscosity
directly. A further delignification step using sodium chlorite (NaClO2), which can
be delignified selectively and does not degrade the fibers, was needed. The bleach
solution was prepared by dissolving NaClO2 (0.6 g) in DI water (65 mL) and adding
0.5 mL of glacial acetic acid. The fibers (2 g) were immersed in the bleach solution
and kept for 30 min at 70 C.

SUPPLEMENTAL INFORMATION
Supplemental Information can be found online at https://doi.org/10.1016/j.matt.
2020.01.016.

ACKNOWLEDGMENTS
We appreciate the Natural Key R&D Program of China (2018YFD0400701), the
Young Scientists Fund of the National Natural Science Foundation of China
(31700508, 21978103), the Natural Science Foundation of Guangdong Province
(2017A030310635), Guangdong Province Science Foundation (2017B090903003),
the Pearl River S&T Nova Program of Guangzhou (201806010141), and the Funda-
mental Research Funds for the Central Universities (2019MS083).

AUTHOR CONTRIBUTIONS
Z.F., Y.L., and X.Q. conceived the idea and designed the experiments; Z.F., Y.L.,
B.L., and J. Zhu carried out the experiments, analyzed data, and wrote the paper;
G.L., G.H., and J. Zhou contributed to scientific discussion of the article.

DECLARATION OF INTERESTS
The authors declare no competing interests.

Received: August 23, 2019

Revised: October 19, 2019
Accepted: January 21, 2020
Published: February 19, 2020

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