Received: 9 February 2022 Revised: 1 April 2022 Accepted: 2 April 2022

DOI: 10.1002/app.52462

RESEARCH ARTICLE

Cellulose and lignin as carbon black replacement in natural

rubber

Hossein Kazemi1 | Maxime Parot2 | Tatjana Stevanovic2 | Frej Mighri1 |

Denis Rodrigue1

1
Department of Chemical Engineering,
Laval University, Quebec, Quebec,
Canada
2
Wood and Forest Science Department,
Laval University, Quebec, Quebec,
Canada
Correspondence
Denis Rodrigue, Department of Chemical
Engineering, Laval University, Quebec,
Quebec G1V 0A6, Canada.
Email: denis.rodrigue@gch.ulaval.ca
Funding information
Natural Sciences and Engineering
Research Council of Canada, Grant/
Award Number: RGPIN-2016-05958
Abstract
Lignocellulosic fillers have gained attention as biofillers due to their low cost,
availability, and eco-friendly nature. Various lignocellulosic fillers from differ-
ent sources having different chemical compositions have been used in natural
rubber (NR) without sufficient comparison. So the objective of this study is to
investigate the effect of two well defined industrial fillers (lignin and cellulose)
along with black spruce cellulosic pulps obtained from an organosolv process
on the properties of NR. To this end, a range (0/100–100/0) of lignin/cellulose
(L/C) ratios is prepared. The biobased materials are chemically extracted from
black spruce sawdust to partially replace carbon black (CB) in NR composites.
The results show that higher L/C ratios provide higher tensile strength and
elongation break, while lower ratios produce higher tensile modulus and hard-
ness. These results indicate that a balance between different mechanical prop-
erties can be achieved by controlling the L/C ratio. A discussion on the total
replacement of CB by lignin or cellulose is also presented to produce a more
biobased compound.

KEYWORDS
carbon black, cellulose, lignin, mechanical properties, natural rubber

1 | INTRODUCTION chemical compositions lead to different mechanical

Carbon black (CB) is the most common filler for natural
rubber (NR) as it can effectively reinforce all the proper-
ties. However, CB is a petroleum-based material and
requires high amounts of energy for its production, lead-
ing to environmental issues and higher production
costs.1,2 On the other hand, lignocellulosic fillers are
readily available, renewable, biodegradable, lightweight
and inexpensive making them promising candidates to
replace conventional fillers in NR composites.3–11 Since
lignocellulosic fillers are extracted from plants, their
main components are similar (cellulose, lignin and hemi-
cellulose), but their ratios depend on the type of plant
(wood, bast, leaf, seed, grass, etc.) These differences in
properties.12,13
Various lignocellulosic fillers, such as maple,14
hemp,15 flax,16 wheat straw,17 aspen wood flour,18 rattan
powder,19 bamboo fiber,20 jute,21 cotton,22 sisal,23 oil
palm,24 coir,25 pineapple leaf,26 isora,27 grass,28 silk,29 pea-
nut shell powder,30 and coconut shell powder,31 have been
used as fillers in NR composites. In addition to natural
fibers, several studies have been conducted on the use of
cellulose,32,33 lignin,34 and regenerated cellulose35–39 on
the properties of rubber composites. The mechanical prop-
erties of selected composites with different lignocellulosic
fillers are listed in Table 1. Surface treatments, such as
alkali26,27,30,40 and acid hydrolysis,41,42 were shown to
modify the chemical compositions, especially by removing

J Appl Polym Sci. 2022;139:e52462. wileyonlinelibrary.com/journal/app © 2022 Wiley Periodicals LLC. 1 of 14

https://doi.org/10.1002/app.52462
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TABLE 1 Mechanical properties of NR composites with different lignocellulosic fillers

Tensile Elongation Modulus at 100% Hardness

Filler Content (phr) strength (MPa) at break (%) elongation (MPa) (shore A) Ref.
Aspen wood flour 0 18.50 593.7 0.89 42 [18]
10 21.33 655.1 1.26 48
20 18.79 567.7 1.72 52
30 14.98 647.4 1.68 56
50 9.68 523.9 2.28 62
Rattan powder 0 24.8 1016 0.70 – [19]
5 21.4 945 0.87 –
10 18.9 893 0.98 –
15 16.8 855 1.21 –
30 11.2 707 1.52 –
Bamboo fiber 0 19.8 749 0.61 35 [20]
10 9.3 421 0.81 41
20 7.4 359 1.19 49
30 5.5 293 1.41 54
50 3.6 181 1.90 64
Jute fiber 0 18.5 ± 1.3 788 ± 18 0.68 ± 0.05 – [21]
1 18.2 ± 0.4 785 ± 15 0.73 ± 0.03 –
2.5 21.0 ± 0.7 779 ± 11 1.09 ± 0.05 –
5 19.0 ± 1.0 775 ± 14 1.12 ± 0.06 –
7.5 15.4 ± 1.3 731 ± 23 1.66 ± 0.09 –
10 14.2 ± 1.7 735 ± 18 1.94 ± 0.12 –
Cotton fiber 0 21.3 ± 0.4 625 ± 4 1.08 ± 0.08 44 ± 0.5 [22]
5 18.6 ± 0.3 600 ± 4 1.52 ± 0.09 55 ± 0.8
10 15.6 ± 0.6 576 ± 4 2.08 ± 0.06 65 ± 0.6
15 12.4 ± 0.4 561 ± 3 2.18 ± 0.13 72 ± 0.1
20 10.3 ± 0.2 554 ± 3 2.67 ± 0.16 77 ± 0.4
Sisal fiber 0 20.1 1347 0.81 40 [23]
10 10.9 1089 1.08 45
20 9.6 1050 1.12 49
30 8.6 916 1.22 55

Abbreviation: NR, natural rubber.

lignin and hemicellulose (amorphous components), lead-
ing to improved mechanical properties.
In general, the results showed that the tensile strength
and elongation at break of NR composites decreased with
increasing natural fiber content due to poor compatibility
between the hydrophilic filler and hydrophobic NR.
On the other hand, the tensile modulus and hardness
increased with lignocellulosic fillers addition because of
their higher stiffness compared to NR.19,20,22,23,25–28,43
Some studies also showed that adding lignocellulosic
fillers can decrease the density, as well as curing time and
biodegradation time of rubber compounds.11,14 Improved
dynamic mechanical properties of rubber composites
was also reported when CB is replaced by cellulose
fibers.32,44–46 The advantages and limitations of lignocellu-
losic fillers have been reported when used as CB replace-
ment alone or as a hybrid filler system (natural and
conventional fillers together).14,32,47–49
Although several studies have been carried out to
study the effect of a single lignocellulosic filler on
NR composites properties, there is no information/
comparison on the effect of their chemical composition
on the NR composites properties. Therefore, this work
investigates two lignocellulosic fillers (cellulose and
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KAZEMI ET AL. 3 of 14

lignin) alone or together (different lignin/cellulose [L/C] TABLE 2 Chemical composition of the lignocellulosic fillers
ratio) to partially replace CB in NR composites. In addi-
Chemical composition (%)
tion, a comprehensive study was performed to quantify
the effect of total CB replacement by purified cellulose or Lignin content Cellulose
purified lignin as fillers. Sample code (Klason) content
Black spruce (A1) 26 51
A2 77 23
2 | EXPERIMENTAL SECTION A3 51 49
A4 48 52
2.1 | Materials
A5 38 62

NR (TSR20), sulfur, stearic acid, zinc oxide (ZnO), N-tert- A6 30 70

butyl-2-benzothiazyl sulfonamide (TBBS), 2,2,4-trimethyl-
1,2-dihydroquinoline polymer (TMQ), N-(1,3-dimethylbutyl)-
N0 -phenyl-p-phenylenediamine (6PPD), and CB (grades
N330 and N550) were all of commercial grades and provided
by a local company (Canada). The purified cellulose grade
(TC90) was prepared from CreaFill Fibers Corporation
(Chestertown, MD). The cellulose fibers contain 99.5%
α-cellulose with an average length and width of 60 and
20 μm, respectively. The purified lignin (81%) was provided
by Renmatix (King of Prussia, PA). The lignin particles were
sieved in the range of 45–90 μm and dried at 100 C for 2 h
before use. The black spruce sawdust and chips was supplied
by a local sawmill (DK carbone, Quebec, Canada).
2.2 | Lignocellulosic fillers preparation
The black spruce chips were treated by an organosolv pro-
cess using ethanol-water catalyzed by FeCl3.50,51 Briefly,
the wood chips were delignified with different ethanol-
water ratios in a reactor for 90 min at 180 C. These
different ethanol ratios lead to different yields in deli-
gnification, thus different ratios of lignin in the cellulose
fibers. The lignin content was determined by the Klason
method according to the NREL procedure.52 Briefly, the
cellulose fibers are treated with sulfuric acid to hydrolyze
the polysaccharides and make them go into solution. The
remaining solid corresponds to lignin which is added to
the amount of acid soluble lignin determined by UV.
The natural fillers were transformed and sieved to keep
only the particles between 125 and 250 μm, then they were
dried at 100 C for 2 h to remove any moisture before their
use. Table 2 reports on the compositions of the raw black
spruce sawdust (A1) and the cellulosic pulps issued from
the described organosolv process (A2–A7).
A7 19 81
Thermo Fisher Scientific, Waltham, MA). In the first step
(masterbatch), the NR was masticated for 2 min and the
fillers (CB and/or cellulose/lignin) were added and mixed
for 3 min. Then, stearic acid, ZnO, 6PPD, and TMQ were
added and mixed for 2 min. The temperature and rotor
speed for the masterbatch were kept constant at 90 C and
60 rpm, respectively. The second step was performed at
least 2 h after the first step (stress relaxation). In this final
batch, the curing agents (sulfur and TBBS) were added to
the rubber compound (masterbatch) and mixed for 3 min
at 70 C and 60 rpm. The contents, in parts per hundred of
rubber (phr), were fixed as: stearic acid (2 phr), ZnO
(4 phr), 6PPD (1.5 phr), TMQ (1.5 phr), sulfur (3 phr), and
TBBS (2 phr). The total filler content was also kept con-
stant at 40 phr, but the filler ratios were changed as
described in Table 3 with their sample code. In all cases,
the rubber compounds were cured via compression mold-
ing (Carver Autoseries 3893, Wabash, IN) under a pres-
sure of 45 kgf/cm2 and 145 C. The mold dimensions were
130  100  1.8 mm3, and the fibers' orientation in the
mold is assumed to be random for all the compounds.
2.4 | Characterization
2.4.1 | Scanning electron microscopy (SEM)
The samples morphology was studied via SEM on a FEI
Inspect F50 (Hillsboro, OR). The samples were cryo-
fractured using liquid nitrogen and then coated with a
conductive Pd/Au layer prior to their analysis under dif-
ferent magnification.

2.3 | Compounding 2.4.2 | Curing characterization

Rubber compounding was carried out in two steps using The curing characteristics were evaluated using an
an internal batch mixer (Haake Büchler Rheomix, oscillatory disc rheometer (ARES, Rheometric Scientific,
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TABLE 3 Compound formulations and their codes

Component (phr)

Sample code NR CB Black spruce (A1) A2 A3 A4 A5 A6 A7 Cellulose Lignin

Ref 100 40 – – – – – – – – –
A1/NR 100 30 10 – – – – – – – –
A2/NR 100 30 – 10 – – – – – – –
A3/NR 100 30 – – 10 – – – – – –
A4/NR 100 30 – – – 10 – – – – –
A5/NR 100 30 – – – – 10 – – – –
A6/NR 100 30 – – – – – 10 – – –
A7/NR 100 30 – – – – – – 10 – –
C10/NR 100 30 – – – – – – – 10 –
C20/NR 100 20 – – – – – – – 20 –
C30/NR 100 10 – – – – – – – 30 –
C40/NR 100 0 – – – – – – – 40 –
L10/NR 100 30 – – – – – – – – 10
L20/NR 100 20 – – – – – – – – 20
L30/NR 100 10 – – – – – – – – 30
L40/NR 100 0 – – – – – – – – 40

Abbreviations: CB, carbon black; NR, natural rubber.

New Castle, DE) based on ASTM D-5289. The samples
(25 mm disk in diameter and 3 mm in thickness) were
analyzed at 145 C under a nitrogen atmosphere. The
scorch time (t0 10), optimum cure time (t0 90), minimum
torque (ML), and maximum torque (MH) were estimated
from the curing curves.
capacity was 500 N and the extension rate was 500 mm/
min. The hardness (Shore A) was determined by a PTC
Instruments 306L (Los Angeles, CA) based on ASTM
D2240 and a minimum of five measurements was
performed.

2.4.3 | Payne effect
An oscillatory disc rheometer (ARES, Rheometric Scien-
tific, New Castle, DE) was used to study the Payne effect
based on ASTM D-8059. The samples were cut in circular
shape (25 mm diameter and 3 mm thickness). All the
tests were performed at a constant temperature (70 C)
and frequency (1 Hz), while the strain amplitude was var-
ied from 0.07% to 300%.
2.4.4 | Mechanical properties
The mechanical properties (tensile strength, elongation
at break and modulus) were obtained using a universal
testing machine (Instron 5565, Norwood, MA) based on
ASTM D412. The samples were cut in a rectangular
shape with dimensions of 33  6.0  1.6 mm3 (die C),
and the average value of five tests was reported with their
standard deviation. For this characterization, the load cell
3 | RESULTS A ND DISCUSSION
3.1 | Partial replacement of CB with
natural fillers
3.1.1 | Morphology
Figure 1 presents the SEM micrographs for fillers A1, A2,
A4, and A7. It can be seen that the raw black spruce fibers
are cylindrical in shape with an aspect ratio of about 5, while
fillers with higher L/C ratio (A2) have a more particle-like
shape because most of the cellulose was extracted leaving
mainly lignin. On the other hand, the fillers with low L/C
ratio (A7) are fibers with higher aspect ratio (around 25)
due to higher delignification (lignin removal). For interme-
diate L/C values (close to unity), Figure 1e,f (A4) show no
definite shape which represents a random combination of
fibers and particles associated to the destruction of the
fibers' structure after partial lignin extraction.
Figure 2 presents the SEM micrographs for selected
composites. Figure 2a,b shows that the raw black spruce
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selected lignocellulosic fillers: A1 (a and

F I G U R E 1 SEM micrographs for

b), A2 (c and d), A4 (e and f), and A7

(g and h). SEM, scanning electron
KAZEMI ET AL.

microscopy
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6 of 14 KAZEMI ET AL.

F I G U R E 2 SEM micrographs for

selected composites: A1/NR (a and b),
A2/NR (c and d), A4/NR (e and f), and
A7/NR (g and h). SEM, scanning
electron microscopy

fibers do not have good compatibility with NR because mechanism is interfacial slip between the reinforcement
voids are observed around the fibers. In addition, fibers and the matrix. On the other hand, Figure 1g,h shows
pull-out is present indicating that the main failure that the well delignified fibers A7 fibers, having higher

KAZEMI ET AL.
L/D ratios than the raw black spruce fibers, lead to better
physical interactions between the fillers and the matrix
(A7/NR vs. A1/NR). Figure 2g,h also confirmed that A7
fibers are well embedded into the rubber matrix.
A comparison of the SEM images for A1 and A7 fibers
with their respective composites (A1/NR vs. A7/NR) con-
firm that the fillers size and shape did not change after
compounding with NR. However, Figure 2c,d shows that
the size of A2 fillers became smaller after mixing with
NR. Even though the same size of fillers was used for all
samples, it appears that A2 particles were broken because
of the high stresses (shear and elongational) applied by
the internal mixer during compounding. But smaller par-
ticle size for A2 produced higher specific surface area and
less voids around them in the rubber matrix. Therefore, a
better filler dispersion and a smoother surface were
observed for A2/NR composites compared to the others.
On the other hand, since A4 fillers are a combination of
fibers and random shape particles, a non-uniform filler
size distribution was observed for A4/NR (Figure 2e,f).
3.1.2 | Curing characteristics
The curing characteristics for samples A1/NR, A2/NR,
A3/NR, A4/NR, A5/NR, A6/NR, and A7/NR are pres-
ented in Figure 3. The curing curves are also shown in
Figure S1. In general, the results show that replacing CB
by a lignocellulosic filler increases the scorch time and
curing time. This is due to the presence of a high amount
of aliphatic hydroxyl functional groups, especially in the
cellulose enriched lignocellulosic fillers structure. These
hydroxyl groups are known to adsorb and deactivate
accelerators (TBBS) during the vulcanization process,
resulting in slower curing kinetics.53,54 The results also
show longer curing time when a higher L/C ratio was
used (Figure 3a). For example, sample A2/NR has 8%
F I G U R E 3 Curing characteristic for samples A1/NR, A2/NR, A3/NR, A4/NR, A5/NR, A6/NR, and A7/NR: (a) scorch time (t0 10) and
optimum curing time (t0 90); (b) minimum torque (ML) and maximum torque (MH) [Color figure can be viewed at wileyonlinelibrary.com]
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7 of 14
longer t0 10 and t0 90 than A7/NR. In fact, cellulose is more
rigid than amorphous lignin due to its crystalline struc-
ture. Therefore, the compounds filled with cellulose show
a higher viscosity compared to the ones filled with lignin,
resulting in higher heat generation caused by friction
(viscous dissipation) leading to shorter curing time.
Higher compound viscosity with lower L/C ratio can be
related to the minimum torque and maximum torque
results (Figure 3b). For instance, sample A7/NR showed
15% and 10% higher ML and MH compared to A2/NR,
respectively.
3.1.3 | Mechanical properties
The mechanical properties of A1/NR, A2/NR, A3/NR,
A4/NR, A5/NR, A6/NR, and A7/NR are compared in
Figure 4. The results show that when the L/C ratio is in
the range of 0.6–1 (A3, A4, and A5), lower tensile strength
and elongation at break were obtained compared to other
samples (Figure 4a,b). This is due to the non-uniform filler
size distribution of these composites as shown via SEM
(Figures 1e,f and 2e,f), resulting in a disturbance of the
filler-matrix stress transfer. For example, A2/NR has 29%
and 20% higher tensile strength and elongation at break
compared to A5/NR, respectively. In addition, the com-
posites filled with delignified fillers (A2–A7) have higher
tensile strength (up to 49%) and elongation at break (up to
27%) than A1/NR (raw black spruce). Lower mechanical
properties for A1/NR could be related to the presence of
hydrophobic and other extractives on the fibers surface.
Previous studies also showed that removing constituents
from lignocellulosic fibers via chemical treatments (such
as alkali) can improve their adhesion/interaction with the
NR matrix.40,55,56
In fact, since lignin is a more hydrophobic material
than cellulose,57,58 fillers with a higher L/C ratio show

8 of 14
F I G U R E 4 Mechanical properties for samples A1/NR, A2/NR, A3/NR, A4/NR, A5/NR, A6/NR, and A7/NR: (a) tensile strength,
(b) elongation at break, (c) M100, and (d) hardness
better compatibility with NR and produce better stress
transfer from the matrix to the fillers, as well as higher
tensile strength and elongation at break. On the other
hand, when an optimal content (10 phr) of purified cellu-
lose is added, a three-dimensional network (cellulose/cel-
lulose network and Zn/cellulose network) can form
inside the matrix (hydrogen bonding) resulting in
improved mechanical properties.59–61 However, both lig-
nin and cellulose seem to have their own advantages, but
a L/C ratio around 1 might not be an interesting filler for
the NR composites based on the experimental results.
Depending on the application, A2/NR (highest L/C ratio)
was found to be the best because of its higher tensile
strength and elongation at break.
The results for the modulus at 100% elongation
(M100) and hardness show that adding lignocellulosic
fillers with a lower L/C ratio leads to higher stiffness
(Figure 4c,d). For example, A7/NR has 24% higher M100
and 4% higher hardness compared to A2/NR, respec-
tively. This sample (A7/NR) also shows 25% higher M100
compared to the reference (sample with 40 phr CB). In
fact, since cellulose has a crystalline structure and lignin
is amorphous, higher stiffness for the rubber compounds
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KAZEMI ET AL.
is expected when fillers with a lower L/C ratio are used.
In addition, the presence of hydroxyl group on the cellu-
lose surface creates strong hydrogen bonds between the
cellulose fibers increasing filler–filler interactions. It can
also be concluded that the best lignocellulosic fillers for
NR composites are those having high purities of a single
component (high or low L/C ratio); that is, it is better to
use highly purified cellulose or highly purified lignin
alone rather than lignocellulosic fillers containing both
components. But the results also show that a higher L/C
ratio provides higher tensile strength and elongation at
break, while a lower L/C ratio is better to improve tensile
modulus and hardness of NR composites. Thus a compro-
mise must be made depending on the final application.
3.2 | Total replacement of CB with
cellulose and lignin
3.2.1 | Morphology
SEM micrographs of the industrial cellulose fibers and
lignin particles are presented in Figure 5. Cellulose fibers

KAZEMI ET AL.
F I G U R E 5 SEM micrographs for:
cellulose (a and b) and lignin (c and d).
SEM, scanning electron microscopy
are fully elongated with an aspect ratio of 8, while lignin
particles are more spherical in shape. In our case, the
fillers were sieved in the range of 45–90 μm to limit size
variations.
Figure 6 presents the SEM micrographs of samples
C10, L10, C40, and L40. Although the same particle size
for cellulose and lignin was used in this study (sieving),
finer lignin particles were observed in SEM images after
mixing with NR. It appears that lignin particles were bro-
ken due to the high stresses applied by the internal mixer
during compounding. On the other hand, the particle size
for cellulose fibers remained constant due to their strong
crystalline structure but flexible nature. The SEM images
also confirmed the poor compatibility between cellulose
fibers and NR as voids are observed at their interface.
Higher filler agglomeration also occurs when more CB
was replaced by cellulose (Figure 6e,g). On the other
hand, better filler-matrix compatibility and fillers disper-
sion were obtained with lignin only as filler due to its
more hydrophobic nature compared to cellulose.
3.2.2 | Curing characteristics
Figure 7 and Figure S2 present the curing characteristics
and the curing curves of NR composites filled with lignin
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9 of 14
and cellulose with different filler contents, respectively.
The results show that replacing CB with cellulose and lig-
nin samples increases the curing time due to the presence
of hydroxyl functional groups in lignocellulosic fillers.
For example, L40 has 94% and 77% longer t0 10 and t0 90
compared to Ref, respectively. In addition, the com-
pounds filled with cellulose have shorter curing time
compared to lignin at the same filler content. This is due
to the higher viscosity of the cellulose-filled rubber com-
pounds compared to the lignin-filled ones, resulting in
more heat generation caused by friction leading to
shorter curing time. For example, L40 has 11% longer
t0 90 compared to C40.
The results also showed that above 10 phr replace-
ment of CB with cellulose samples, ML and MH
decreased by 18% and 12%, respectively. However, fur-
ther CB replacement with cellulose did not change the
MH of NR compounds. The maximum torque (MH) is
related to the degree of crosslinking and stiffness of rub-
ber compounds. Here, CB produces more physical cross-
links than cellulose because of better filler-matrix
interaction, while cellulose fiber is stiffer than CB and
has a higher modulus. Combining both materials can
lead to intermediate properties (degree of crosslinking
and stiffness), but replacing CB with cellulose does not
significantly change the MH. On the other hand,
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10 of 14 KAZEMI ET AL.

F I G U R E 6 SEM micrographs for

selected composites: C10 (a and b), L10
(c and d), C40 (e and f), and L40 (g and
h). SEM, scanning electron microscopy

replacing CB by lignin substantially decreases both ML than those containing lignin at the same filler content.
(down by 57%) and MH (down by 58%). In addition, the For example, C40 has 187% and 114% higher ML and
composites filled with cellulose have a higher torque MH than L40, respectively. This is due to the crystalline
 10974628, 2022, 26, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.52462 by UFMS - Fundacao Universidade Federal de Mato Grosso do Sul, Wiley Online Library on [13/12/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
KAZEMI ET AL. 11 of 14

F I G U R E 7 Curing characteristics
of NR composites filled with lignin and
cellulose at different filler contents:
(a) scorch time (t0 10) and optimum
curing time (t0 90); (b) minimum torque
(ML) and maximum torque (MH). NR,
natural rubber [Color figure can be
viewed at wileyonlinelibrary.com]

F I G U R E 8 Payne effect analysis

(strain sweep) for samples: (a) C10, C40,
L10, L40 and (b) C20, C30, L20, L30
[Color figure can be viewed at
wileyonlinelibrary.com]

structure of cellulose and the strong hydrogen bonding T A B L E 4 Results of the Payne effect analysis and Kraus
between cellulose particles increasing filler-filler interac- modeling of NR composites filled with lignin and cellulose at
tions and the stiffness of rubber compounds. different filler content

Sample G00 (kPa) G0∞ (kPa) ΔG0 (kPa) Υ c (%)

3.2.3 | Payne effect C10 321 4 317 8

L10 309 11 298 12
The Payne effect analysis is reported in Figure 8 to C20 312 3 309 7
study filler-filler interactions in rubber composites. L20 248 6 242 22
According to the Payne effect theory, the storage mod- C30 348 2 346 5
ulus (G0 ) strongly depends on filler-filler interactions in
L30 221 6 215 24
an unvulcanized filled compound. As the deformation
C40 367 1 366 3
amplitude (dynamic oscillatory test) increases, G0
decreases due to interactions breakdown between the L40 205 4 201 20
filler aggregates. Therefore, higher storage modulus var- Abbreviation: NR, natural rubber.
iation (ΔG0 ) indicates more filler-filler interactions and
higher amount of filler agglomerations in the rubber
matrix.62–64 The value of ΔG0 is calculated as the differ-
ence between the storage modulus at the beginning of filler-filler interactions and filler agglomerations in a rub-
the test (G0 [0]) and the storage modulus at the end of ber compound. The results also show that higher CB
the test (G0 [∞]). replacement by cellulose led to higher ΔG0 . On the other
Table 4 shows that ΔG0 is higher for the composites hand, ΔG0 continuously decreases by replacing CB with
filled with cellulose samples compared to their lignin lignin. For instance, ΔG0 for C40 is 15% higher than C10,
samples containing counterparts. For example, C40 has while ΔG0 for L40 is 33% lower than L10. This indicates
82% higher ΔG0 than L40 because cellulose has a high that lignin generates weaker filler-filler interactions
density of hydroxyl groups on its surface, creating strong even compared to CB, while cellulose produces stronger
hydrogen bonding between the particles leading to strong filler-filler interactions.

12 of 14
Following the Payne effect analysis, Kraus Equation
was used to determine the critical strain (Υc) at which
50% of the filler network is broken down. This value is
obtained by fitted the data to the model65:
G0Υ  G0∞ 1 79% and 45% lower tensile strength and elongation at
¼  2m ð1Þ
G00  G0∞ Υ break, while 12% and 9% higher M100 and hardness com-
1þ Υc
where, G0Υ , G0∞ and G00 refer to the storage modulus at a
strain of Υ , maximum strain and zero strain, respectively.
In all cases, the correlation coefficients (R2) are above 0.95
confirming a reliable curve fitting by the Kraus model. As
shown in Table 4, C40 has 63% lower Υ c compared to
C10, while L40 has 67% higher Υ c compared to L10. This
is attributed to a higher amount of filler agglomeration in
the rubber matrix when cellulose is used.
3.2.4 | Mechanical properties
Figure 9 presents the mechanical properties of NR com-
posites filled with different lignin and cellulose content.
The replacement of 10 phr of CB with cellulose slightly
increases the tensile strength, elongation at break, M100,
and hardness by 9%, 35%, 5%, and 3%, respectively. How-
ever, as shown in the SEM micrographs (Figure 6e,g) and
the Payne effect results (Table 4), a high amount of filler
agglomerations was observed when more than 10 phr cel-
lulose was added. The mechanical properties result also
10974628, 2022, 26, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.52462 by UFMS - Fundacao Universidade Federal de Mato Grosso do Sul, Wiley Online Library on [13/12/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
KAZEMI ET AL.
F I G U R E 9 Mechanical properties
of NR composites filled with lignin and
cellulose at different filler contents:
(a) tensile strength, (b) elongation at
break, (c) M100, and (d) hardness. NR,
natural rubber
show that the tensile strength rapidly decreased when
higher amounts of cellulose were used. On the other
hand, the values for M100 and harness increased with
increasing cellulose content due to strong hydrogen
bonding between cellulose fibers. For example, C40 has
pared to Ref, respectively.
Figure 9 also shows that total replacement of CB with
lignin results in higher elongation at break (118%), but
lower tensile strength (32%), M100 (43%), and hardness
(11%). This is due to weaker filler–filler interactions in
rubber compounds filled with lignin as shown by the
Payne effect results (Table 4). As discussed in the mor-
phology section, cellulose has lower compatibility with
NR than lignin. Therefore, the tensile strength reduction
by replacing CB with cellulose is more important com-
pared to lignin. On the other hand, at the same filler con-
tent, the addition of cellulosic fillers results in higher
M100 and hardness than does the lignin samples addition
due to higher filler-filler interactions (Figure 8). For
example, L40 shows 231% and 295% higher tensile
strength and elongation at break, but 49% and 18% lower
M100 and hardness compared to C40, respectively.
4 | CONCLUSION
In this study, the effect of two lignocellulosic fillers on
the properties of NR composites was investigated. In the

KAZEMI ET AL.
first part, cellulosic pulps with different lignin/cellulose
(L/C) ratios were prepared using black spruce sawdust as
a starting material by chemical (organosolv) pulping to
partially replace CB for a typical NR compound (total
filler content of 40 phr). The results showed that using
cellulosic material with a higher L/C ratio led to longer
curing time (up to 8%), but lower maximum torque
(down to 9%). Furthermore, using higher L/C ratio
resulted in higher tensile strength and elongation break,
but lower tensile modulus and hardness. For example,
the tensile strength and elongation at break of A2/NR
(L/C = 3.3) are 12% and 6% higher than A7/NR
(L/C = 0.2), while the M100 and hardness are 19% and
4% lower. All the results indicate that a balance between
rigidity and elasticity can be achieved by simply control-
ling the L/C ratio depending on the final application.
In the second part, purified industrial cellulose and lig-
nin were used to fully replace CB in the rubber compound.
The results showed that replacing CB with both cellulose
and lignin increased the curing time, but decreased the
maximum torque. In addition, CB replacement by cellulose
increased the tensile modulus (up to 13%) and hardness
(up to 9%), but decreased the tensile strength (down to
79%). On the other hand, replacing CB by lignin generated
higher tensile strength and elongation at break, but lower
tensile modulus and hardness compared to cellulose-filled
composites. For instance, the composite filled with 40 phr
lignin showed 231% and 295% higher tensile strength and
elongation at break, but 49% and 18% lower M100 and
hardness compared to 40 phr cellulose.
All the results presented indicate that fully biobased
biocomposites using NR and lignocellulosic reinforce-
ment are interesting, but more work is needed to opti-
mize the formulation and the processing conditions
depending on the final application. Also, decoupling the
effect of particle size/geometry and chemical composition
must be further studied to fully understand all the inter-
actions involved in these complex compounds.
A C K N O WL E D G M E N T S
The authors would like to acknowledge Camso (Canada)
and the Natural Sciences and Engineering Research
Council of Canada (NSERC) for their financial support,
as well as the research center on advanced materials
(CERMA) for technical support.
A U T H O R C ON T R I B U T I O NS
Hossein Kazemi: Formal analysis (lead); investigation
(lead); methodology (equal); writing – original draft
(lead). Maxime Parot: Resources (supporting); validation
(supporting); writing – review and editing (supporting).
Tatjana Stevanovic: Resources (supporting); validation
(supporting); writing – review and editing (supporting).
10974628, 2022, 26, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.52462 by UFMS - Fundacao Universidade Federal de Mato Grosso do Sul, Wiley Online Library on [13/12/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
13 of 14
Frej Mighri: Funding acquisition (supporting); supervi-
sion (supporting); writing – review and editing (equal).
Denis Rodrigue: Conceptualization (lead); data curation
(lead); funding acquisition (lead); project administration
(lead); resources (lead); supervision (lead); validation
(lead); writing – review and editing (lead).
DA TA AVAI LA BI LI TY S T ATE ME NT
The data that support the findings of this study are avail-
able from the corresponding author upon reasonable
request.
ORCID
Denis Rodrigue https://orcid.org/0000-0002-3969-2847
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SU PP O R TI N G I N F O RMA TI O N
Additional supporting information may be found in the
online version of the article at the publisher's website.
How to cite this article: H. Kazemi, M. Parot, T.
Stevanovic, F. Mighri, D. Rodrigue, J. Appl. Polym.
Sci. 2022, 139(26), e52462. https://doi.org/10.1002/
app.52462