polymers

Article
Valorisation of Underutilized Grass Fibre (Stem) as a Potential
Material for Paper Production
Chuan Li Lee 1 , Kit Ling Chin 1, *, Paik San H’ng 1,2, *, Mohd Sahfani Hafizuddin 1 and Pui San Khoo 3

1 Institute of Tropical Forestry and Forest Products, Universiti Putra Malaysia, Serdang 43400, Malaysia
2 Faculty of Forestry and Environment, Universiti Putra Malaysia, Serdang 43400, Malaysia
3 Centre for Advanced Composite Materials, Universiti Teknologi Malaysia, Johor Bahru 81310, Malaysia
* Correspondence: c_kitling@upm.edu.my (K.L.C.); ngpaiksan@upm.edu.my (P.S.H.)

Abstract: An integrated and feasible approach was proposed using the underutilized grass fibre
(stem) derived from Napier grass and sugarcane for paper production in this study. To enhance
paper strength, pre-hydrolysis and beating techniques have been used to improve the chemical
pulps and mechanical pulping process, respectively. Napier grass and sugarcane are promising
non-wood sources for pulp production, owing to their high cellulose and low lignin and extractive
content. With the additional mild alkaline pre-treatment to the mechanical pulping process, the lignin
content was greatly reduced. The results reveal that the mechanical pulping with alkaline pre-
treatment may indeed potentially replace the most prevalent pulping process (chemical pulping). As
evidenced by the paper strength properties, mechanical pulping is far more suitable for grass-type
biomass, particularly Napier grass, which had a folding endurance capability five times greater than
chemical pulping. Furthermore, the remaining high hemicellulose content from mechanical pulping
contributed to a high pulp yield, while also facilitating the fibrillation on the sugarcane’s laboratory
paper handsheet. The findings also demonstrated that the additional beating process from chemical
pulping causes the fibres to be drawn toward each other, resulting in a more robust fibre network that
contributes to good paper strength. Consequently, this work sheds new light on the development of
Citation: Lee, C.L.; Chin, K.L.; H’ng,
advanced paper derived from grass fibre.
P.S.; Hafizuddin, M.S.; Khoo, P.S.
Valorisation of Underutilized Grass
Fibre (Stem) as a Potential Material
Keywords: Napier grass; sugarcane; grass fibre; chemical pulping; mechanical pulping; alkaline
for Paper Production. Polymers 2022, pre-treatment; beating
14, 5203. https://doi.org/10.3390/
polym14235203

Academic Editor: Ana Paula Costa

1. Introduction
Received: 17 October 2022 Grasslands are among the most common types of covered vegetation, accounting for
Accepted: 23 November 2022 more than 31.5% of the world’s land mass. It is one of the sustainable resources and provides
Published: 29 November 2022 a significant portion of livestock with a food source [1]. Among all the grasses, Napier grass
Publisher’s Note: MDPI stays neutral (Pennisetum purpureum) is a fast-growing monocot grass in the Poaceae family of which is
with regard to jurisdictional claims in morphologically stout, tall, and a deep-rooted perennial bunchgrass, primarily propagated
published maps and institutional affil- by stem cutting [2–4]. Owing to its high productivity and nutritive value, Napier grass
iations. is currently the most popular fodder grass in dairy and feedlot production systems in
Malaysia [5,6]. This grass is productive, easy to cultivate, drought-tolerant, and adaptable
to a variety of soil and climatic conditions, particularly in tropical soils. The wildlife
department of Sabah state even cultivated Napier grass for grazing as part of efforts to
Copyright: © 2022 by the authors. minimize human–animal conflict and crop destruction [7]. Given its high cellulose content,
Licensee MDPI, Basel, Switzerland. Napier grass has the potential to produce biofuels such as alcohol, ethanol, butanol, and
This article is an open access article
methane [8,9]. In addition, another fascinating grass which is currently used as primary raw
distributed under the terms and
material for biofuel products is the giant grass known as sugarcane (Saccharum officinarum).
conditions of the Creative Commons
Sugarcane is distinct from other types of grass in that it can store vast amounts of sugar
Attribution (CC BY) license (https://
as sweet juice in its fibrous stalk/stem. Sugarcane ethanol is produced from sugarcane
creativecommons.org/licenses/by/
fermentation and can effectively be used as an ethanol-gasoline blend or as a 100% pure
4.0/).

Polymers 2022, 14, 5203. https://doi.org/10.3390/polym14235203 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, 5203 2 of 18

ethanol fuel in spark ignition engine vehicles. The favourable climate and agricultural
capabilities of Malaysia enable the production of a high yield of sugarcane, which opens
up the possibility of an alternative fuel source [10].
Aside from the biofuel implementation programme, Malaysia is in an urge to start
introducing green and sustainable pulping processes, and grass fibre-based paper products
may sound promising. In recent years, there have been some major breakthroughs in
Malaysia’s papermaking industry with the use of oil palm biomass in two notifiable
companies producing pulp and paper products from empty fruit bunch fibres [11,12].
However, Malaysia is still highly dependent on the imports of pulp to meet the domestic
demand of paper products. Wood is the primary source of cellulose fibre used in the paper
industry in Malaysia, with 80% of the virgin pulp imported [13]. Due to a recent global
shortage of woody products, pulp supplies have been one of the major issues in the paper
industry [14]. Thus, the use of non-wood fibres that can be processed into pulp with less
chemicals or energy input is a promising cost-effective strategy in producing pulp and
paper. Napier grass and sugarcane have two primary parts in terms of structure—the leaf
and the stem. Due to its high protein content, nutrition, and desirable texture, the Napier
grass leaf is suitable for use as animal fodder (e.g., softness). The stem, on the other hand,
is underutilized due to its hardness, high density, and high lignin content [15,16]. In the
case of sugarcane, the dry pulpy residue left after extracting juice from the stem was also
underutilized as well. The valorisation of all this underutilized biomass via a pulping
process could be the solution to an enhanced biomass conversion.
Paper pulp can be divided into two types based on the pulping method used: chemical
pulp and mechanical pulp. Chemical pulp is made using the chemical pulping process,
whereas mechanical pulp is made using the mechanical pulping process. Mechanical
pulping is appealing to pulp producers because it is less expensive and easier to implement
than chemical pulping [17]. To improve the efficacy of fibrillation, the fibre may be pre-
softened by heat prior to mechanical pulping, known as thermo-mechanical pulping.
Despite the fact that thermo-mechanical pulping is a mainstay of the pulping industry,
thermo-mechanical pulping mills face a number of challenges as a result of rising electricity
costs and a push to reduce greenhouse gas emissions [18]. The pulp and paper industry
is one of the world’s largest users of energy and water. The paper and pulp industry
was reported as the fourth largest emitter of greenhouse gases in the manufacturing
sector of the United States of America. It was also reported in India that this industry
produces approximately 100 million kg of hazardous pollutants annually [19]. Common
solid pollutants include wood waste, sodium salts from the recovery boiler, pulp screening
rejects, dregs, and grit from causticizing plants [20,21]. Researchers in the pulp and paper
sector are always in an effort to improve the pulping technique, with an emphasis of
not only to replace wood resources as a raw material, but also to provide insights into
environmental practices that can move beyond the conventional pulping methods.
Malaysia’s paper consumption is growing steadily, putting a large and constant de-
mand on the supply of fibres for pulp and paper production. At this juncture, with the
fascinating characteristics such as abundance volume, a short cycle growth, and environ-
mental friendliness, grass fibres may act as a great alternative to replace wood fibres. We
believe that the advanced pulping technique will enable grass-type fibre to be a game
changer in the pulp and paper industry. To fully comprehend the potential of grass fibre
(stem) for pulp and paper production, chemical and mechanical pulping were applied to
two grass-type biomasses, Napier grass and sugarcane stem. The characteristics for both
grass fibres’ laboratory paper handsheets produced using varying pulping techniques were
also evaluated. The strength of the paper made from grass fibre presents another challenge
in the production of paper. Pre-hydrolysis techniques and beating techniques have been
used to improve chemical pulps and the mechanical pulping process, respectively. Thus,
this research will also investigate into the efficacy of pulp and fibre modification via the
beating process on chemical pulping and alkaline pre-treatment on mechanical pulping.
Polymers 2022, 14, 5203 3 of 18

2. Materials and Methods

2.1. Raw Materials Preparation
Samples of Napier grass and sugarcane were supplied by Regu Yakin Sdn. Bhd.
(Pahang, Malaysia). Both plants were propagated vegetatively through stem cuttings in
Pahang. The Napier grass and sugarcane were harvested after 4 and 6 months, respectively.
The harvested Napier grass stems were washed before being dried in a forced-air drying
oven at 60 ◦ C overnight, whereas the sugarcane stems were collected and dried after the
sugar extraction process. The dried stems were then chipped using a chipper machine
(PZ 8, Pallmann Maschinenfabrik GmbH & Co, Zweibrücken, Germany) and screened to a
width of approximately 2 cm to enable better chemical penetration during pulping. The
samples were then air-dried to 10% moisture content (storage) prior to pre-treatment.

2.2. Pulping Process

2.2.1. Mechanical Pulping
The fibres were pre-treated by being fully immersed in a 3% sodium hydroxide (NaOH)
solution with a solid-to-liquid ratio of 1:10. The impregnation process was held for 24 h.
The fibres were then washed with tap water for approximately 30 min, or until the soapy
condition diminished. The Refiner Mechanical Pulper (RMP) machine (Andritz Sprout
Bauer, Muncy, PA, USA) with 1/65-inch disc gap was used to refine the washed fibres. The
refining process was carried out with the disc plate gaps set at 2.5 mm between the refining
plates. The two-cycle refining process was designed to reduce the negative impact of the
plates’ harsh actions on the fibres. The wet fibres were manually squeezed after refining to
remove the water.

2.2.2. Chemical Pulping (Kraft Pulping)

Table 1 summarises the chemical pulping conditions for Napier grass and sugarcane
stem. The chemical pulping was carried out using Twin Digester (MK Twin Tub Digester,
model GTD-15L, GIST Co Ltd., Korea). Both mechanical and chemical pulping machines
were provided by the Institute of Tropical Forestry and Forest Products (INTROP), Univer-
siti Putra Malaysia, Selangor, Malaysia. Notably, the entire chemical pulping process was
in a closed system.

Table 1. Pulping condition for the Napier grass and sugarcane.

Pulping Condition Chemical Pulping

Weight of sample 300 g
Sulphidity 25.0%
Active alkali 17% 17%
Fibre: liquor 1:7
Temperature during cooking 170 ◦ C
Time to maximum temperature 60 min
Time at maximum temperature 120 min

2.3. Screening
Prior to screening, these pulps were dispersed in a Hydropulper (Sheng Feng, Henan,
China). The pulps were screened using PTI Sommerville Fractionators with 0.30 mm slots.
The oversized debris particles from the stem pulp were removed via screening.

2.4. Spin Drying

Both types of pulps were spin-dried to remove residual water using a spinning ma-
chine. The screened pulps were spin-dried for 5–10 min in a fabric bag. After the spinning
process was completed, the pulps were weighed to determine the pulp yield percentage.
Finally, the pulp was stored in a freezer at 6 ◦ C. A specific weight of the pulp was placed in
an oven to dry at 105 ◦ C overnight to establish the oven-dry mass. The screened pulp yield
was calculated using the formula:
Polymers 2022, 14, 5203 4 of 18

Oven dry mass o f pul p

Pulp yield (%) = × 100 (1)
Initial oven dry mass o f wood chips

2.5. Laboratory Handsheet Making Process

Beaten samples were prepared in accordance with standard condition TAPPI T 248
sp-00 [22]. A total of 500 revolutions were used as the beating degree. A specified mass
of Napier grass and sugarcane (beaten and unbeaten pulp) were fiberized in a disinte-
grator at room temperature and 10% consistency for 20 min using a laboratory PFI mill
machine. Finally, laboratory paper handsheet production was conducted using a laboratory
handsheet machine based on the TAPPI Standard, T 205 sp-02 [23] to produce 60 g/m2 of
laboratory paper handsheets. Before any evaluation, these laboratory paper handsheets
were conditioned for 24 h at a temperature of 23 ◦ C ± 1 ◦ C and 50% ± 2% relative humidity.

2.6. Evaluation
2.6.1. Chemical Composition
The chemical composition of the raw materials and produced pulps from Napier grass
and sugarcane stems were determined according to TAPPI standard. All experiments were
carried out in five replicates to obtain an accurate result.

Extractives
The extractive content of the sample was determined according to TAPPI T 204 cm-
97 standard. The ethanol-acetone solution was prepared by a mixture of approximately
95% ethyl alcohol and acetone as a reagent in the ratio of 3:1. A sufficient amount of the
sample equivalent to 2 g of the powder of CS and PKS was weighted separately and placed
into the thimble. The thimble with the sample was then placed in a dry Soxhlet extraction
apparatus. The extraction flasks were then filled with 200 mL of the ethanol-acetone
solution. The flasks were connected to the extraction apparatus with water flowing to the
condenser section. The heater was set to 100 ◦ C and the boiling process took around 4 to
5 h. After the extraction process, the solution was dried using a desiccator and further
dried in an oven for 24 h before the extraction content was calculated. The percentage of
extractive in lignocellulosic biomasses was calculated as follows:
Weight o f f lask (g) + Extraction − Weight o f f lask (g)
% of Extractive = × 100 (2)
ODW sample (g)
Weight o f air dried sample (g) − Weight o f crucible (g)
ODW = (3)
100

Lignin Content
The lignin content of samples was determined according to TAPPI T 222 om-98
standard. Approximately 1 g of oven-dried extraction free sample (Napier grass and
sugarcane stem) was added into a beaker with 2% H2 SO4 . The mixture was occasionally
stirred in a water bath at room temperature and rested for 2 h to ensure a complete
dissolution occurred. The solution was then added into distilled water until the total
volume of 575 mL. The mixture was then boiled for 4 h by maintaining a constant volume
using a reflux condenser. After boiling, the solution was filtered with the aid of a suction
machine and washed using hot water. The lignin residue was dried for 1 h at 110 ◦ C and
then allowed to cool in a desiccator. The percentage of lignin was calculated as follows:
W4 − W3
% of Lignin = × (100 − W1 ) (4)
100 × W2
where,
W1 = alcohol-acetone extractive content, %;
W2 = weight the of oven-dried extractive-free sample, g;
W3 = weight of oven-dried crucible, g;
Polymers 2022, 14, 5203 5 of 18

W4 = weight of oven-dried residue and crucible, g.

Holocellulose
A total of 2 g of the residue from the ethanol-acetone extraction was placed into a
250 mL beaker and closed with a watch glass. The specimen was added with 100 mL of
distilled water, 1.5 g of sodium chlorite, and 5 mL of 10% acetic acid. The beaker was
placed in a hot water bath or on a hot plate maintained at 70 ◦ C; the contents were swirled
vigorously once every 5 min. The flask was kept closed with a small, inverted Erlenmeyer
flask. The whole experiment was carried out in a fume hood. After 30 min, 5 mL of
10% acetic acid was added. After 30 min, 1.5 g of sodium chlorite was additionally added
on and acetic acid and sodium chlorite were continued until 6 g of sodium chlorite was
incorporated in the solution. Then, the mixture was heated for 30 min after the last addition
of sodium chlorite. The suspension was cooled in an ice bath. It was filtered into a weighed
fruited glass crucible and washed with iced distilled water. Finally, it was washed with
acetone. The residue was air dried for one to two days until it was free of acetone and
covered by perforated aluminium foil. It was transferred to a desiccator and weighed at
daily intervals until the sample reached a constant weight. The percentage of holocellulose
was calculated as follows:
W4 − W3
% of Holocellulose = × (100 − W1 ) (5)
100 × W2
where,
W1 = alcohol-acetone extractive content, %;
W2 = weight of oven-dried extractive-free sample, g;
W3 = weight of oven-dried crucible, g;
W4 = weight of oven-dried residue and crucible, g.

Alpha-Cellulose
The cellulose content in both samples were carried out according to TAPPI 203 stan-
dard using 8.3 and 17.5% NaOH and 2 N of acetic acid (CH3 CO2 H). A total of 2 g of the
sample was put into a 250 mL beaker. Then, 15 mL of 17.5% NaOH was added and gently
macerated with a flattened glass rod for 1 min. A total of 10 mL NaOH was further added
into the solution and stirred for 45 s, then 10 mL of NaOH was added and stirred for 15.
The mixture was stirred and allowed to stand for another 3 min. A total of 10 mL of NaOH
was added and mixed with a stirring rod every 21/2 min. These steps were repeated for
three times until the total time reached 15 min. The beaker was covered with a watch glass
and the mixture was left in a water bath for 30 min. Then, 100 mL of distilled water was
added quickly at 20 ◦ C and thoroughly mixed, and the diluted mixture was left in the water
bath for a further 30 min. The mixture was filtered into a weighed fruited glass crucible
with coarse porosity. The beaker and residue were rinsed with 25 mL of 8.3% NaOH and
650 mL of distilled water. Then, the residue was rinsed with 2N CH3 CO2 H and rinsed
again with distilled water. The crucible was placed in the oven at 105 ◦ C. The α-cellulose
was calculated as a percentage, as shown in Equation (5). The amount of hemicellulose was
calculated by subtracting alpha-cellulose from holocellulose.
W4 − W3
% of Alpha − cellulose = × W1 (6)
100 × W2
where,
W1 = Holocellulose content, %;
W2 = weight of oven-dried holocellulose sample, g;
W3 = weight of oven-dried crucible, g;
W4 = weight of oven-dried residue and crucible, g.
Polymers 2022, 14, 5203 6 of 18

2.6.2. Laboratory Handsheet Properties Determination

Laboratory paper handsheets were examined in terms of their physical, mechanical,
and optical properties. To ensure the uniform distribution of Napier and sugarcane stem
fibres, the pulp slurry was disintegrated using a Pulp Disintegrator (Regmed DSG 200) at
25,000 rpm before the production of laboratory paper handsheets. All results in this study
were expressed as mean ± standard deviation of three replicates. The sample was prepared
with the required testing size in accordance with the relevant standard, and the following
parameters were evaluated:
(a) The bursting test was performed by bursting strength tester (GT-7013-ADP) according
to TAPPI T403 om-02 [24].
(b) The opacity test was performed by Technidyne Brightimeter (Micro S-5) according to
TAPPI Standard, T 425 om-01 [25].
(c) The brightness test was performed by Technidyne Brightimeter (Micro S-5) according
to TAPPI T425 Om-02 [26].
(d) The tensile test was performed by a universal testing machine (UTM Twin Column
Lyod 2.5 kN) according to TAPPI Standard, T 494 om-01 [27].
(e) The tearing test was performed by Elmendorf ProTear Tester (Thwing-Albert) accord-
ing to TAPPI Standard, T 414 om-98 [28].
(f) A morphological observation of the laboratory paper handsheet.
(g) The morphological properties of handsheets were observed via Scanning Electron
Microscopy (SEM) (Hitachi S-3400N and Jeol JXA 840A) under an accelerating voltage
of 15 kV. Before scanning, samples were coated with gold using a sputter coater
system (Edwards Sputter Coater; BOC Edwards, Crawley, West Sussex, UK) to obtain
an excellent image by avoiding any charging effect.

2.7. Statistical Analysis

Statistical analyses were conducted using the statistical package SPSS for Windows,
version 16.0 (SPSS, Chicago, IL, USA), which was used to evaluate the adsorption property
data of the laboratory paper handsheet properties for analysis of variance (ANOVA) at a
95% confident level (p ≤ 0.05). Results were analysed using one-way ANOVA, followed
by Tukey’s test as a post hoc test [29]. The Tukey–Kramer multiple comparisons test was
applied to analyse the differences between the treatment effects when significance was
observed. The effects were considered to be not statistically significant when the p-value
was higher than 0.05 at the 95% confidence level.

3. Result and Discussion

3.1. Chemical Composition Analysis
Table 2 summarizes the contents of cell wall structural constituents (cellulose, hemicel-
luloses, and lignin) in Napier grass, sugarcane biomass, and pulp obtained. Despite their
high ash content, both biomasses are ideal for pulping, owing to their low lignin content.
According to Kontturi et al. [30], cellulose is the primary structural component of plant cells.
As shown in Table 1, both biomasses have a high α-cellulose content, which has the poten-
tial to result in high pulp fibre yields. Sugarcane contains a higher ash content than Napier
grass (refer to Table 1). The use of non-wood as a pulping raw material in conventional
processes is limited by the presence of high silica levels [31]. The chemical analysis also
revealed that both biomasses had a low extractive content. Materials with a low extractive
value are more likely to generate a high yield during the cooking process [32]. A chemical
composition comparison reveals a significant difference between the raw fibre and the
obtained pulp. The obtained pulp contained more cellulose, while other content, particu-
larly lignin content, was highly removed. The disruption of lignin–carbohydrate complex
(lignin-hemicelluloses) linkages during the alkaline treatment significantly reduced the
lignin and hemicellulose content [33] from both of the grass-type fibres.
Polymers 2022, 14, 5203 7 of 18

Table 2. Chemical composition analysis of biomass and pulp obtained.

Type of Pulping Lignin α-Cellulose Hemicellulose Extractive Ash Content

Biomass Technique (%) (%) (%) (%) (%)
Raw Fibre 21.77 (0.07) 46.58 (0.23) 31.04 (0.05) 3.42 (0.00) 4.16 (0.10)
Napier grass Chemical Pulping 3.31 (0.01) 89.42 (0.16) 3.38 (0.12) 1.18 (0.01) 1.31 (0.00)
Mechanical Pulping 11.21 (0.02) 73.97 (0.08) 11.76 (0.02) 1.98 (0.02) 2.56 (0.01)
Raw Fibre 22.32 (0.00) 40.34 (0.02) 33.39 (0.01) 3.95 (0.00) 8.27 (0.00)
Sugarcane Chemical Pulping 2.76 (0.01) 87.98 (0.01) 3.56 (0.00) 1.30 (0.01) 4.52 (0.01)
Mechanical Pulping 9.67 (0.00) 74.09 (0.01) 12.92 (0.00) 2.34 (0.00) 2.81 (0.00)
Note: The values in parentheses are the standard deviation of the mean values.

Undoubtedly, a higher lignin content necessitates a large amount of energy and

chemicals [34]. The presence of lignin is detrimental to the stability of chemical and
mechanical paper properties [35]. It was even necessary to bleach for some applications.
The lignin content of Napier grass is 21.77% and that of sugarcane is 24.32%, both of which
are low, implying that both biomasses ought to be fairly easy to pulp than wood with a
lignin content of 26–30%. Furthermore, biomass fibre with a low lignin content is easier
to delignified and requires milder and faster cooking conditions [36]. With the additional
mild NaOH pre-treatment to the mechanical pulping process, the lignin content was greatly
reduced. Ultimately, the high cellulose and low lignin and extractive content of non-wood
resources of Napier grass and sugarcane stem qualify them as promising raw materials for
pulp production. This result is benefitted by using low-cost biomass and, more notably,
environmentally benign pulping processes (with mild chemical usage from the mechanical
pulping process), which could be the new market trend for the pulping industry.

3.2. Yield of Pulp

The pulp yield for Napier grass and sugarcane stem are illustrated in Figure 1. Sug-
arcane has a higher yield than Napier grass due to the presence of more hemicelluloses.
Higher hemicellulose content appears to improve the pulp yield [37]. Xylan, which makes
up approximately 24–25% of the main hemicellulose in the sugarcane holocellulose struc-
Polymers 2022, 14, x FOR PEER REVIEW 8 of 18
tures, is important because it contributes to increase pulp yield [38]. In comparison to
chemical pulping, mechanical pulping offers a higher pulp yield. Table 2 shows that the
chemical pulping process led to a significant delignification effect on both samples. The
demonstrated
removal to be
of lignin anda carbohydrates
more environmentally
may leadfriendly method decrease
to a significant that helpsinto produce
pulp yield a[39].
la-
boratory
Since paper
a higher handsheet
yield that degrades
was obtained, naturally
it is evident and lowers
that mechanical the levels
pulping of pollution
is preferable as it
worldwide
will increasethrough this study.
the producer’s profit margin.

Total Pulp Yield

40

30
Yield (%)

20

10

0
Napier grass Sugarcane

Chemical pulping Mechanical pulping

Figure 1.
Figure 1. Pulp
Pulp yield
yield of
of the
the Napier
Napier grass
grass and
and sugarcane
sugarcane stem.
stem.

3.3. Mechanical Properties

Table 3 summarizes the laboratory handsheet properties derived from Napier grass
and sugarcane stem. The Tukey–Kramer multiple comparisons test was applied to analyse
Polymers 2022, 14, 5203 8 of 18

Mechanical pulping uses less chemicals than chemical pulping. Chemical activity
devalues and solubilizes biomass components, primarily lignin and hemicellulose, resulting
in lower pulp yield and lignin content [40]. Furthermore, chemical pulping necessitated
the recovery of chemicals from spent cooking liquor, the recovery of heat energy from
the heating of recovered lignin and other organic materials from the black liquor, and
the reduction in air and water pollution [41]. The mechanical pulping process has been
demonstrated to be a more environmentally friendly method that helps to produce a
laboratory paper handsheet that degrades naturally and lowers the levels of pollution
worldwide through this study.

3.3. Mechanical Properties

Table 3 summarizes the laboratory handsheet properties derived from Napier grass
and sugarcane stem. The Tukey–Kramer multiple comparisons test was applied to analyse
the differences between the treatment effects when significance was observed. The ANOVA
analysis revealed significant effects (p < 0.01) for the type of biomass, pulping technique,
and the interaction of the two factors.

Table 3. Mechanical properties of characterization of a laboratory paper handsheet derived from

Napier grass and sugarcane stem.

Type of Pulping Burst Tensile Test Tear Index

Folding Test
Biomass Technique (Lbf/cm2 ) (KNm/g) (Mn)
Chemical
23 cd 5.7169 d 15.4624 c 286.4880 d
Pulping
Chemical and
Napier Grass 46 b 7.1414 c 28.5712 a 396.8563 b
Beating
Mechanical
106 a 8.3044 a 19.3793 c 363.9777 c
Pulping
Chemical
8e 6.9662 c 17.2697 c 259.3740 d
Pulping
Chemical and
Sugarcane 14 de 7.7335 b 23.7757 b 426.9640 a
Beating
Mechanical
37 cd 8.7850 a 19.1720 c 373.6127 bc
Pulping
p-value <0.001 <0.001 <0.001 <0.001
Note: Means followed by the same letter (a–e) in the same column are not significantly different at p ≤ 0.05
according to Tukey’s multiple comparisons test.

Table 3 depicts the mechanical properties of a laboratory paper handsheet made

from Napier grass and sugarcane stem using various pulping techniques. This study
found that a laboratory paper handsheet derived from mechanical pulping outperforms
chemical pulping in terms of folding endurance. Folding endurance is an empirical test that
determines how many folds a piece of laboratory paper handsheet can withstand before
its tensile strength drops below a certain level [42]. The result reveals that mechanical
pulping remarkably enhanced the folding endurance of the laboratory paper handsheets
from these two types of biomass, particularly Napier grass, for which mechanical pulping
is five times better than chemical pulping. Throughout, in regard to folding properties,
chemical pulping had lower tensile, tear, and burst indexes than mechanical pulping.
Chemical pulping was the most widely used method in the pulp and paper industry.
However, the currently used chemical pulping procedures are primarily adapted from
wood pulping; with this procedure, the operating mills face difficulties accepting other
raw materials such as grass-type biomass [43]. Many published researches have stated the
distinct advantages of mechanical and chemical pulping, with mechanical pulp providing
paper with higher bulk properties, while chemical pulp provides paper with higher tensile
stiffness [44]. Nonetheless, the results from this study show that the tensile strength of both
Polymers 2022, 14, 5203 9 of 18

grass-type laboratory paper handsheets prepared by chemical pulping is extremely low

compared to laboratory paper handsheets from mechanical pulping. The tensile strength
of laboratory paper handsheets derived from chemical pulping was increased with the
additional beating process. With an additional beating treatment, the tensile strength of
laboratory paper handsheets derived from chemical pulping was doubled. This could
be due to the fact that tensile strength is primarily affected by inter-fibre bonding force
and fibre strength, and beating clearly promoted inter-fibre bonding [45,46]. Furthermore,
improved fibrillation induced by the beating process may also lead to improved fibre
conformability, resulting in a stronger fibre network structure [47].
The results demonstrate that laboratory paper handsheets made from both unbeaten
pulps have a low tearing resistance. Unbeaten pulp commonly has poor inter-fibre contacts
during the laboratory paper handsheet formation, which results in poor laboratory paper
handsheet properties. Beaten pulps have highly improved the mechanical properties of
laboratory paper handsheet specimens significantly. The enhancement is also ascribed to
the increase in the bonded area of the sheet, resulting from internal and external fibrillation
that occurs during beating. Inter-fibre bonding is crucial to sheet strength because it is
determined by two factors: the strength of an individual fibre and the inter-fibre bonds.
They make a significant contribution to the internal cohesion of paper. As inter-fibre
bonding strengthens, it is more likely that a fibre in the path of an advancing tear will be
severed rather than pulled out. Additionally, all the while, stress is concentrated at the apex
of the tear and is challenging to share with the rest of the structure [44,48,49]. Defibrillation
and delamination occur during the beating process, resulting in an increased fibre surface
area, improved contact quality, and flexibility [50]. Respectively, fibre flexibility increases
the number of bonds required to provide the bonding area, resulting in a larger surface area
for bonding [51,52]. Because of internal and external fibrillation, the development of fibre
surfaces for bonding may be enhanced during the beating of chemical pulp. Since the good
inter-fibre contact was created by the beating process, the laboratory paper handsheets can
withstand more stress before tearing.
The amount of hydrostatic pressure applied to a circular sample area is defined as
bursting strength. It indicates the resistance of the laboratory paper handsheet to rupturing,
and laboratory paper handsheet with a low burst strength cannot easily retain packed
goods and tears [53]. Besides, the bursting strength also determined the capability of
packaging when it was subjected to stacking, collapsing, striking, tearing, and squeezing,
all of which were greatly improved multiple times in both dry and wet states [54]. This
study reveals that fibre obtained directly from pulping is simply inadequate for laboratory
paper handsheet production. They must first be refined through the beating process or the
alkaline pre-treatment. The burst strength resistance of the laboratory paper handsheets
improved with the beating process and mechanical refining process. The knife-edges or
bars in the refiner or beater abrade and fibrillate the fibres. Mechanical squeezing and
pounding of cellulose fibre allow water to penetrate its structure, causing swelling and
making the fibre more flexible. The pulp fibres are separated, crushed, frayed, fibrillated,
and cut during refining or beating. They absorb water and expand, becoming more flexible
and pliable. Their ability to bond with one another after drying is greatly enhanced, partly
due to the modification of the fibre surfaces and partly due to the creation of the new surface
area, which increases the fibre-to-fibre bonding during the laboratory paper handsheet-
making process [55]. Remarkably, the results indicate that mechanical pulping is best suited
for grass-type biomass because it can achieve higher strengths than the most conventional
pulping methods, such as chemical pulping for paper production.

3.4. Optical Properties

Figures 2 and 3 had shown the optical properties (brightness and opacity) of the
laboratory handsheet made from Napier grass and sugarcane stem. The Tukey–Kramer
multiple comparison test was employed to determine the interaction among the indepen-
dent variables.
 conventional pulping methods, such as chemical pulping for paper production.
conventional pulping methods, such as chemical pulping for paper production.
3.4. Optical Properties
3.4. Optical Properties
Figures 2 and 3 had shown the optical properties (brightness and opacity) of the la-
Figureshandsheet
boratory 2 and 3 had shown
made theNapier
from opticalgrass
properties (brightnessstem.
and sugarcane and opacity) of the la-
The Tukey–Kramer
Polymers 2022, 14, 5203 boratory handsheet made from Napier grass and sugarcane stem. The 10 of 18
Tukey–Kramer
multiple comparison test was employed to determine the interaction among the inde-
multiple
pendentcomparison
variables. test was employed to determine the interaction among the inde-
pendent variables.

Brightness Properties
Brightness Properties
50%
50%
a a a
40% a a a
Brightness Value (%)

a a
40%
Brightness Value (%)

30%
30%
b b
b b
20%
20%

10%
10%

0%
0%
Chemical Chemical & Mechanical Chemical Chemical & Mechanical
Chemical Chemical & Mechanical Chemical Chemical & Mechanical
Beating Beating
Beating Beating
Napier grass Sugarcane
Napier grass Sugarcane

Figure 2. Brightness values of produced laboratory paper handsheets. Means followed by the same
Figure
Figure 2. Brightness
2. Brightness values
values of of produced
produced laboratory
laboratory paper
paper handsheets.
handsheets. Means
Means followed
followed byby
thethe same
same
letter (a, b) in the same column are not significantly different at p ≤ 0.05 according to Tukey’s multi-
letter (a,(a,
letter b)b)
inin
the
thesame column
same columnarearenot
notsignificantly
significantlydifferent at pp ≤≤0.05
differentat 0.05according
accordingtotoTukey’s
Tukey’s multi-
multiple
ple comparisons test.
plecomparisons
comparisonstest.test.

Opacity Properties
Opacity Properties
100% a
100% ab b a
ab b b
b
80%
80% c
Opacity value (%)

c c
Opacity value (%)

c
60%
60%

40%
40%

20%
20%

0%0%
Chemical
Chemical Chemical
Chemical & & Mechanical
Mechanical Chemical Chemical
Chemical Chemical
& & Mechanical
Mechanical
Beating
Beating Beating
Beating
Napier
Napier grass
grass Sugarcane
Sugarcane

Figure 3. Opacity values of produced laboratory paper handsheets. Means followed by the same
letter (a–c) in the same column are not significantly different at p ≤ 0.05 according to Tukey’s multiple
comparisons test.

Figures 2 and 3 illustrate the Tukey-Kramer multiple comparisons test, which was
used in this study to classify various mean levels of brightness and opacity for six different
laboratory paper handsheets. The ANOVA analysis revealed significant effects (p < 0.01)
for biomass type, pulping technique, and the interaction of the two factors. It clearly shows
that the laboratory handsheets made from mechanical pulp had the lowest brightness
and opacity. The low value for both opacity tests on the mechanical laboratory paper
handsheet was due to the fact that the majority of the original lignin in the raw pulp
was still present [56]. The lignin substrate contains many chromophore groups, such
as quinoids, catechols, aromatic ketones, stilbenes, conjugated carbonyls with phenolics,
and metal complexes, and some additional chromophores within paper can be oxidised
Polymers 2022, 14, 5203 11 of 18

from leucochromophores and remnant carbohydrates [57–61]. Chromophores are coloured

substances with a high degree of stability that reduce brightness in pulp and fibre [62,63].
The goal of mechanical pulping is to achieve a high yield with high strength properties.
Although the lignin may cause the mechanical pulp to turn yellow with exposure to air and
light, they are less expensive to produce and yield a higher pulp content [64]. Furthermore,
mechanical pulp can be used without bleaching to produce printing papers for applications
where low brightness is acceptable, such as newsprint.
A new discovery was made in this current study, as there is a growth in tensile strength
but a reduction in the opacity of laboratory paper handsheets from chemical pulping. As
stated by [65], laboratory paper handsheets with a high light scattering coefficient indicate
small bonding areas. The breaking length, which expresses tensile strength, increases
linearly as bond strength per unit area and relative bonded area increase. As a result,
enhancing the surface area through the beating process is a crucial method for improving
the bonding strength of the fibre and forming a fibrous network. Due to the small bonding
area, the opacity degree of laboratory paper handsheets prepared via chemical pulping
was reduced. The opacity of Napier grass and sugarcane laboratory paper handsheets
was reduced with the additional beating process shown in Figure 3. Figure 3 also shows
that the beaten laboratory paper handsheet produced the same brightness as the unbeaten
laboratory paper handsheet. As a result, it is concluded that the beating process only affects
the opacity properties of the laboratory paper handsheet and not the brightness properties.

3.5. Surface Morphology

The visual observation in Figure 4 also shows that beating causes changes in labo-
ratory paper handsheet characteristics. All laboratory paper handsheets produced with
beaten pulp fibres were denser than those made with unbeaten pulp fibres. This appears
that the pulp fibre has a high felting power but a low flexibility and collapsibility of the
fibre wall [66,67]. Through the visual observation, the brightness of the laboratory paper
handsheet clearly reflects the efficiency of lignin removal from chemical pulping from both
grass-type biomasses. As shown in Figure 2, the laboratory paper handsheet derived from
chemical pulping is much brighter as compared to mechanical pulping. The factor that
leads to the change in brightness of papers is the presence of lignin. When lignin content
is low, the paper will appear brighter [68]. Despite the fact that the high lignin content
was responsible for the low brightness on the laboratory paper handsheet derived from
mechanical pulping, it provided an interesting feature. When the Napier grass’ laboratory
paper handsheets are pressed and folded by hand, the laboratory paper handsheet prepared
by chemical pulping is softer than the laboratory paper handsheet prepared by mechanical
pulping. A high removal of lignin, hemicellulose, and cellulose through chemical pulping
causes the fibres to become soft and more loosened, and therefore, unsuitable for paper-
making. This observation explained why the foldance capability of mechanical laboratory
paper handsheets derived from Napier grass is far greater than that of chemical pulping.
To better comprehend the distinctions between the laboratory paper handsheets, this
study depicts SEM images of laboratory handsheets from Napier grass and sugarcane.
Long-fibre materials, as shown in the SEM image of the laboratory handsheet, were made
from Napier grass (Refer Figure 4a). The mechanical properties of the paper are influenced
by the length of the fibre. According to Gomes et al. [69], long fibre will improve the
mechanical properties of the paper. Long fibre pulps have high folding endurance because
they have more fibre joints that are able to form a strong network as well as a larger surface
area to form bondings with their length spans and width of the fold line [70,71]. The
strength of the fibre itself is affected by the packed arrangement of the fibre matrix on the
surface and fibre of Napier grass. Inside the Napier grass, there were many matrix fibres
and long fibres that crossed with each other (Figure 4b). In this study, lower tensile and
tearing indexes occurred in laboratory paper handsheets produced by chemical pulping.
As a result, additional mechanical treatment, including the use of beating, could well
be needed to improve the paper properties. Paper with an additional beating process
 Polymers
Polymers 2022,
2022, 14, 14,
5203x FOR PEER REVIEW 12 of1218of 18

of mechanical
has significantly laboratory paperstrength,
higher paper handsheets derivedin
as shown from
TableNapier grass
3. The is far greatercould
improvement than be
that of chemical pulping.
attributed to the changes in fibre structure induced by the beating process. The SEM results
revealTo better
that comprehend
the additional the distinctions
beating between
process causes thethe laboratory
fibres paper handsheets,
to be drawn toward eachthisother,
study depicts SEM images of laboratory handsheets from Napier
resulting in a more robust fibre network that contributes to good paper strength. grass and sugarcane.
The long
Long-fibre materials, as shown in the SEM image of the laboratory handsheet, were made
fibre (Figure 4b(ii)) and abundance fibre (Figure 4b(iii)) from Napier grass pulp has greatly
from Napier grass (Refer Figure 4a). The mechanical properties of the paper are influenced
contributed to the folding test value.
by the length of the fibre. According to Gomes et al. [69], long fibre will improve the me-
Furthermore, pulping process conditions, such as high alkalinity, temperature, and
chanical properties of the paper. Long fibre pulps have high folding endurance because
mechanical forces, or a combination of these, can result in non-homogeneous zones in the
they have more fibre joints that are able to form a strong network as well as a larger surface
fibre wall, such as deformations [72]. The surface of the chemical pulp of sugarcane was
area to form bondings with their length spans and width of the fold line [70,71]. The
noticeable with prominent deformation, kinks, and curls (refer to Figure 4d(iii)). It has
strength of the fibre itself is affected by the packed arrangement of the fibre matrix on the
been reported that an increase in fibre deformations such as curls and kinks reduces tensile
surface and fibre of Napier grass. Inside the Napier grass, there were many matrix fibres
strength
and long[47]. Such
fibres thatacrossed
deformation wasother
with each resolved
(Figure by 4b).
an additional beating
In this study, lowerprocess. After
tensile and
the beating process, large parts of the fibre deformation were removed,
tearing indexes occurred in laboratory paper handsheets produced by chemical pulping. and the strength
properties
As a result, were restored
additional to undeformed
mechanical treatment,pulp values the
including [73].useWhen beaten
of beating, samples
could were
well be
compared
needed toto unbeaten
improve the samples, the fibresPaper
paper properties. werewith straighter and had
an additional fewer process
beating deformations
has
(refer Figure 4e).
significantly higherSomepaperdeformations are known
strength, as shown to be
in Table 3. straightened
The improvement during thebe
could beating
at-
process. The beaten sample’s fibres were found to be flatter than the unbeaten
tributed to the changes in fibre structure induced by the beating process. The SEM results sample. This
could be because the fibre wall became more flexible as a result of lumen
reveal that the additional beating process causes the fibres to be drawn toward each other, collapse [74].
In addition
resulting to fibre
in a more robust straightening,
fibre networkbeating causes fibrillation
that contributes to good paperalong the fibre
strength. Thesurfaces.
long
Fibrillation,
fibre (Figure 4b(ii)) and abundance fibre (Figure 4b(iii)) from Napier grass pulp surface
or the exposure of cellulose fibrils, will certainly improve the accessible has
area, enhance
greatly fibre-fibre
contributed to thebonding,
folding test and ultimately, improve laboratory paper handsheet
value.
mechanics [75–77]. Aside from the tear index, fibre fibrillation significantly increased all of
the strength properties (refer to Table 2). The bonding of fibre became increasingly tight,
and the fibrillation became more visible with the additional beating process (Figure 4e). As
stated by Jiang et al. [78], over half of the increase in fibre strength is due to beating, which
straightens the fibre during the pulping process, removing curls and kinks. Additionally,
fibrillation can also be attributed to the removal of lignin and other structural effects [79].

Pulping Physical observation Scanning electron micrographs Scanning electron micrographs

technique (magnification ×100) (magnification ×200)
Napier grass

Kraft Pulping

a (i) a (ii) a (iii)

Kraft Pulping &

Beating

b (i) b (ii) b (iii)

Figure 4. Cont.
 Polymers 2022, 14, x FOR PEER REVIEW 13 of 18
Polymers 2022, 14, 5203 13 of 18

Mechanical
Pulping

c (i) c (ii) c (iii)

Sugarcane

Kraft Pulping

d (i) d (ii) d (iii)

e (i) e (ii) e (iii)

Kraft Pulping &
Beating

Mechanical
pulping

f (i) f (ii) f (iii)

Figure4.4.Visual
Figure Visualobservation
observation and
and SEM
SEM micrographs
micrographsofofproduced
producedlaboratory paper
laboratory handsheets.
paper handsheets.

Furthermore,
Fibrillation pulping explained
is actually process conditions, such asmechanism
as a peeling-off high alkalinity, temperature,
in shearing andthe
refiners;
mechanical forces, or a combination of these, can result in non-homogeneous
primary wall and S1 layer are peeled off, exposing the S2 layer to inter-fibre bonding zones in the[80].
fibre wall, such as deformations [72]. The surface of the chemical pulp of
This result indicates that the refining process of mechanical pulping resulted in fibresugarcane was
noticeable with
fibrillation. prominent
A highly fibrousdeformation,
network-like kinks, and curls
structure (refer to
composed of Figure 4d(iii)).
cellulose It has is
microfibrils
been reported
visible that an increase
in the micrograph in fibre deformations
for mechanical such handsheets
laboratory paper as curls and(Figure
kinks reduces ten-
4c,f). Bunches
sile strength [47]. Such a deformation was resolved by an additional beating process.
of fibres in the suspension are squeezed and sheared between the refiner’s working surfaces. After
As a result of this action, parts of the fibre’s outer layers unravel, resulting in fibrillated
fibre surfaces. Furthermore, delamination within the cell wall tends to make the fibres
more flexible while they are still wet [81]. Apart from that, the removal of lignin and
Polymers 2022, 14, 5203 14 of 18

hemicelluloses by alkaline pre-treatments may also be responsible for the morphological

changes in the fibre surface. Aside from contributing to a high pulp yield, hemicellulose has
a significant impact on sugarcane surface characteristics. The high hemicellulose content of
the sugarcane facilitated fibrillation during the mechanical pulping process, as shown in
Figure 4f(iii). This can be explained by hemicelluloses acting as inhibitors of microfibril
coalescence, and thus, facilitating fibrillation [7,82].
Apparently, the current research reveals that the mechanical pulping with alkaline
pre-treatment could indeed replace the most prevalent pulping process (chemical pulp-
ing) in producing pulps from Napier grass and sugarcane. As evidenced by the surface
morphology and mechanical properties results, mechanical pulping is far more suitable
for the grass-type biomass. Furthermore, the high yield value has proven that mechanical
pulping is best suited for commercial scale production. This study discovered that the
mechanical pulping process on Napier grass and sugarcane could meet the quantity and
quality concerns in paper production. This discovery was extremely plausible for indus-
trial paper production because it does not only make economic sense, but it is also more
environmentally conscious for this money-generating and constantly expanding industry.

4. Conclusions
This research employed fibre from the underutilized discarded grass-type biomass,
Napier grass and sugarcane stem, via a pulping process for enhanced biomass conversion
in order to establish a zero-waste environment. The concept of using pre-hydrolysis tech-
niques and beating techniques in conjunction with the chemical and mechanical pulping
processes, respectively, opens up new possibilities to improve the paper strength. The
low lignin content of Napier grass and sugarcane stem emphasizes that both grass-type
biomasses ought to be the new frontier materials for the pulping industry. The introduction
of alkaline pre-treatment to the mechanical pulping process not only effectively reduced
the lignin content of both biomasses, but it also markedly increased the mechanical prop-
erties of the paper. Undoubtedly, chemical pulping is more advanced in terms of optical
preference, but the high reduction in hemicellulose has resulted in a low pulp yield, which
is an important consideration for the pulp and paper industry. The visual observation
reveals that the laboratory paper handsheet produced by chemical pulping is softer than the
laboratory paper handsheet produced by mechanical pulping. Moreover, the surface of the
chemical pulp derived from sugarcane was noticeable with prominent deformation, kinks,
and curls, rendering it unsuitable for papermaking. Additional beating is required to make
it more suited for paper production as it causes the fibres to be drawn toward each other,
resulting in a more robust fibre network. Furthermore, the beating would be attributed to
fibre straightening, which improves fibre bonding and contributes to good paper strength.
Overall, mechanical pulping combined with alkaline pre-treatment is an ideal technique
for producing paper for grass-type biomass as compared to chemical pulping. Chemical
pulping may be more suitable for making pulp from wood, however, from this study, it was
too harsh to be applied on grass-type biomasses which are lower in lignin and extractive
content. The high removal of lignin, whilst also maintaining hemicellulose content via
the mechanical pulping process, has a significant impact on the surface characteristics
of the laboratory paper handsheet derived from Napier grass and sugarcane stem. The
high hemicellulose content of sugarcane-facilitated fibrillation will enormously improve
the accessible surface area, fibre–fibre bonding, and eventually, hand-sheet mechanics.
This work establishes a solid foundation of knowledge regarding the actual potential of
grass-type biomass for paper production and presents an efficacious method for improving
the conventional wood-pulping method.

Author Contributions: Conceptualization, C.L.L. and K.L.C.; validation, P.S.K. and M.S.H.; writing—
original draft preparation, C.L.L.; writing—review and editing, K.L.C.; supervision, P.S.H.; project
administration, P.S.H.; funding acquisition, K.L.C. All authors have read and agreed to the published
version of the manuscript.
Polymers 2022, 14, 5203 15 of 18

Funding: The authors are grateful for the financial support given by the Putra Grant Scheme from
the Universiti Putra Malaysia, under the grant GP-IPM/2022/9716400.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All relevant data are within the manuscript.
Acknowledgments: The authors sincerely thank the postgraduate students who participated in
this research.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Muhammad Zumo, I.; Hashim, M.; Hassan, N.D. Mapping and estimation of above-ground grass biomass using Sentinel 2A
Satellite Data. Int. J. Built Environ. Sustain. 2021, 8, 9–15. [CrossRef]
2. Malahubban, M.; Jalil, N.Z.A.; Zakry, F.A.A.; Kamaludeen, J.; Hassan, M.N.; Saupi, N. Some nutritional properties of Taiwan
Napier grass leaves (Pennisetum purpureum) harvested at different time. J. Phytol. 2021, 13, 72–74. [CrossRef]
3. Zhao, G.; Wu, H.; Li, L.; He, J.; Hu, Z.; Yang, X.; Xie, X. Effects of applying cellulase and starch on the fermentation characteristics
and microbial communities of Napier grass (Pennisetum purpureum Schum.) silage. J. Anim. Sci. Technol. 2021, 63, 1301–1313.
[CrossRef] [PubMed]
4. Desta, S.T.; Yuan, X.J.; Li, J.; Shao, T. Ensiling characteristics, structural and nonstructural carbohydrate composition and
enzymatic digestibility of Napier grass ensiled with additives. Bioresour. Technol. 2016, 221, 447–454. [CrossRef]
5. Sultan, U.; Abidin, Z.; Composition, C.; Stages, D.G. Chemical composition of Taiwan Napier grass at different growth stages. J.
Agrobiotechnol. 2018, 9, 166–172.
6. Bakar, N.A.; Sultan MT, H.; Azni, M.E.; Ariffin, A.H. Investigation of the mechanical properties of Napier-grass-reinforced
composites for the aerospace industry: A review. In Durability and Life Prediction in Biocomposites, Fibre-Reinforced Composites and
Hybrid Composites; Woodhead Publishing: Sawston, UK, 2019; pp. 321–334. [CrossRef]
7. Dias, M.C.; Zidanes, U.L.; Martins, C.C.N.; de Oliveira, A.L.M.; Damásio, R.A.P.; de Resende, J.V.; Boas, E.V.D.B.V.; Belgacem,
M.N.; Tonoli, G.H.D.; Ferreira, S.R. Influence of hemicellulose content and cellulose crystal change on cellulose nanofibers
properties. Int. J. Biol. Macromol. 2022, 213, 780–790. [CrossRef]
8. Jomnonkhaow, U.; Sittijunda, S.; Reungsang, A. Enhanced simultaneous saccharification and fermentation of Napier grass and
Napier silage for two stage bio-hydrogen and methane production using organosolv and hydrothermal. Mater. Chem. Phys. 2021,
267, 124614. [CrossRef]
9. Bizuneh, T. Genetic Diversity Study in Napier Grass (Cenchrus purpureus) Collections and Progenies; Addis Ababa University: Addis
Ababa, Ethiopia, 2020.
10. Faizal, M.; Umaruddin, A.H.; Bakar, N.A.; Sivakumar, S. Potential of sugarcane ethanol as fuel for vehicle in Malaysia. Int. J. Appl.
Eng. Res. 2019, 14, 4410–4414.
11. Daud, W.R.W.; Law, K.N. Oil palm fibers as papermaking material: Potentials and challenges. BioResources 2011, 6, 901–917.
[CrossRef]
12. Malaysian Industry-Government Group for High Technology (MIGHT). Malaysian Biomass Industry Action Plan 2020: Driving
SMEs towards Sustainable Future; Malaysian Industry Government Group for High Technology (MIGHT): Selangor, Malaysia, 2013.
13. Masrol, S.R.; Ibrahim, M.H.I.; Adnan, S.; Tajudin, M.S.A.A.; Raub, R.A.; Razak, S.N.A.A.; Md Zain, S.N.F. Characteristics of
linerboard and corrugated medium paper made from durian rinds chemi-mechanical pulp. MATEC Web Conf. 2016, 51, 02007.
[CrossRef]
14. Adnan, N.A.; Sapuan, S.M.; Ilyas, R.A. Pulp and paper production: A review. In Proceedings of the Advanced Bio- and Mineral
based Natural Fibre Composites (SBMC2021), Serdang, Malaysia, 25 January 2021; pp. 9–13.
15. Pérez-Boada, M.; Prieto, A.; Prinsen, P.; Forquin-Gomez, M.P.; del Río, J.C.; Gutiérrez, A.; Martínez, Á.T.; Faulds, C.B. Enzymatic
degradation of Elephant grass (Pennisetum purpureum) stems: Influence of the pith and bark in the total hydrolysis. Bioresour.
Technol. 2014, 167, 469–475. [CrossRef] [PubMed]
16. Phitsuwan, P.; Sakka, K.; Ratanakhanokchai, K. Structural changes and enzymatic response of Napier grass (Pennisetum purpureum)
stem induced by alkaline pretreatment. Bioresour. Technol. 2016, 218, 247–256. [CrossRef] [PubMed]
17. Talebjedi, B.; Laukkanen, T.; Holmberg, H.; Vakkilainen, E.; Syri, S. Advanced energy-saving optimization strategy in thermo-
mechanical pulping by machine learning approach. Nord. Pulp Pap. Res. J. 2022, 37, 434–452. [CrossRef]
18. Harinath, E.; Biegler, L.T.; Dumont, G.A. Control and optimization strategies for thermo-mechanical pulping processes: Nonlinear
model predictive control. J. Process Control 2011, 21, 519–528. [CrossRef]
19. Sharma, P.; Tripathi, S.; Chandra, R. Metagenomic analysis for profiling of microbial communities and tolerance in metal-polluted
pulp and paper industry wastewater. Bioresour. Technol. 2021, 324, 124681. [CrossRef]
Polymers 2022, 14, 5203 16 of 18

20. Buitrago-Tello, R.; Venditti, R.A.; Jameel, H.; Yao, Y.; Echeverria, D. Carbon footprint of bleached softwood fluff pulp: Detailed
process simulation and environmental life cycle assessment to understand carbon emissions. ACS Sustain. Chem. Eng. 2022, 10,
9029–9040. [CrossRef]
21. Haile, A.; Gelebo, G.G.; Tesfaye, T.; Mengie, W.; Mebrate, M.A.; Abuhay, A.; Limeneh, D.Y. Pulp and paper mill wastes:
Utilizations and prospects for high value-added biomaterials. Bioresour. Bioprocess. 2021, 8, 35. [CrossRef]
22. TAPPI T248 sp-00; Laboratory Beating of Pulp (PFI Mill Method). TAPPI Press: Atlanta, GA, USA, 2000.
23. TAPPI T205 om-88; Forming Handsheets for Physical Tests of Pulp. TAPPI Press: Atlanta, GA, USA, 2002.
24. TAPPI T403 om-02; Bursting Strength of Paper. TAPPI Press: Atlanta, GA, USA, 2000.
25. TAPPI T425 om-01; Opacity of Paper. Technical Association of the Pulp and Paper Industry: Norcross, GA, USA, 2007.
26. TAPPI T425 Om-02; Standard Test Method for Brightness of Pulp, Paper, and Paperboard (Directional Reflectance at 457 nm)
15 (Reapproved). Technical Association of the Pulp and Paper Industry: Norcross, GA, USA, 2002; pp. 1–6.
27. TAPPI T494 om-01; Tensile Properties of Paper and Paperboard (Using Constant Rate of Elongation Apparatus). TAPPI Press:
Atlanta, GA, USA, 2006.
28. TAPPI T414 om-04; Internal Tearing Resistance of Paper (Elmendorf-Type Method). TAPPI Press: Atlanta, GA, USA, 2004.
29. Hilton, A.; Armstrong, R.A. Statnote 6: Post-hoc ANOVA tests. Microbiologist 2006, 2006, 34–36.
30. Kontturi, E.; Meriluoto, A.; Penttilä, P.A.; Baccile, N.; Malho, J.M.; Potthast, A.; Rosenau, T.; Ruokolainen, J.; Serimaa, R.; Laine, J.;
et al. Degradation and crystallization of cellulose in hydrogen chloride vapor for high-yield isolation of cellulose nanocrystals.
Angew. Chem. Int. Ed. 2016, 55, 14455–14458. [CrossRef]
31. Jahan, M.S.; Rahman, M.M.; Ni, Y. Alternative initiatives for non-wood chemical pulping and integration with the biorefinery
concept: A review. Biofuels Bioprod. Biorefin. 2021, 15, 100–118. [CrossRef]
32. Gomes, F.J.B.; Colodette, J.L.; Burnet, A.; Batalha, L.A.R.; Barbosa, B.M. Potential of elephant grass for pulp production.
BioResources 2013, 8, 4359–4379.
33. Obi Reddy, K.; Uma Maheswari, C.; Shukla, M.; Muzenda, E. Preparation, chemical composition, characterization, and properties
of napier grass paper sheets. Sep. Sci. Technol. 2014, 49, 1527–1534. [CrossRef]
34. Sarkar, A.M.; Jahan, M.S.; Nayeem, J.; Arafat, K.M.Y.; Rahman, M.M.; Popy, R.S.; Shofiul Islam Molla Jamal, A.H.M.; Quaiyyum,
M.A. Chemical and morphological characterization and pulping of Casuarina equisetifolia. Nord. Pulp Pap. Res. J. 2021, 36,
559–569. [CrossRef]
35. Małachowska, E.; Dubowik, M.; Boruszewski, P.; Łojewska, J.; Przybysz, P. Influence of lignin content in cellulose pulp on paper
durability. Sci. Rep. 2020, 10, 19998. [CrossRef]
36. Cordeiro, N.; Belgacem, M.N.; Torres, I.C.; Moura, J.C.V.P. Chemical composition and pulping of banana pseudo-stems. Ind. Crops
Prod. 2004, 19, 147–154. [CrossRef]
37. Brännvall, E.; Aulin, C. CNFs from softwood pulp fibers containing hemicellulose and lignin. Cellulose 2022, 29, 4961–4976.
[CrossRef]
38. Djafari Petroudy, S.R.; Ghasemian, A.; Resalati, H.; Syverud, K.; Chinga-Carrasco, G. The effect of xylan on the fibrillation
efficiency of DED bleached soda bagasse pulp and on nanopaper characteristics. Cellulose 2015, 22, 385–395. [CrossRef]
39. Esmaeil, M.H.K.; Talaeipour, M.; Bazyar, B.; Mirshokraei, S.A.; Eslam, H.K. Two-step delignification of peracetic Acid and Alkali
from sugar cane bagasse. BioResources 2019, 14, 9994–10003.
40. Nkwonji, S.N. How to Minimize the Impact of Bleaching Pulp in Pulp Mill on Water Quality on River; Centria University of Applied
Sciences: Hindon, India, 2022.
41. Pathak, P.; Sharma, C. Processes and problems of pulp and paper industry: An overview. Phys. Sci. Rev. 2021. [CrossRef]
42. Khair, F.N.K.; Masrol, S.R. The characteristics of pulp and paper made from top section of Betong (Dendrocalamus Asper) bamboo
by soda pulping method. Prog. Eng. Appl. Technol. 2022, 3, 849–857.
43. Leponiemi, A. Non-wood pulping possibilities—A challenge for the chemical pulping industry. Appita Technol. Innov. Manuf.
Environ. 2009, 61, 234–243.
44. Karlsson, H. Some Aspects on Strength Properties in Paper Composed of Different Pulps; Karlstad University: Karlstad, Sweden, 2007.
45. Sheng, J.; Li, J.; Zhao, L. Fabrication of grease resistant paper with non-fluorinated chemicals for food packaging. Cellulose 2019,
26, 6291–6302. [CrossRef]
46. Vainio, A.K.; Paulapuro, H. Interfiber bonding and fiber segment activation in paper. BioResources 2007, 2, 442–458.
47. Esteves, C.V.; Sevastyanova, O.; Östlund, S.; Brännvall, E. Differences and similarities between kraft and oxygen delignification of
softwood fibers: Effects on mechanical properties. Cellulose 2021, 28, 3775–3788. [CrossRef]
48. Xian, L.J.; Geng, B.J.; Nadhari, W.N.A.W.; Peng, L.C. Optimal hypochlorite bleaching duration for Sesbania grandiflora pulp. IOP
Conf. Ser. Earth Environ. Sci. 2020, 596, 012011. [CrossRef]
49. Jani, S.M.; Rushdan, I. Effect of bleaching on coir fibre pulp and paper properties. J. Trop. Agric. Food Sci. 2014, 42, 51–61.
50. Geng, B.J.; Ramle, S.F.M.; Ibrahim, N.I.; Zaudin, N.A.C.; Young, L.J.; Hamzah, Z. Effect of beating on kraft pulp of Sesbania
grandiflora. Songklanakarin J. Sci. Technol. 2019, 41, 1356–1359.
51. Mossello, A.A.; Harun, J.; Tahir, P.M.; Resalati, H.; Ibrahim, R.; Fallah Shamsi, S.R.; Mohmamed, A.Z. A review of literatures
related of using kenaf for pulp production (beating, fractionation, and recycled fiber). Mod. Appl. Sci. 2010, 4, 21–29. [CrossRef]
52. de Assis, T.; Reisinger, L.W.; Pal, L.; Pawlak, J.; Jameel, H.; Gonzalez, R.W. Understanding the effect of machine technology and
cellulosic fibers on tissue properties—A review. BioResources 2018, 13, 4593–4629. [CrossRef]
Polymers 2022, 14, 5203 17 of 18

53. Kopacic, S.; Walzl, A.; Hirn, U.; Zankel, A.; Kniely, R.; Leitner, E.; Bauer, W. Application of industrially produced chitosan in
the surface treatment of fibre-based material: Effect of drying method and number of coating layers on mechanical and barrier
properties. Polymers 2018, 10, 1232. [CrossRef]
54. Xie, H.; Zhang, H.; Liu, X.; Tian, S.; Liu, Y.; Fu, S. Design and preparation of multiple function-integrated lignin/tannin/ZnONP
composite coatings for paper-based green packaging. Biomacromolecules 2021, 22, 3251–3263. [CrossRef] [PubMed]
55. Mohd Hassan, N.H.; Muhammed, S.; Ibrahim, R. Properties of Gigantochloa scortechinii paper enhancement by beating
revolution. J. Trop. Resour. Sustain. Sci. 2014, 2, 59–67. [CrossRef]
56. Kasmani, J.E.; Samariha, A. Effect of nano-cellulose on the improvement of the properties of paper newspaper produced from
chemi-mechanical pulping. BioResources 2019, 14, 8935–8949.
57. Ajao, O.; Jeaidi, J.; Benali, M.; Restrepo, A.M.; El Mehdi, N.; Boumghar, Y. Quantification and variability analysis of lignin optical
properties for colour-dependent industrial applications. Molecules 2018, 23, 377. [CrossRef]
58. Zhang, H.; Fu, S.; Chen, Y. Basic understanding of the color distinction of lignin and the proper selection of lignin in color-
depended utilizations. Int. J. Biol. Macromol. 2020, 147, 607–615. [CrossRef] [PubMed]
59. Azadfallah, M.; Mirshokraei, S.A.; Latibari, A.J. Photodegradation of acidolysis lignin from BCMP. Molecules 2008, 13, 3129–3139.
[CrossRef] [PubMed]
60. Kumar, A.; Srivastava, N.K.; Gera, P. Removal of color from pulp and paper mill wastewater—Methods and techniques—A
review. J. Environ. Manag. 2021, 298, 113527. [CrossRef]
61. Guan, M.; An, X.; Zhang, H.; Yang, G.; Tian, Z.; Nie, S.; Liu, L.; Cheng, Z.; Cao, H.; Liu, H. Lignin emulsifying rosin for improved
sizing performance and mechanical properties of liquid packaging board. Ind. Crops Prod. 2022, 187, 115276. [CrossRef]
62. Tofani, G.; Cornet, I.; Tavernier, S. Multiple linear regression to predict the brightness of waste fibres mixtures before bleaching.
Chem. Pap. 2022, 76, 4351–4365. [CrossRef]
63. Budischowsky, D.; Zwirchmayr, N.S.; Hosoya, T.; Bacher, M.; Hettegger, H.; Potthast, A.; Rosenau, T. Degradation of cellulosic
key chromophores by ozone: A mechanistic and kinetic study. Cellulose 2021, 28, 6051–6071. [CrossRef]
64. Bajpai, P. Biermann’s Handbook of Pulp and Paper: Volume 1: Raw Material and Pulp Making; Elsevier: Amsterdam, The Netherlands, 2018.
65. Fišerová, M.; Illa, A.; Boháček, Š.; Kasajová, M. Handsheet properties of recovered and virgin fibre blends. Wood Res. 2013, 58,
57–65.
66. Tofanica, B.M.; Cappelletto, E.; Gavrilescu, D.; Mueller, K. Properties of rapeseed (Brassica napus) stalks fibers. J. Nat. Fibers 2011,
8, 241–262. [CrossRef]
67. Khantayanuwong, S.; Boonpitaksakul, W.; Chitbanyong, K.; Pisutpiched, S.; Puangsin, B. Physical properties of handsheets
derived from Coi (Streblus asper Lour.) pulp fiber as papermaking material traced from ancient times. Bioresource 2021, 16,
6201–6211. [CrossRef]
68. Madung, Z.; Soloi, S.; Majid, M.H.A.; Sarjadi, M.S. Production and characterization of Imperata cylindrica paper using potassium
hydroxide as pulping agent. Biodiversitas 2022, 23, 1490–1494. [CrossRef]
69. Gomes, F.J.B.; Colodette, J.L.; Burnet, A.; Batalha, L.A.R.; Santos, F.A.; Demuner, I.F. Thorough characterization of Brazilian new
generation of Eucalypt clones and grass for pulp production. Int. J. For. Res. 2015, 2015, 814071. [CrossRef]
70. Johansson, A. Correlations between Fibre Properties and Paper Properties; KTH Royal Institute of Technology: Stockholm,
Sweden, 2011.
71. Shakourian, G. Effects of Continuous Sample Conditioning on the Folding Endurance of Paper: Schopper Tester; University of Mas-
sachusetts Lowell: Lowell, MA, USA, 2003.
72. Joutsimo, O.P.; Giacomozzi, D. Changes in cell wall structure during kraft processing of Pinus radiata. BioResources 2015, 10,
2461–2478. [CrossRef]
73. Zeng, X.; Vishtal, A.; Retulainen, E.; Sivonen, E.; Fu, S. The elongation potential of paper—How should fibres be deformed to
make paper extensible? BioResources 2013, 8, 472–486. [CrossRef]
74. Ismail, F.S.; Mohamed Asa’ari, A.Z.; Mohd Yussof, N.A.; Chin Hao, L.; Mohammad Padzil, F.N.; Hua, L.S.; Abdullah, L.C.; Jawaid,
M. Physical and mechanical properties of paper made from beaten empty fruit bunch fiber incorporated with microcrystalline
cellulose. J. Nat. Fibers 2022, 19, 999–1011. [CrossRef]
75. Sheikhi, P.; Talaeipour, M. Comparison mechanical and chemical treatments on properties of low yield bagasse pulp during
recycling. World Acad. Sci. Eng. Technol. 2011, 81, 490–493.
76. Winter, A.; Gindl-Altmutter, W.; Mandlez, D.; Bauer, W.; Eckhart, R.; Leitner, J.; Veigel, S. Reinforcement effect of pulp fines and
microfibrillated cellulose in highly densified binderless paperboards. J. Clean. Prod. 2021, 281, 125258. [CrossRef]
77. Emrith, P.D.; Ramasawmy, H.; Surroop, D.; Das, D.B. Substantial size reduction of banana fibres and enhancement of fibre
properties achieved through a single mechanical treatment. Waste Biomass Valorization 2022, 1–25. [CrossRef]
78. Jiang, Y.; Wu, Q.; Wei, Z.; Wang, J.; Fan, Z.; Pang, Z.; Zhu, Z.; Zheng, S.; Lin, X.; Chen, Y. Papermaking potential of Pennisetum
hybridum fiber after fertilizing treatment with municipal sewage sludge. J. Clean. Prod. 2019, 208, 889–896. [CrossRef]
79. Daud, Z.; Hatta, M.Z.M.; Kassim, A.S.M.; Aripin, A.M.; Awang, H. Analysis of Napier grass (Pennisetum purpureum) as a potential
alternative fibre in paper industry. Mater. Res. Innov. 2014, 18, S6-18–S6-20. [CrossRef]
80. Afra, E.; Yousefi, H.; Hadilam, M.M.; Nishino, T. Comparative effect of mechanical beating and nanofibrillation of cellulose on
paper properties made from bagasse and softwood pulps. Carbohydr. Polym. 2013, 97, 725–730. [CrossRef] [PubMed]
Polymers 2022, 14, 5203 18 of 18

81. Hubbe, M.A.; Venditti, R.A.; Rojas, O.J. What happens to cellulosic fibers during papermaking and recycling? A review.
BioResources 2007, 2, 739–788.
82. Wang, T.; Jung, J.; Zhao, Y. Isolation, characterization, and applications of holocellulose nanofibers from apple and rhubarb
pomace using eco-friendly approach. Food Bioprod. Process. 2022, 16, 166–175. [CrossRef]