Chemistry Africa

https://doi.org/10.1007/s42250-022-00574-3

ORIGINAL ARTICLE

Functionalized Cellulose Nanofibrils Obtained from Cellulose

Oxypropylated
Mário H. A. Lima1 · Marcelo A. Pereira‑da‑Silva2,3 · Marcos Mariano4 · Mercês Coelho da Silva5 ·
Aparecido Junior de Menezes1

Received: 11 October 2022 / Accepted: 15 December 2022

© The Tunisian Chemical Society and Springer Nature Switzerland AG 2022

Abstract
The present study aimed to functionalize cellulose nanofibrils (CNFs) through the oxypropylation reaction and compare
the number of cycles required to obtain the functionalized material in comparison to pristine cellulose pulp. Thereunto, the
cellulose was submitted to an initial activation step with a sodium hydroxide solution, and reacted with propylene oxide in
different values of molar ratio ­[OHcellulose]/[PO], in autoclave, maintaining the constant temperature at approximately 135 °C.
After obtaining the functionalized cellulose, the nanocellulose is obtained by passing its suspension (2% in distilled water)
through a microfibrillator mill. Functionalized nanocellulose, as well as the cellulose pulp used throughout the process, were
characterized by Fourier Transform Infrared Spectroscopy (FTIR), aiming to analyze whether the oxypropylation reaction
was effective, evidenced by the appearance of new characteristic bands of the graft of the polyol chains. The samples were
also characterized for their mass gain, Atomic Force Microscopy (AFM), X-Ray Diffraction (DRX) and Thermogravimetry
(TG). The functionalized CNFs in comparison to non-functionalized CNF were obtained in fewer passes in the grinder,
indicating that the functionalization of CNFs is attractive in terms of costs, since this fibrillation process impacts on a large
energy demand in each pass through the grinder.
Graphical Abstract

Extended author information available on the last page of the article

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Keywords Functionalized cellulose nanofibrils · Oxypropylation reaction · Cellulose
1 Introduction
Natural polymers have aroused great interest in the scientific
community, not only due to their biodegradability, but also
due to their availability as a renewable raw material [1–3].
Cellulose, representing about 1.5 trillion tons of the total
annual production of biomass, is considered an almost inex-
haustible source of raw material for the growing demand
for ecological and biocompatible products [4]. Numerous
advantages justify the growing interest in its use, in addition
to being considered the most important renewable polymer
resource [5], such as: availability, good mechanical proper-
ties, low density, modest abrasiveness and biodegradability
[6].
Cellulose nanofibrils (CNFs) are cellulose-derived struc-
tures that have at least one dimension smaller than 100 nm
[7]. These nanofibers can be obtained through different pro-
cesses that require intensive mechanical treatments. The use
of grinders, refiners or high-pressure homogenizers are com-
monly reported, however, each pass impacts a large energy
demand implying a high energy consumption during its
obtaining. Nevertheless, reducing the general interest in the
large-scale production of such materials [8].
In order to optimize such mechanical treatments, Spence
et al. [9] performed an accurate comparative study, analyzing
the energy consumption related to the physical properties of
cellulose microfibrils produced by a homogenizer, a micro-
fluidizer and a mill. For bleached and unbleached wood
kraft pulps, the energy cost was compared as a function of
mechanical treatment, number of cycles (or passes), pressure
and speed. They concluded that the films produced by the
microfluidizer and the microfibrillator presented physical,
optical and water interaction properties superior to those
obtained with the homogenizer, suggesting that these materi-
als could be produced more economically on a large scale.
Additionally, chemical treatments can be used prior to
mechanical treatments facilitating the mechanical fibrilla-
tion process. Depending on the chosen pre-treatment, it sig-
nificantly reduces the overall energy consumption aiming
large-scale applications.
Among the pre-treatments, stands out the chemical
modification of the cellulose surface [5], or the function-
alization of the cellulosic materials, in which the objective
is the insertion of molecules (from low molar mass to oli-
gomeric chains) in the cellulose surface, thus reducing the
intensity of the bonds of hydrogen between the fibers.
The oxypropylation process of materials such as cellulose
aims to increase access to the OH groups of these materials,
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Chemistry Africa
which are generally difficult to access. It is a well-known
and commonly applied process for conversion of polysac-
charides into liquid and viscous polyols. The most common
oxypropylation reactions employ a strong base, which has
the purpose of activating the hydroxyl groups of the polysac-
charide, causing the formation of an alkoxide ion initiator for
the polymerization of the oxide of propylene [10].
The tethering of the arisen polymer chains to cellulose
units can facilitate the defibrillation of the native structure at
the same time that brings new functionality to the obtained
nanofibers. For example, it’s well reported that the grafting
of nanofibers by polymer chains can modify the rheological
properties of such materials [11]. Additionally, the presence
of this polymer can be observed in several systems of inter-
est, such as water-based acrylic paints. Therefore, its pres-
ence can be beneficial for such applications.
In this work, oxypropylation reactions were used to func-
tionalize the exposed hydroxyl groups present on commer-
cially available samples of cellulose pulp in order to reduce
the number of mechanical cycles required to obtain CNF.
Different cellulose-to-monomer ratios were used as start
material to produce nanofibrillated materials using a reduced
number of mechanical cycles. The general characteristics of
the obtained samples are presented.
2 Experimental
Bleached eucalyptus cellulose pulp was kindly provided by
Suzano Papel & Celulose. The sodium hydroxide (NaOH)
and propylene oxide (­ C3H6O) were purchased from Synth
and Merck respectively. All chemicals were used as received.
2.1 Cellulose Functionalization
Firstly, Cellulose pulp was grinded in a water solution
through a knife mill in order to increase the specific sur-
face area. Afterwards, it was dried in a vacuum oven at
60 °C until reaching constant weight. In sequence, 10 g of
dried cellulose pulp was activated with a solution of 7.4 g
(190 mmol) of sodium hydroxide, [NaOH]/[OH cellulose]
molar ratio of 1:1, in 20 mL of water for one hour at room
temperature.
Subsequently, the activated pulp was placed in a stainless-
steel autoclave reactor together with the desired amount of
propylene oxide. Different molar ratios between cellulose
hydroxyl groups (OH) and the monomer (PO) were used.
The sealed autoclave, equipped with a thermocouple,
Chemistry Africa
a manometer and a heating controller system, was then
heated for one hour, keeping the temperature constant at
about 135 °C, while the corresponding pressure rise was
monitored.
Due to propylene oxide being a volatile liquid, a liq-
uid–vapor equilibrium is established upon reaching the
reaction temperature, generating a corresponding pressure.
The end of reaction was determined by the lowering of the
pressure in the manometer due to the consumption of the
modifying agent (propylene oxide) during the reaction. The
oxypropylated cellulose was dried in a vacuum oven at 60 °C
until constant weight. The success of the oxypropylation
reaction, was confirmed by infrared analysis.
2.2 Nanocellulose Obtainment
To obtain the nanocellulose, a suspension with a concen-
tration of 2% of the total mass in distilled water of each
sample was stirred with the IKA-T25 Digital Ultra Turrax
equipment for 5 min (the first 2 minutes at 12,000 RPM, the
second two at 16,000 RPM, and the final minute at 20,000
RPM). Afterwards, the fibers were processed in an Ultra-fine
friction grinder Masuko “Supermasscolloider” in cycles to
obtain the oxypropylated nanocellulose. All samples were
prepared in triplicate and the schematic representation is
presented in the Fig. 1.
Fig. 1  Schematic representation of oxypropylated and CNFs obtain-
ing process
Cellulose suspensions were manually passed through the
friction grinder for micro fibrillation until it obtained the
appearance of a viscous and translucent gel-like material as
also reported by Gestranius et al. [12], and this same process
was used to Jasmani et al. [13] to obtain NFC. For pristine
pulp, approximately 30 cycles are typically required. Func-
tionalized materials were processed using 20 cycles. This
number as well as all the conditions of the grinder were kept
constants for all modified samples.
2.3 Characterizations
2.3.1 Mass Gain (MG)
The material was weighed before and after the chemical
modification reaction and the mass gain (GM) was calcu-
lated according to the Eq. 1:
Mfinal − Minitial
MG = × 100 (1)
Minitial
where MG is the mass gain (%), M ­ initial is the initial mass
of the sample before activation (g), M
­ final is the mass after
oxypropylation reaction (g) subtracted the mass of NaOH
used for the activation step.
2.3.2 Fourier Transform Infrared Spectroscopy (FTIR)
The measurements were performed in a spectrophotometer
model i2S10 Nicolet Thermofisher with 32 scans, 4 ­cm−1
resolution in attenuated total reflectance (ATR) mode.
2.3.3 X‑Ray Diffraction (XRD)
XRD analyzes were performed by Rigaku MiniFlex-II
equipment at 30 kV, 15 mA and scan speed of 0.02º/min,
Cu Ka radiation (k = 1.5418 Å).
2.3.4 Atomic Force Microscopy (AFM)
The AFM measurements were performed on a Bruker equip-
ment, Dimension ICON model, with a rectangular silicon
tip. The suspensions containing the nanocellulose were
diluted to a concentration of 0.05% and deposited on pre-
viously cleaved mica. After were taken to a vacuum oven
at 60 °C for 1 h. The micrographs obtained were analyzed
using the Gwyddion data analysis software (version 2.48)
and the fibers diameter were measured by height to avoid
effect of tip size on the measurement of microfibril diameter.
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2.3.5 Thermogravimetry (TG)
The TG analyzes were performed in Discovery series equip-
ment of the TA Instruments brand at a heating rate of 10 °C/
min under from 25 to 600 °C in nitrogen flow 50 c­ m3 ­min−1.
The derivatives of the data are used to simplify the discus-
sion of results.
3 Results and Discussions
3.1 Mechanisms of Surface Modification
Cellulose fiber pretreatments or functionalization have
become popular due to the possibility to reduce the amount
of energy required to obtain derivate nanofibrils. It has been
shown that energy consumption in defibrillation processing
can be greatly reduced using these pre-treatments. Under
certain conditions, processing energy can be reduced from
20,000 to 30,000 kWh/ton to around 1000 kWh/ton [14].
Here, cellulose treatments are initiated by the called pre-
functionalization or substrate activation step (Scheme 1).
The cellulose is placed in contact with an aqueous solution
of NaOH (strong Bronsted base) for the “activation” of the
Scheme 1  Simplified representation of the cellulose reaction activation step
Scheme 2  Oxypropylation of
the cellulose and the secondary
reaction of homopolymerization
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Chemistry Africa
hydroxyl groups, which is then deprotonated. It generates an
oxyanion in the corresponding alkoxide anion, which acts as
an anionic initiator for the polymerization reaction.
During the oxypropylation reaction, the alkoxide anion
formed previously in the activation step reacts with the pro-
pylene oxide attacking the least sterically hindered carbon,
causing the oxirane ring to open, thus forming an oxyanion
that will remain reactive in the medium. With this, the chain
length will continue to grow until all the propylene oxide
is consumed or the reaction is interrupted, for example, by
lowering the temperature of the autoclave. In the end, oxy-
propylated cellulose is obtained, as can be seen in Scheme 2,
with the growth of polyol chains grafted onto the cellulose
molecule. The homopolymerization of propylene oxide
occurs simultaneously as a by-product of the oxypropyla-
tion reaction.
Six samples were produced under similar experimental
conditions (i.e., temperature, pretreatment and reaction
times) and different molar ratios of propylene oxide to cel-
lulose hydroxyls groups, as can be seen in Table 1.
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Table 1  Cellulose samples and its respectively molar ratio of the oxy- of polyols chains in highly oxypropylated samples. In these
propylation reaction systems, the arisen of homopolymers due to secondary reac-
Sample molar ratio Pre-treatment Reaction tions is unavoidable, leading to the formation of polypropyl-
[OHcellulose]/[PO] Time (hour) Time (hour) ene glycol [15].
At this [­ OHcellulose]/[PO] range, all obtained samples pos-
– – –
sess the expected aspect of gel-like suspensions. It is related
[1: 0.3] 1 1
to cellulose’s ability to retain water in its internal and exter-
[1: 0.5] 1 1
nal structures. After defibrillation, its nanofibers can retain
[1: 0.8] 1 1
a significantly higher amount of water than the pristine pulp
[1: 1.0] 1 1
due to the exponential increase of exposed hydroxyl groups
[1: 3.0] 1 1
[16].
[1: 5.0] 1 1
However, samples acquired a highly viscous consistency
and darker colour when higher PO to OH molar ratios were
used (Fig. 3a, b). Such unexpected modification on the sam-
3.2 Samples Appearance and Mass Gain ples appearance indicates the arisen of different structures in
the suspension. It can be related to a drastic increase in the
Figure 2 shows the aspect of the cellulose suspensions pre- homopolymers present in the system.
paring using mild oxypropylation conditions. A progres- The increase in sample mass after oxypropylation reac-
sive modification in sample color towards brown can be tions using different monomers ratios can be established
observed. It is probably related to the uncontrolled growth as indicative of a proportional surface modification level

Fig. 2  Aspect of the obtained

samples and its different molar
ratio

Fig. 3  Aspect of the samples of

molar ratio [1:3.0] and [1:5.0]

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Fig. 4  Evolution of mass gain according to the initial PO to OH ratio.
The red line is only a guide to the eyes
in given experimental conditions. Roughly, the gain of
mass reflects the amount of polymer chain attached to the
nanofiber surface.
A general tendency of increase in mass gain with the
increase of PO is observed in Fig. 4. Those results suggest
that two regimes of mass increase are possible, depending
on the initial amount of the monomer. To values samples
containing a OH/ratio smaller than 1:1, an initial mass gain
of 89% is followed by a linear increase toward 105% in the
sample [1:0.8].
For higher polymer-to-cellulose ratios (especially sam-
ples with 3× and 5× more PO), an exponential increase is
observed, with a plateau being observed in the most modi-
fied sample. Menezes et al. [17] also observed that for the
molar ratio [1:3.0], the value is close to the value measured
for samples with higher molar ratio, in a clear indication that
from this proportion there are no significant changes in the
mass gain, this can be determined as a threshold value of
the molar ratio for these working conditions. This behavior
Fig. 5  FTIR spectra of the
cellulose before and after the
oxypropylation reaction in dif-
ferent OH/PO molar ratio
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Chemistry Africa
also can be associated with the modification of the sample
structure, corroborating the visual observations.
The process of functionalized cellulose nanofibrils
obtained from cellulose oxypropylated sought to be as direct
and easy as possible, thus avoiding additional steps neces-
sary to remove residual homopolymers through n-hexane,
ether or dichloromethane purifications, for example. There-
fore, samples with higher molar ratio values proved to be
unfeasible due to the amount of homopolymer incorporated
into the sample. As a result, lower values of molar ratio were
explored due to the lower amount of homopolymer incorpo-
rated into the sample.
3.3 Fourier Transform Infrared Spectroscopy (FTIR)
The effective chemical modification of pristine fibers could
be observed by FTIR analysis. Cellulose sample presented
traditional spectra expected for these materials, Fig. 5.
At lower wavenumbers, β bonds at 898 ­cm−1, which
are characteristics of glycosidic bonds of cellulose, are
observed. The central region of the spectra present peaks at
1027, 1334, 1367 and 1431 ­cm−1 belong to the bending and
stretching vibrations C–O, OH, CH and ­CH2 bonds present
in cellulose.
The band around 2900 ­cm−1 is attributed to the CH elon-
gation vibration of all hydrocarbon constituents in the poly-
saccharides. It also can be observed that the pristine cellu-
lose sample present a broad band in the range from 3500 to
3200 ­cm−1, which involves the stretching of intramolecular
OH groups. The peak at 3338 ­cm−1 also includes vibrations
of inter- and intra-molecular hydrogen bonding of cellulose
[18].
The FTIR is a great way to demonstrate the success of the
cellulose oxypropylation reaction, with the appearance of a
discreate new peaks in the 2970 ­cm−1 region. Those peaks
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are usually associated with the methyl groups due to the
grafting of PO units, as can be seen in more detail in Fig. 5b.
Additionally, it is also possible to notice in Fig. 5c
the increase and broadening of the peak between
1171–1076 ­cm−1. These bands correspond to the vibrations
by elongation of the C–O–C bond of ether groups associ-
ated with the inclusion of the polyoxide of propylene, as
well as the peak around 1375–1380 ­cm−1 also attributed to
the methyl group of the polyol incorporated into the mate-
rial [6].
3.4 Atomic Force Microscopy (AFM)
The observation of the obtained samples at nanoscale was
used to ensure that the reduction in the number of cycles
from 30 to 20 passes was not a barrier in the obtainment
of CNF. The morphology of the obtained CNFs can be
observed through AFM topography (Fig. 6).
The images are able to provide several information about
the structure and composition of these nanofibers. For
example, the observed particles clearly present the charac-
teristic aspect of long rod-like objects usually attributed to
cellulose nanofibers [19]. The height measurement of ca.
Fig. 6  Atomic Force Micros-
copy images of sample [1:3]
(a–c) and its average diameter
size distribution (d)
150 individual nanofibers provides an average diameter
of 34 ± 19 nm. This value is close to the superior limit of
diameters suggested by the TAPPI for cellulose nanofibrils,
reported being in the range of 5–30 nm [20].
The observation of an entangled network of very long
nanofibers can attest the potential of the proposed process
oxypropylation/higher shearing to isolate CNF with high
aspect ratio. It suggests a very interesting and wide range of
applications as reported by Eichhorn et al. [21] for cellulose
as a functional nanomaterial, in particular can be pointed out
composites which cellulose is the main part of both matrix
and fibers as already reported by Gandini et al. [6].
Furthermore, a mixture among predominant nanostruc-
tures and residual microfibers is observed. Figure 6a, b
show different stages of the defibrillation and the transi-
tion from microfibers to branched aggregates of nanofi-
brils is observed. It also calls attention that several of these
observed branched nanofibers possess a sort of soft material
on their surface, as shown in Fig. 6a–c. This observation cor-
roborates the presence of homopolymers in the suspension.
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 Chemistry Africa

Fig. 7  Derivate of the thermal

gravimetric analysis of cellulose
pulp and different oxypro-
pylated nanofibers

Table 2  Samples and its respectively temperature event [25], suggesting that the presence of less stable polyol
Sample Low temperature Secondary low Higher tempera-
groups that can trigger earlier degradation reactions.
event (max.), °C temperature event ture event (max.), Other samples with higher oxypropylation degrees pre-
(max.), °C °C sent a different profile, with a secondary event at low tem-
peratures (around 100 °C). The arisen of such second stage
CNF 80 – 349
of mass loss indicate a change in the thermal behaviour of
[1:0.3] 53 – 239
the samples after higher degrees of modification. It can be
[1:0.5] 57 104 235
related to the arisen of a new and distinct chemical environ-
[1:0.8] 46 99 233
ment on the sample, where new PO groups are available
[1:1.0] 54 98 232
and modify how the water interacts with the nanofibers. As
observed in sample [1:0.3], the first event can be related to
the removal of residual PO monomers or water molecules
3.5 Thermogravimetric Analysis (TG) weakly bonded to cellulose/tethered polymeric chains. The
second event (around 100 °C) can be related to the loss of
The thermal properties of the samples were accessed by water strongly bonded to regions of uncoated cellulose sur-
thermogravimetric analysis (Fig. 7) in order to evaluate pos- face or to the earlier degradation of free macromolecules.
sible effects of the oxypropylation and nanofibrilation pro- Further characterizations are necessary to fully comprehend
cess on samples behavior. It can be observed that the pristine such thermal behaviour.
cellulose sample present the expected degradation profile Those samples also presented early thermal degradation
expected for bleached pulps, with a first event related to the temperatures (around 230–240 °C) A slight tendency to
loss of water around 80 °C and a second sharp event related temperature decrease with a higher oxypropylation rate is
to the cellulose degradation with a maximum temperature observed.
around 350 °C [22].
A similar two-stage weight loss behavior can be observed 3.6 X‑Ray Diffraction (XRD)
in the sample with the smaller oxypropylation degree (sam-
ple [1:0.3]). However, both temperatures of water loss and The effect of cellulose functionalization with PO on the
thermal degradation are considerably lower if compared to crystallinity of the biopolymer was studied by XRD, whose
the pristine sample (Table 2). diffractograms are reported in Fig. 8.
Strongly interactions among pristine cellulosic materials The unfunctionalized cellulose showed centralized peaks
and water are known to be responsible to preserve some mol- at 2θ = 15.9 and 2θ = 22.8 assigned to crystallographic
ecules attached to cellulose surface until 120 °C (similar to planes 101 and 002 of type I cellulose [26], respectively.
the range found in Fig. 7) [23]. The reduction of this temper- The presence of crystalline plane 002 was also observed in
ature range in [1:0.3] sample can suggest a decrease in the all the functionalized nanocellulose samples, however these
nanofiber-water affinity, allowing an earlier water removal samples also showed crystallographic plane peaks at approx-
from the sample. At same time, it also can be influenced by imately 2θ = 12° and at 2θ = 20°, corresponding to crystal-
the presence of residual PO monomers. lographic planes 101 and 10–1 of type II cellulose [26], indi-
At higher temperatures, similar early degradation was cating a mixture of cellulose I and II polymorphs resulting
previously described by Rosa et al. [24] and Menezes et al. from the conversion of cellulose I into its allomorph as a

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Fig. 8  Diffractogram of the non-functionalized cellulose compared
to the functionalized samples from different propylene oxide molar
ratios
Table 3  Crystallinity index and the respective crystallite sizes of
the unfunctionalized and functionalized nanocellulose with different
molar ratios of propylene oxide
Sample Crystallinity index (%) Crystallite
sizes (nm)
CNF 74.7 3.37
[1:0.3] 59.9 1.92
[1:0.5] 70.7 1.79
[1:0.8] 88.1 5.08
[1:1.0] 69.7 4.38
result of the employment of strong alkaline solution in the
nanocellulose functionalization process [27, 28]. In addition
to the mentioned crystalline planes the samples functional-
ized in the molar ratio of [1:0.8] and [1:1.0] also showed
peaks at 2θ near 15° characteristic of crystallographic plane
101 of type I cellulose [29].
Although the crystalline structure of type I cellulose was
preserved after the oxypropylation reactions, the changes
in intensity and definitions of the peaks referring to their
crystalline planes reflect a change in the diffraction pat-
terns, which may be due to the presence of the grafted polyol
chains on the surface of the fibers, and which was evaluated
from their crystallinity indices and crystallite sizes reported
in Table 3. The crystallinity index (CI) of the samples was
obtained by the ratio of the difference between the crystal-
line and amorphous phase at 2θ = 22° and the valley that cor-
respond only to amorphous phase at 2θ = 18.5° and the peak
at 22° as can be seen in Eq. 2, while the crystallite size (CS)
of cellulose calculated from the peak width around 2θ = 22,
5° by means of Scherrer’s formula, Eq. 3, where λ is the
wavelength of X-ray radiation (Cu Kα, λ = 1.5418 Å), Δθ
is the peak width at half maximum height (FWHM—Full
Width at Half Maximum, in radians) and θ is the Bragg
angle for reflection (002).
Cl(%) = [l(22◦ ) − l(18.5◦ ) ∕l(22◦ ) ] × 100 (2)
CS = 0.9 𝜆∕Δ𝜃 cos𝜃 (3)
Among the functionalized samples, the one obtained
after oxypropylation at molar ratio [1:0.8] showed higher
crystallinity index and crystallite size. This increase in
crystallinity may be due to a higher defibrillation inducing
an increase in crystallinity. As already reported for wood,
rice straw and potato tuber compared to untreated puri-
fied fibers [30–32], this is due to the partial degradation
and removal of amorphous cellulose during mechanical
treatment. This same effect can be attributed to the higher
crystallinity index values of the samples prepared at molar
ratios of [1:0.5] and [1:1.0] when compared to the sample
oxypropylated at molar ratio of [1:0.3], Gu et al. [33] also
observed a high crystallinity index (68.5%) for nanocel-
lulose extracted from isolated bamboo parenchyma using
deep eutectic solvent.
The crystallite size of the unfunctionalized nanocellulose
is consistent with that reported in the literature. Andersson
et al. [34] obtained an average crystallite size of 3.2 ± 0.1 nm
for Norway spruce cellulose. Whereas Szymańska-Chargot
et al. [35] obtained a crystallite size of 2.28 nm for pure cel-
lulose obtained from apple pomace. The CNF functionalized
with molar ratios of ­[OHcellulose]/[PO] at [1:0.3] and [1:0.5]
showed a reduction in crystallite size consistent with the
loss of crystallinity of these materials, while the samples
obtained at molar ratios of [1:0.8] and [1:1.0] showed larger
crystallite sizes. The higher proportion of PO in the oxy-
propylation reactions of these samples may have resulted
in larger poly(propylene oxide) chains on the surface of the
fibers or even this free polymer, which may have minimized
the effects of shear on the crystalline structure of cellulose.
4 Conclusions
In this study, hydroxy groups present at the surface of
cellulose fibers were activated through a basic treatment.
These activated fibers were modified with propylene
oxide to obtain the functionalized material. Such reaction
allowed the obtainment of functionalized CNFs through
the use of a mechanical grinder.
It was observed that the thermal and polymorphic pro-
prieties of these nanofibers are strongly dependent on the
chosen monomer-to-cellulose ration during functionalization
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reaction. Due to the unavoidable presence of homopolymers,
a further purification step should be analyzed case-by-case
in dependence of the desired application.
However, it is observed that the introduction of PO
moieties to the cellulose surface can be used to reduce
the energy costs requested to obtain CNFs by allowing a
33% reduction in the number of mechanical cycles. Such
reduction makes the mechanical fibrillation process sig-
nificantly more attractive in terms of energy expenditure
and possible large-scale application as the arisen of green
chemistry cellulose-based materials has emerged as a good
option in terms of applications and sustainability.
Acknowledgements We are grateful to Eurofarma Laboratories,
Suzano Papel & Celulose and PPGCM-So/UFSCar, for the support.
Declarations
Conflict of interest Authors have no conflict of interest.
References
1. Sadasivuni KK, Saha P, Adhikari J, Deshmukh K, Ahamed MB,
Cabibihan J-J (2019) Recent advances in mechanical properties
of biopolymer composites: a review. Polym Compos. 1–28
2. Padinjakkara A, Thankappan A, Souza FG Jr., Thomas S (2017)
Biopolym Biomater Sabu 25:2017
3. Vroman I, Tighzert L (2009) Biodegradable Polym Mater
2(2):307–344
4. Klemm D, Heublein B, Fink H-P, Bohn A (2005) Cellulose: fas-
cinating biopolymer and sustainable raw material. Angew Chem
Int Ed 44(22):3358–3393
5. Heinze T, Koschella A, Liebert T, Harabagiu V, Coseri S (2012)
Cellulose: chemistry of cellulose derivatization. The European
polysaccharide network of excellence (EPNOE), 283–327
6. Gandini A, Curvelo AS, Pasquini D, Menezes AJ (2005) Direct
transformation of cellulose fibres into self-reinforced composites
by partial oxypropylation. Polymer 46(24):10611–10613
7. Ilyas R, Sapuan S, Norrrahim M, Yasim-Anuar T, Kadier A, Kalil
M, Atikah M, Ibrahim R, Asrofi M, Abral H, Nazrin A, Syafiq
R, Aisyah H, Asyraf M (2020) Nanocellulose/starch biopolymer
nanocomposites: processing, manufacturing, and applications.
Adv Process, Properties, Appl Starch Other Bio-Based Polym,
65–88
8. Nair S, Zhu J, Deng Y, Ragauskas A (2014) Charaterization of
cellulose nanofibrillation by micro grinding. J Nanoparticle Res
9. Spence K, Venditti R, Rojas O, Habibi Y, Pawlak J (2011) A
comparative study of energy consumption and physical proper-
ties of microfibrillated cellulose produced by different processing
methods. Cellulose 18(4):1097–1111
10. Belgacem M, Gandini A (2002) Biomacromol 3:57–62
11. Gauche C, Felisberti M (2019) Colloidal behavior of cellulose
nanocrystals grafted with Poly(2-alkyl-2-oxazoline). ACS Omega
4(7):11893–11905
12. Gestranius M, Otsuka I, Halila S, Hermida‐Merino D, Solano
E, Borsali, R, Tammelin T (2020) High‐resolution patterned
biobased thin films via self‐assembled carbohydrate block copoly-
mers and nanocellulose. Adv Mater Interfaces, 1901737
13. Jasmani L, Jamaluddin NAN, Rusli R, Adnan S, Zakaria S (2022)
Different preparation method of nanocellulose from macaranga
13
Chemistry Africa
gigantea and its preliminary study on packaging film potential.
Polym (Basel) 14(21):4591
14. Siró I, Plackett D (2010) Microfibrillated cellulose and new nano-
composite materials: a review. Cellulose 17:459–494. https://​doi.​
org/​10.​1007/​s10570-​010-​9405-y
15. Joshi G, Rana V, Naithani S, Varshney VK, Sharma A, Rawat
JS (2019) Chemical modification of waste paper: an optimiza-
tion towards hydroxypropyl cellulose synthesis. Carbohyd Polym
223:115082
16. Ioelovich M (2008) Cellulose as a nanostructured polymer: a short
review. 389 Bio Res 3:1403–1418
17. Menezes A (2007) Preparação e caracterização de sistema bifásico
mono-componente (SBM) a partir da reação de oxipropilação
de fibras celulósicas e amido. Tese de Doutorado, Instituto de
Química de São Carlos, Universidade de São Paulo, São Carlos.
https://​doi.​org/​10.​11606/T.​75.​2007.​tde-​11052​007-​161843
18. Popescu M, Popescu C, Lisa G, Sakata Z (2011) Evaluation of
morphological and chemical aspects of different wood species by
spectroscopy and thermal methods. J Mol Struct 988:65–72
19. Babi M, Palermo A, Abitbol T, Fatona A, Jarvis V, Nayak A et al
(2022) Direct imaging of the alternating disordered and crystal-
line structure of cellulose fibrils via super-resolution fluorescence
microscopy. ChemRxiv. Cambridge Open Engage, Cambridge
20. Tappi WI 3021. (2012) Proposed new TAPPI standard: standard
terms and their definition for cellulose nanomaterial
21. Eichhorn S, Etale A, Wang J, Berglund A, Li Y, Cai Y, Chen C,
Cranston E, Johns M, Fang Z, Li G, Hu L, Khandelwal M, Lee
K-Y, Oksman K, Pinitsoontorn S, Quero F, Sebastian A, Titirici
M, Xu Z, Vignolini S, Frka-Petesic B (2022) Current international
research into cellulose as a functional nanomaterial for advanced
applications. J Mater Sci 57:5697–5767
22. Mariano M, Cercená R, Soldi V (2016) Thermal characteriza-
tion of cellulose nanocrystals isolated from sisal fibers using acid
hydrolysis. Ind Crops Prod 94:454–462. https://d​ oi.o​ rg/1​ 0.1​ 016/j.​
indcr​op.​2016.​09.​011
23. Mariano M, El Kissi N, Dufresne A (2015) Melt processing of
cellulose nanocrystal reinforced polycarbonate from a masterbatch
process. Eur Polym J 69:208–223
24. Rosa JR, Silva ISV, Lima CSM, Pasquini D (2015) Production of
polyols and new biphasic mono-component materials from soy
hulls by oxypropylation. Ind Crops Prod 72:152–158. https://​doi.​
org/​10.​1016/j.​indcr​op.​2014.​12.​044
25. Menezes AJ, Pasquini D, Curvelo AA, Gandini A (2009) Self-
reinforced composites obtained by the partial oxypropylation of
cellulose fibers. 1. Characterization of the materials obtained with
different types of fibers. Carbohydr Polym 76:437–442
26. Ford E, Mendon S, Thames S, Rawlins J (2010) X-ray diffraction
of cotton treated with neutralized vegetable oil-based macromo-
lecular crosslinkers. Cellulose 9(11):18–23
27. Kadla J, Gilbert R (2000) Cellulose structure: a review. Cellul
Chem Technol 34:19
28. Youssef H, Lucian A, Orlando R (2010) Cellulose nanocrystals:
chemistry, self-assembly, and applications. Chem Rev 110:3479
29. Neto W, Silvério H, Dantas N, Pasquini D (2013) Extraction and
characterization of cellulose nanocrystals from agro-industrial
residue–soy hulls. Ind Crops Prod 42:480–488
30. Cheng Q, Wang S, Rials T, Lee SH (2007) Physical and mechani-
cal properties of polyvinyl alcohol and polypropylene composite
materials reinforced with fibril aggregates isolated from regener-
ated cellulose fibers. Cellulose 14:593–602
31. Abe K, Yano H (2009) Comparison of the characteristics of cel-
lulose microfibril aggregates of wood, rice straw and potato tuber.
Cellulose 16:1017–1023
Chemistry Africa

32. Cheng Q, Wang S, Han Q (2009) Novel process for isolating
fibrils from cellulose fibers by high-intensity ultrasonication. II.
Fibril characterization. J Appl Polym Sci 115:2756–2762
33. Gu W, Zeng S, Dauletbek A, Xu B, Wang X, Yuan M, Gu Y
(2021) Study on preparation of lignin-containing nanocellulose
from bamboo parenchyma. J Renew Mater 10(2):385–399
34. Andersson S, Serimaa R, Paakkari T (2003) Crystallinity of wood
and the size of cellulose crystallites in Norway spruce (Picea
abies). J Wood Sci 49:531–537
35. Szymańska-Chargot M, Ciesla J, Chylinska M (2018) Effect
of ultrasonication on physicochemical properties of apple
based nanocellulose-calcium carbonate composites. Cellulose
25:4603–4621
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Authors and Affiliations

Mário H. A. Lima1 · Marcelo A. Pereira‑da‑Silva2,3 · Marcos Mariano4 · Mercês Coelho da Silva5 ·

Aparecido Junior de Menezes1

3
* Aparecido Junior de Menezes Paulista Central University Center, UNICEP, São Carlos, SP,
jrmenezes@ufscar.br Brazil
4
1 Pharmaceutical and Molecular Biotechnology Research
Graduate Program in Materials Science-PPGCM/UFSCar,
Centre, SETU, Waterford, Ireland
Sorocaba, SP, Brazil
5
2 Federal University of Itajubá, UNIFEI, Itabira, MG, Brazil
Institute of Physics of São Carlos, IFSC/USP, São Carlos, SP,
Brazil

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