Cellulose

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ORIGINAL RESEARCH

Effect of chemical treatments on properties of raffia palm

(Raphia farinifera) fibers
Opeoluwa Fadele . Ikechukwuka N. A. Oguocha . Akindele G. Odeshi .
Majid Soleimani . Lope G. Tabil

Received: 17 November 2018 / Accepted: 21 September 2019

Ó Springer Nature B.V. 2019

Abstract Chemical treatment is used to improve calorimetry, universal testing machine and Fourier
interfacial bonding of natural fibers to polymers to transform infrared spectroscopy. Chemical treatment
produce natural fiber reinforced polymer matrix reduced the tensile strength of the fibers. Some non-
composites with enhanced mechanical properties. In cellulosic components were partially or fully removed
the present study, raffia palm (Raphia farinifera) fibers as a result of chemical treatment. There was an
intended for use in composite manufacture was increase in the degradation temperature of the fibers
subjected to chemical treatments with NaOH and due to chemical treatment. Water absorption capacity
H2SO4 solutions. Morphological, thermal, tensile, of the fibers decreased as a results of chemical
physical and structural changes in the fibers before treatment, which will be beneficial in composite
and after treatment were investigated using scanning synthesis.
electron microscopy, differential scanning

O. Fadele (&)  I. N. A. Oguocha  A. G. Odeshi

Department of Mechanical Engineering, College of
Engineering, University of Saskatchewan, 57 Campus
Drive, Saskatoon, SK S7N 5A9, Canada
e-mail: [email protected]

M. Soleimani  L. G. Tabil
Department of Chemical and Biological Engineering,
College of Engineering, University of Saskatchewan, 57
Campus Drive, Saskatoon, SK S7N 5A9, Canada

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Graphic abstract

Keywords Raffia palm fiber  Mechanical thermoplastic and thermoset matrices have been
properties  Thermal properties  Fourier transform embraced by European car makers and suppliers for
infrared spectroscopy door panels, seat backs, headliners, package trays,
dashboards, and other interior parts (Holbery and
Houston 2006).
In spite of the aforementioned attractive proper-
Introduction ties of NFs, their use in several structural applica-
tions are limited. They have high variability in
The mechanical properties of polymers are inadequate properties (Chinga-carrasco et al. 2011); these
for many structural purposes; their strength and properties depend strongly on age (maturity level),
stiffness are lower than those of ceramics and metals climate, weather and location. They are hydrophilic,
(Santhosh et al. 2014). As such, they are often which results in poor interfacial bonding between
reinforced with strong but expensive synthetic fibers, the polymer matrix and fiber, and swelling of NF-
whiskers or particles to achieve improved mechanical reinforced PMCs thereby leading to poor mechan-
properties and widen their structural applications ical performance. To overcome the latter problems,
(Thiruchitrambalam et al. 2010). However, polymer NFs are often chemically treated to modify the
composites made from synthetic reinforcements pose surface properties (Bledzki and Gassan 1999;
severe environmental pollution problems as they are Benyahia and Merrouche 2014). Chemical surface
not readily recyclable (Elenga et al. 2009). Hence, the treatment of NFs cleans the fibers by removing
increasing interest in the use of plant-based natural pectin, waxes, proteins, natural oils and other
fibers (NFs) for making polymer matrix composites impurities; it also increases their surface roughness
(PMCs). NFs are lightweight, inexpensive, renewable which is vital in developing good bonding to
and biodegradable. Some NFs have mechanical prop- polymer matrices. Good bonding in composites
erties comparable to those of some synthetic fibers enhance load transfer from the fibers to the matrix
(Mohammed et al. 2015). NF composites with via interfacial shear stresses.

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Raffia palm fibers (RPFs) traditionally find appli- NaOH concentration and treatment time and temper-
cations in products such as ropes, yarns, dresses, ature was based on the results of several tests
carpets, mats, ligatures as well as in reinforcements for conducted in-house to optimize the cellulose content
bricks, cements and concretes (Sandy and Bacon of RPF through alkalization treatment. Similarly,
2001; Elenga et al. 2009; Odera et al. 2015). Studies by another set of ground RPFs was immersed in 0.6
Elenga et al. (2009) and Sandy and Bacon (2001) molar aqueous solution of H2SO4 (with a solution to
showed that RPFs have good potential as reinforce- fiber ratio of 10 ml to 1 g) at 100 °C for 2 h. Again,
ment for polymers in composites manufacture. Nev- this treatment gave the largest amount of cellulose
ertheless, before they are used for this application, it is without causing lignin hydrolysis from a set of tests
imperative to understand how chemical surface mod- conducted in-house. After the immersion, the fibers
ification affects their properties. This will help in were washed in laboratory water and then in distilled
optimizing the properties of polymer composites in water. Drying of the washed samples was carried out
which they will be used. Currently, there is dearth of in an air furnace at 60 °C for 24 h. The particle density
information regarding how various chemical treat- of the washed and dried fibers was measured at room
ments adopted for other NFs affect the properties of temperature using a gas pycnometer (Quanta-chrome
fiber reinforced polymers. The purpose of this study is Instruments, Boynton Beach, FL). The average parti-
to investigate the effects of sodium hydroxide and cle densities obtained for untreated, NaOH treated,
sulphuric acid treatments on the properties of RPFs. and H2SO4 treated fiber were 1.50 ± 0.01 g/cm3,
Changes in properties can be used for forensic 1.53 ± 0.01 g/cm3 and 1.52 ± 0.01 g/cm3, respec-
comparison of RPFs to determine fiber origin and tively. A slight positive increase was observed in the
counterfeit as well as ranking the suitability of a given densities of the treated fibers in comparison to
batch of RPFs for making biocomposites. untreated fiber. This increase is primarily due to the
densification of the treated fibers cell wall (Aziz and
Ansell 2004; Hashim et al. 2017).
Materials and methods
Chemical composition
Material
Chemical composition of untreated and chemically
The RPFs used in the present study were obtained treated RPFs were determined using a Ankom 200
from the rainforest region of Nigeria in partially Fiber AnalyzerTM (ANKOM Technology, Macedon,
processed form. Remnant binders sticking to the fibers NY) in accordance with the detergent fiber analysis
were manually removed with 3M ProGrade Precision method developed by Peter Van Soest (Soleimani
3.7 9 9 Sanding Sheets 220 grit papers (3MTM, USA). et al. 2008; Jin et al. 2013). Ankom 200 Method 5
After this, the fibers were soaked in 2% formulated (Ankom Technology 2000), Method 6 (Ankom Tech-
detergent solution for 10 min and cleaned to remove nology 2011) and Method 8 (Ankom Technology
oily substances and other impurities on the fiber 2013) procedures were used to obtain the standard acid
surface. After cleaning, the fibers were dried in an air detergent fiber (ADF), neutral detergent fiber (NDF)
oven at 70 °C for 24 h and subsequently cooled to and acid detergent lignin (ADL) data, respectively.
room temperature before further testing. Fibers used 0.5 g of ground untreated and treated dried fibers was
for chemical composition, density determination, used for each analysis. The difference between ADF
thermal analysis, X-ray diffraction and FTIR analyses and ADL readings gave the cellulose content, the
were ground with Retsch cutting mill SM100 (Retsch, hemicellulose content was based on the difference
Retsch-Allee, Haan) and sieved using a 1 mm screen. between the NDF and ADF readings, while ADL
reading provided the lignin content. The data reported
Chemical treatment in this study for each test are the average values of
three measurements (dry-matter basis).
Some ground RPFs were immersed in 10% w/v
aqueous NaOH solution (with a solution to fiber ratio
of 10 ml to 1 g) at 60 °C for 5 h. The selection of the

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Colour measurements of RPFs mounted specimens were initially polish using 320
(46 lm), 500 (30 lm) and 1200 (15 lm) SiC grit
The natural colour of NF is due to the presence of non- emery papers and followed by fine polishing using
cellulosic constituents (Reddy and Yang 2005); this 2000 (10 lm) and 4000 (5 lm) SiC grit emery papers.
may be affected by chemical treatments thereby Finally, they were polished using 1 lm MD-Nap cloth
leading to improper identification by visual examina- with 1 lm MD-Nap suspension. The polished speci-
tion. Also, since colour is an important property in a mens were gold-coated using an Edwards S150B
product, the colour analysis of the fibers before and sputter coater (BOC Edwards, Burgess Hill, UK) and
after chemical treatments is necessary. Colour mea- imaged in the SEM using an accelerating voltage of
surements were carried out to ascertain the difference 3 kV.
in colour between untreated and treated RPFs. A
HunterLabTM ColorFlex EZ spectrophotometer (Hun- FTIR spectroscopy
ter Associates Laboratory Inc., Reston, VA) with a
port size of 30 mm in diameter was used for the Fourier transform infrared (FTIR) spectroscopy was
measurement. The test was conducted in accordance used to characterize the chemical structures of
with ASTM E1164-12 standard (ASTM E1164-12 untreated and treated RPF in order to determine any
2017) and the determination of whiteness and yellow- structural changes caused by alkaline and acid treat-
ness indices was done according to ASTM E313-15 ments. A Renishaw Raman inVia Reflex Microscope
standard (ASTM E313-15 2015). Approximately 2 g (Renishaw Inc, West Dundee, IL) coupled to a Smiths
of ground untreated and treated dried fibers was used IllumminantIR IITM spectrometer equipped with an all
to determine the Hunter L*, a* and b* coordinates. reflective objective (ARO) and a diamond attenuated
The value of L* coordinate represents the whiteness total reflection (ATR) objective was used for both
component (0 = black, and 100 = white); the a* analyses. The FTIR data were acquired at a resolution
coordinate represents greenness to redness ð a = of 4 cm-1 and 512 scans per sample.
green, and þ a = red); and b* coordinate represents
blueness to yellowness ð b = blue, and þ b = yel- Tensile test
low). Therefore, an increase in L*, a* and b* denotes
more white, red and yellow colours, respectively. The The effect of chemical treatment on the tensile
variation of colour (DE) was estimated in comparison properties of unground RPF was investigated using a
to the raw fiber using Eq. 1 (Soleimani et al. 2008). 5 kN capacity Model 3366 InstronÒ universal testing
h 2  2  2 i0:5 machine (Instron Corp., Norwood, MA). The test was
DE ¼ Lt  L þ at  a þ bt  b ð1Þ conducted at room temperature and a relative humidity
of 35% according to ASTM D3822-14 standard
where the coordinates with subscript t are for treated (ASTM D3822M-14 2014). The crosshead speed used
RPFs, while those without subscripts are for untreated was 1 mm/min and the fiber length used was 45 mm.
RPFs. The whiteness (L*) and chromacity coordinates The diameter of each tested fiber was measured at five
(a* and b*) for each sample were measured in 10 locations along the length and the average diameter
replicates and the average values of the results are obtained was then used in area calculation for tensile
presented. strength determination. To avoid slip from or damage
by the sample grip system of the testing machine, the
Microstructure fibers were covered with tissue papers at both ends and
a cellophane tape was used to fasten them to the fibers.
The microstructures of untreated and chemically
treated RPFs were examined using a Hitachi FE-
SEM SU8010 (Hitachi High-Technologies Corp.,
Tokyo, Japan) scanning electron microscope (SEM).
For the cross-sectional imaging, RPF specimens were
cold mounted using acrylic resin to produce a smooth
Fig. 1 A schematic drawing of a single raffia palm fiber
fiber cross sectional surface for imaging. The cold- prepared for tensile test

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Figure 1 shows a drawing of how each fiber was The diffractometer was operated at 40 kV and 44 mA.
prepared for testing. The measurements were carried out on the Multipur-
Ten fibers were tested for each group of sample (i.e. pose Attachment, with parafocusing mode. A Kb filter
untreated and chemically treated) and the reported (Ni foils) was placed at the receiving end. The
tensile data are the averages of the ten measurements. diffraction patterns were measured from 5° to 50°,
The tensile test data were further analyzed statistically with a scan rate of 0.5° per minute (step size: 0.02°),
by one-way analysis of variance (ANOVA) to deter- for all the samples.
mine if the tensile properties (tensile strength and Assignment of Miller indices to the diffraction
percent elongation) of the fibers were significantly peaks was done with the assistance of Mercury
affected by chemical treatment. The SigmaPlot soft- software (version 4.1.0) program (Bruno et al. 2002;
ware for Windows Version 13 (Systat Software Inc., Macrae et al. 2008; French 2014). The crystal
San Jose, CA) was used in the ANOVA test. information file (.cif) for cellulose Ib, which was
obtained from the Cambridge Crystallographic Data-
Water absorption base with Reference code JINROO01 (cellulose Ib),
was used to simulate representative spectra of cellu-
Water absorption test was carried to determine how lose Ib. The selection of cellulose 1b crystal file for the
chemical treatment affected the water absorption present analysis was because it is the dominant
capability of dry unground RPFs. Several fibers, each cellulose polymorph in land plants (Nishiyama et al.
weighing approximately 0.50 g, were first dried for 2002; Lee et al. 2015; Nam et al. 2016). The
60 h at 70 °C, cooled to room temperature and then parameters used for the simulated XRD patterns were
weighed before immersing in distilled water at room Cu–Ka wavelength of 0.154 nm (1.54056 Å) and full
temperature. The water absorption test was carried out width at half maximum (FWHM) values of 3.0°, 3.5°
based on similar studies (Ramadevi et al. 2012; and 4.0°. The three FWHM values were chosen to
Ronald Aseer et al. 2013; Nayak and Mohanty 2018) determine which one yields a XRD pattern that best
found in literatures on natural fibers by subsequently fits the experimental data for the untreated raffia palm
immersing the dried fibers in a water bath containing fiber. The simulated spectra obtained are shown in
distilled water maintained at room temperature. At Fig. 2. The two crystalline diffraction peaks (1 - 1 0)
different times, five fibers were removed from the and (1 1 0) at 2h * 15.1° and 2h * 16.6°, respec-
water bath, cleaned to remove any water on the fiber tively, coalesce into a single peak at 2h * 15.7° as
surface and reweighed within 30 s to minimize FWHM value increased from 3.0 to 4.0 (French and
evaporation effect. The weight data were collected Santiago Cintrón 2013).
as a function of immersion time until saturation was
reached. The water intake content (WC) of the fibers
(in wt%) was calculated using Eq. 2 (Nayak and
Mohanty 2018).
Wt  W0
WCt ðwt%Þ ¼  100 ð2Þ
W0
where Wt and W0 denote the weight of the fibers after a
specific time, t, and the dry weight of the fibers
respectively.

X-ray diffraction (XRD)

The effect of chemical treatment on crystallinity of

RPFs was investigated using a Rigaku Ultima IV
X-Ray Diffractometer (Rigaku Americas Corporation,
Texas, USA), equipped with a Cu source (1.54056 Å), Fig. 2 Calculated diffraction pattern of crystalline cellulose Ib
a CBO optical, and a Scintillation Counter detector. at FWHM values of 3.0°, 3.5° and 4.0°

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Thermal analysis which could not be quantified using the Ankom 200
Fiber AnalyzerTM. The cellulose content of untreated
The effect of chemical treatment on thermal behavior RPFs is higher than those of wheat straw (43.2%)
of RPFs was studied using both differential scanning (Alemdar and Sain 2008), wheat straw (38–40.8%)
calorimetry (DSC) and thermogravimetric analysis (Bjerre et al. 1996); coconut coir (32.7%) (Jústiz-
(TGA). DSC analysis was done using a model 2910 Smith et al. 2008), banana (43.5%) (Jústiz-Smith et al.
V4.4E TA Instruments modulated differential scan- 2008), and alfa grass (46 ± 3%) (Mabrouk et al. 2012)
ning calorimeter (MDSC) (TA Instruments, New which have been used to fabricate polymer compos-
Castle, DE). Both the untreated and chemically treated ites. Mechanical properties of NF depend strongly on
RPFs were oven-dried at 60 °C for 24 h before the their cellulose content since it provides strength and
test. Each scan was performed under argon gas in an stability to the fibers (Bledzki and Gassan 1999). A
open aluminum pan from room temperature to 400 °C close look at the data in Table 1 shows that neither
at a heating rate of 5 °C/min. Approximately 10 mg of alkaline treatment nor sulfuric acid treatment could
ground untreated and treated RPFs were used and the delignify RPFs completely. Relative to the untreated
measurement was repeated twice to ensure fiber, there was a 22% increase in the cellulose
reproducibility. content, a slight increase (* 3%) in hemicellulose
TGA test was conducted using a TA instruments content, while there was * 8% decrease in lignin
TGA Q5000 operated between room temperature and content after NaOH treatment. On the other hand, after
600 °C at a heating rate of 10 °C/min with a nitrogen H2SO4 treatment, there was a 22% increase in
gas flow rate of 25 mL/min. The main purpose was to cellulose content, roughly 32% increase in lignin
compare the desorption and degradation behaviour of content while the hemicellulose content reduced by
untreated raffia palm fibers with that of chemically 97%. Changes in cellulose, hemicellulose and lignin
treated fibers. About 20 mg of each ground fiber contents of NF subjected to chemical treatments have
sample was used. The mass loss rate (in wt%/°C) for been well documented in the literature (Arsène et al.
each sample was derived from derivative TG (DTG) 2007; Vardhini et al. 2016; Soleimani et al. 2017). The
data. amount of cellulose, hemicellulose and lignin
removed by a chemical treatment depends on the
nature of the fiber, concentration and temperature of
Results and discussion the chemical and the length of treatment time.
Vardhini et al. (Vardhini et al. 2016) reported a 20%
Chemical composition of raffia palm fibers increase in cellulose content and a 50% decrease in
hemicellulose content of banana fibers after treatment
The chemical composition (dry matter basis) of RPFs in 11 g/L solution of NaOH at 90 °C for 2.5 h.
before and after chemical treatments in wt% are Soleimani et al. (Soleimani et al. 2017) reported about
presented in Table 1. Untreated RPFs comprise cellu- 70% increase in cellulose content and about 95%
lose (53 wt%), hemicellulose (13 wt%) and lignin (24 decrease in hemicellulose content after pretreating oat
wt%). The remaining 10 wt% is attributed to other hull fibers with 0.1 N of H2SO4 at 130 °C for 40 min.
components (e.g. pectin, wax, protein, oil, and ash)

Table 1 Chemical composition of untreated and chemically treated raffia palm fibers (dry matter basis)
Fiber Soaking time Cellulose Hemicellulose Lignin Others Dry matter Moisture
(h) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%)

Untreated fiber 0 53.4 12.3 23.8 10.5 93.9 6.1

10% NaOH at 5 65.3 12.7 21.9 0.2 95.2 4.8
60 °C
0.6 M H2SO4 at 2 65.3 0.4 31.3 3.1 98.6 1.4
100 °C

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However, Arsène et al. (Arsène et al. 2007) reported responsible for the natural colours of NF (Reddy and
that the hemicellulose content of banana trunk fibers Yang 2007; Rokbi et al. 2011).
mercerized by boiling in 5% Ca(OH)2 for 1 h followed
by rinsing in deionized water and drying remained Microstructure
practically the same as that of the untreated fibers.
Figure 3 shows typical SEM micrographs of the
Colour of raffia palm fiber transverse section of untreated and treated RPFs.
After chemical treatment, the microstructure of cross-
One of the physical changes accompanying the sections of alkaline (Fig. 3b) and acid (Fig. 3c) treated
chemical treatment of RPFs is a change in colour of RPFs are essentially the same as that of the untreated
the fibers. The results of colour measurements which fiber (Fig. 3a). The surfaces of fibers treated with
were obtained using the Hunter L*, a* and b* NaOH and H2SO4 as shown in Fig. 4, are much
coordinates are presented in Table 2. The value of cleaner, rougher and porous than those of untreated
L* coordinate represents the whiteness component fibers, which is an indication that these chemicals
(0 = black, and 100 = white); the a* coordinate removed wax, protein, pectin, oil and other impurities
represents greenness to redness ð a = green, and from the surfaces of the fibers. It was reported that the
þ a = red); and b coordinate represents blueness to use of chemical treatment led to the removal of non-
yellowness ð b = blue, and þ b = yellow). The cellulosic components and also resulted in changes in
results show that the fiber became 23% darker after both surface chemistry and thermal properties of NFs
alkaline treatment, which is consistent with the results (Gonzalez et al. 1999; Cicala et al. 2010). The removal
obtained by Elenga et al. (Elenga et al. 2013) who of these non-cellulosic materials as well as the
reported that Raphia textilis fiber became darker by increased surface roughness is expected to promote
13% after alkaline treatment. Also, the redness and strong bonding between the fibers and polymer
yellowness of the fibers were reduced respectively by matrices when used in composite manufacture (Kabir
27% and 14% in comparison with the untreated fiber. et al. 2012).
After acid treatment, the fibers became 28% darker;
the redness increased by 17%; while the yellowness FTIR spectroscopy
reduced by 27% in comparison with the untreated
fiber. Furthermore, RPFs that were given H2SO4 The extent of chemical changes associated with the
treatment had brightness that is 6% lower compared to use of alkaline and acid treatments of RPFs was
those subjected to NaOH treatment. The redness of analyzed using FTIR spectroscopy. Typical absor-
acid treated fibers is 60% higher than that of alkaline bance spectra obtained from this study are presented in
treated fibers. However, the yellowness of acid treated Fig. 5 for untreated and treated fibers, with the
fibers is 15% lower than that of alkaline treated fibers. absorbance peaks of interest clearly marked. The
The change in colour of alkaline and acid treated RPFs peaks shown in Fig. 5 have been baseline-corrected
is due mainly to the removal of non-cellulosic and normalized to 2900 cm-1.
constituents of RPFs which are reported to be

Table 2 Variation of colour parameters of raffia palm fibers with NaOH and H2SO4 treatment
Fiber DL* Da* Db* DE

Untreated fiber 51.73 ± 0.55 9.76 ± 0.38 20.98 ± 0.71 0

Alkaline treated fiber 39.86 ± 1.44 7.13 ± 0.13 18.10 ± 0.62 12.49
Acidic treated fiber 37.38 ± 0.41 11.40 ± 0.08 15.30 ± 0.12 15.52
DL* coordinate represents the whiteness component (0 = black, and 100 = white); Da* coordinate represents greenness to redness
ð a = green, and þ a = red); Db* coordinate represents blueness to yellowness ð b = blue, and þ b = yellow); and DE
represents the variation of colour

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Fig. 3 Typical scanning electron microscope micrographs of the transverse section of a untreated, b alkaline treated and c acid treated
raffia palm fibers

Some of the characteristic peaks are summarized in gain in cellulose content after both chemical treat-
Table 3. In general, the spectra of the treated RPFs are ments as presented in Table 1. It is an indication of the
similar to that of the untreated fiber. However, after removal of some alkaline and acid-sensitive compo-
NaOH and H2SO4 treatments, there were reductions in nents of natural raffia palm fibers, thereby increasing
the intensity of certain characteristic peaks in com- the number of hydroxyl groups (Das and Chakraborty
parison with the untreated fiber. 2006). The –OH groups were reported to be involved
The absorption peak at approximately 3380 cm-1 in the formation of hydrogen bonds with carboxyl
in the untreated raffia palm fiber is attributed to O–H groups found on the surface of natural fibers
stretching vibrations in lignin (Kubo and Kadla 2005; (Mwaikambo and Ansell 2002; Hao 2013). The
Xu et al. 2013) and carbohydrate (cellulose and intensity of the absorption peak at approximately
hemicellulose) (Das and Chakraborty 2006; Chen 2900 cm-1 in the untreated fiber, which is attributed to
et al. 2009; Fahma et al. 2010; Ramadevi et al. 2012; C–H and CH2 stretching in hemicellulose, cellulose
Sathishkumar et al. 2014). It indicates the presence of and lignin (Himmelsbach and Akin 1998; Taha et al.
O–H groups in RPFs (Ouajai and Shanks 2005; Tibolla 2007; Tibolla et al. 2014) did not change significantly
et al. 2014). Its peak position shifted to the right to a with chemical treatment as that at 3380 cm-1. The
lower wavenumber (* 3337 cm-1) while its intensity absorption peak at approximately 1730 cm-1 in the
increased after NaOH and H2SO4 treatments. The untreated fiber is attributed to C=O stretching of
increase in intensity can be related to the observed methyl ester and carboxylic acid in pectin (Ouajai and

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Fig. 4 Typical scanning electron microscope micrographs showing the surface of a untreated b alkaline treated and c acid treated raffia
palm fibers

Shanks 2005) or C=O stretching of acetyl and uronic the peak at * 1510 cm-1 in the untreated raffia palm
ester groups in hemicellulose (Cherian et al. 2008; fibers, attributed to C=C stretching of aromatic rings in
Chen et al. 2011; Xu et al. 2013). Its disappearance lignin (Moore and Owen 2001; Colom et al. 2003;
after NaOH treatment, which did not result in signif- Taha et al. 2007; Chen et al. 2011), remained after
icant reduction in hemicellulose content as shown in alkaline and acid treatments. This shows that none of
Table 1, suggests that it was pectin or wax and fats that the treatments was capable of removing lignin com-
was removed. Ouajai and Shanks (Ouajai and Shanks pletely from raffia palm fibers. Chemical treatment
2005) reported that pectin was removed from hemp caused a slight increase in the intensity of the peak
fibers after treatment in 8% NaOH solution at 30 °C at * 1425 cm-1, which is attributed to CH2 symmet-
for 1 h. The absorption peak at approximately ric bending in cellulose (Taha et al. 2007; Yue et al.
1606 cm-1 in the untreated raffia palm fiber is 2012; Xu et al. 2013). The intensity of the absorption
attributed to the adsorbed free water from cellulose peak at 1370 cm-1 in the untreated fiber, attributed to
in the fiber (Carrillo et al. 2004; Tibolla et al. 2014) aliphatic C–H bending in cellulose, hemicellulose and
and it also reveals aromatic ring vibration and C=O lignin (Kondo and Sawatari 1996; Carrillo et al. 2004;
stretching in lignin (Moore and Owen 2001; Kubo and Chen et al. 2010; Xu et al. 2013) increased in the acid
Kadla 2005; Cherian et al. 2008; Xu et al. 2013). Its treated fibers but was reduced in the alkaline treated
intensity decreased slightly with alkaline treatment but fibers. The intensity of the peak at * 1320 cm-1 in
increased slightly with acid treatment. The intensity of the untreated fiber, which is attributed to C–H and C–

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OH stretching in cellulose, hemicellulose and lignin

(Morán et al. 2008), appeared prominently only in the
acid and alkaline treated fibers. An increase in the
intensity of the prominent absorption peak at
1028 cm-1, attributed to C–O deformation in primary
alcohols (Chen et al. 2010), C–H deformation in
guaiacyl with C–O deformation in the primary alcohol
in hardwood lignin (Kubo and Kadla 2005) and C–O,
C–O–C and C=C stretching in cellulose, hemicellu-
lose and lignin (Xu et al. 2013), occurred after acid and
alkaline treatments. The peak at 897 cm-1 in the
untreated fibers, attributed to the presence of cellulose
p-chains and C–H stretching of out of plane aromatic
rings in cellulose and hemicellulose (Colom et al.
2003; Chen et al. 2010), remained after both acid and
alkaline treatments. It is also attributed to the defor-
mation of C–O–C antisymmetric stretch of the glyco-
sidic linkage in pectin (Himmelsbach and Akin 1998).
The intensity of the absorption peak at 770 cm-1,
attributed to C–H out of plane bending in lignin
(Politou et al. 1990; Bilba and Ouensanga 1996;
Morán et al. 2008), was attenuated slightly by
chemical treatment. The presence of an absorption
peak at * 710 cm-1 is an indication that the domi-
nant cellulose polymorph in raffia palm fibers is
cellulose Ib (Persson et al. 1991; Kataoka and Kondo
1998; Elenga et al. 2013).
Fig. 5 Fourier transform infrared spectra between
a 2500–4000 cm-1 and b 650–1900 cm-1 of untreated, alkaline Mechanical properties of raffia palm fibers
and acid treated raffia palm fibers
Typical stress–strain curves obtained for both
O bending vibration in polysaccharides (cellulose and untreated and chemically treated RPFs are presented
hemicellulose) (Le Troedec et al. 2008; Fiore et al. in Fig. 6, while Table 4 summarizes their tensile
2015), increased with both alkaline and acid treat- properties. The profiles of the curves are similar to
ments. The peak around 1236 cm-1 in the untreated those published in the literature for banana fibers
fiber, attributed to the C–O–C stretching in cellulose (Mukhopadhyay et al. 2009); flax, linen and bamboo
and lignin (Morán et al. 2008), reduced after chemical yarns (Yan et al. 2012) and five different natural fibers
treatments. The intensity of the peak at 1160 cm-1 in (Symington et al. 2009). It is seen that the deformation
the untreated fiber, attributed to C–O–C asymmetrical behaviour of both untreated and treated fibers is
stretching in cellulose and hemicellulose (Colom et al. similar. The fibers deformed inelastically at the
2003; Chen et al. 2010; Xu et al. 2013), increased after beginning after which the deformation became mostly
chemical treatments. The fact that chemical treatment elastic until the maximum stress was attained.
caused no shift of this peak to a lower wave number is The initial non-linear deformation behavior can be
an indication that the two treatments did not result in attributed to a collapse of the weak primary cell walls
the conversion of cellulose I to cellulose II (Yue et al. and delamination between the elemental fibers in the
2012). The peak at 1109 cm-1, attributed to C–O–C fiber bundle (de Andrade Silva et al. 2008). RPFs
glycosidic or antisymmetric in-phase ring stretching in possess tensile properties comparable to those
cellulose (Kubo and Kadla 2005; Chen et al. 2010) and reported in the literature for several natural fibers

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Cellulose

Table 3 Main infrared transitions obtained for untreated and treated raffia palm fibers
Wave number (cm-1) Vibration assignment Source

3370–3336 O–H stretching Cellulose, hemicellulose, lignin

2930 C–H, CH2 stretching Cellulose, hemicellulose, lignin
1730 C=O stretching vibration of carboxylic acid and ester groups Hemicellulose, pectin
1606 Aromatic ring vibration ? C=O stretching and H–O–H of water Free water, lignin
1510 C=C aromatic ring stretching Lignin
1425 C–H deformation Lignin
1370 C–H bending Cellulose, hemicellulose, lignin
1320 C–H and C–O bending vibration Cellulose, hemicellulose
1236 C–O–C stretching vibration Cellulose, lignin
1160 C–O–C stretching of ester groups Cellulose, hemicellulose
1109 C–O–C glycosidic stretching and C–OH Cellulose, hemicellulose, lignin
1028 C–O–C stretching ring Hemicellulose
897 C–H deformation and C–O–C glycosidic stretching (b-glycosidic bonds) Cellulose, hemicellulose, pectin
770 C–H out-of-plane bending Lignin

Table 4 Mechanical properties of untreated and chemically

treated raffia palm fibers
Fiber Tensile strength Elongation
(MPa) at break (%)

Untreated fiber 236.1 ± 45.7 2.5 ± 1.9

Alkaline treated fiber 129.3 ± 31.4 2.1 ± 0.8
Acidic treated fiber 26.9 ± 4.9 2.5 ± 0.6

which have been applied in polymer matrix composite

manufacture.
The tensile strength of RPFs is higher than
142.9 MPa and 138.7 MPa reported respectively for
banana and coconut coir fibers (Jústiz-Smith et al. Fig. 6 Typical stress–strain curves obtained for untreated,
2008), 89.9 MPa for bagasse fibers (Shibata et al. alkaline and acid treated raffia palm fibers at room temperature
2005), 146.3 ± 53 MPa for wheat straw fibers (Pan-
thapulakkal et al. 2006) and 19–135 MPa for rice husk The fracture (tensile) strength of a natural fiber
(Chen et al. 2018). It can be seen from Table 4 that depends not only on the strength of its polymer but
after chemical treatment, the tensile strength of also on the distribution and type of existing flaws. It
alkaline and sulfuric acid treated fibers reduced by was previously shown on Fig. 3 that although treat-
47% and 89%, respectively. The decrease in percent of ment of RPFs with NaOH and H2SO4 removed certain
elongation at fracture is not as dramatic. Furthermore, chemical components which may interfere with
the results of one-way ANOVA (Table 5) indicate that bonding to plastics, it certainly made the fiber surface
the reduction in tensile strength with chemical treat- rougher and more porous. The dissolution of hemi-
ments is statistically significant at p values \ 0.05. cellulose during acid treatment could have created
However, change in percent elongation with chemical local disordering and voids in the fiber structure (Chae
treatment is not statistically significant at p val- et al. 2003). These flaws are sources of stress
ues [ 0.05 (Table 5). concentration which degrade the strength of fibers. It
is also possible that the concentration and treatment

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 Cellulose

Table 5 Analysis of variance results of the effect of treatment on tensile strength and percent elongation of raffia palm fibers
Property Source of variation df SS MS F p value

Tensile strength Between groups 2 170,182.9 85,091.4 70.4 0.000

Within groups 23 27,799.7 1208.7
Total 25 197,982.5
Percent elongation Between groups 2 1.0 0.5 0.28 0.760
Within groups 23 42.3 1.8
Total 25 43.3
df degree of freedom, SS sum of squares, MS mean square, F F test statistic, and p value calculated probability. Fiber length used for
tensile test = 45 mm while that used for percent elongation = 25 mm

time and temperature used in the present study, both saturation occurred earlier than in the untreated fibers
NaOH and H2SO4 solutions were able to penetrate into between 106 and 178 h, while the onset of the second
the crystalline regions of the cellulose and degraded saturation occurred later than in the untreated fibers
the inter- and intra-hydrogen bonds between cellulose (between 298 and 494 h). For the acid treated fibers,
molecules and the adjoining crystalline regions (Chae the onset of the first saturation occurred earlier than for
et al. 2003; Suryanto et al. 2014). Reports about the untreated and alkaline treated fibers (between 82
degradation of tensile strength of natural fibers after and 154 h), while the second saturation occurred
chemical treatment abound in the open literature. between 274 and 494 h. The rapid water uptake
Symington et al. (Symington et al. 2009) reported that observed for the fibers at the early stage is attributed to
tensile strengths of flax and abaca fibers reduced with the presence of large lumens at the inner region of the
increasing treatment time in 3% NaOH solution. The fibers (see Fig. 3) which facilitated the rapid absorp-
tensile strains to failure for flax, abaca, kenaf and sisal tion of water by capillary action (Jacob et al. 2005).
fibers also decreased with increasing soaking time in The continued exposure of the fibers to water allowed
3% NaOH. Edeerozey et al. (Edeerozey et al. 2007) the internal pores of the elemental fibers to absorb
reported that increasing alkali concentration from 6 to water and this process occurred much more gradually
9% resulted in subtantial reduction in the tensile than at the initial stage of immersion. This probably
strength of kenaf fibers (from 239 to 165 MPa). Chae led to the second saturation stage. The average
et al. (Chae et al. 2003) reported a continual decrease percentage of water absorbed by the untreated fiber
in the break strength of lyocell fibers with increasing at the first and second saturation stages are 56 wt% and
concentration of alkaline. Similar results were 62 wt%, respectively.
reported for kenaf fibers by Mahjoub et al. (Mahjoub With chemical treatment, the average equilibrium
et al. 2014). They reported a decrease in the tensile water content for both first stage and second stage
strength of kenaf fiber due to increasing concentration saturation processes dropped. For alkaline treated
(5, 7, 10 and 15%) of NaOH solution and immersion fibers, it is 39 wt% for the first stage and 44 wt% for the
time. second stage. Since alkalization did not result in the
removal of either lignin or hemicellulose (see
Water uptake Table 1), it is believed that the observed reduction in
water content is due to the removal of pectin, wax and
Figure 7 shows the water uptake plots obtained for oily components of the fibers. On the other hand, the
untreated and chemically treated fibers. Both the percentage of water absorbed in the acid treated fibers
untreated and treated fibers experienced a two-stage at the first and second saturation stages are 30 wt% and
saturation behaviour during exposure. For the 35 wt%, respectively. Acid treatment removed hemi-
untreated fiber, first saturation occurred between 130 cellulose, pectin, wax and oils as shown in Table 1.
and 202 h and the second occurred between 274 and The further decrease in the maximum absorbed water
494 h. For the alkaline treated fibers, the first content (i.e., second saturation stage water content) in

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Cellulose

Fig. 7 Water absorption

behaviour of untreated,
alkaline and acid treated
raffia palm fibers at room
temperature

the acid treated fibers is believed to be due to the

almost complete removal of hemicellulose (Sam-
pathkumar et al. 2012).

X-ray diffraction

The XRD patterns obtained for the untreated and

treated raffia palm fibers are shown in Fig. 8. They
exhibit three main peaks, with the main peak occurring
at 2h * 22.2° in the untreated fibers. These XRD
patterns are consistent with what were previously
reported for several NFs, particularly that obtained by
Elenga et al. (Elenga et al. 2009) for untreated raffia
textilis fiber. When compared with the calculated Fig. 8 Typical X-ray diffraction spectra obtained for untreated,
pattern for cellulose Ib in Fig. 2, it is seen that the alkaline and acid treated raffia palm fibers
XRD profile generated with FWHM = 4.0° best fits
the experimental XRD obtained for the untreated fiber. cellulose type Ib structure (Yue et al. 2012; French and
The single peak occurring at 2h* 15.7° is caused by Santiago Cintrón 2013; Li et al. 2014), was not
the overlapping of (1 1 0) and (1 - 1 0) peaks because changed by chemical treatment at the level of
the two peaks are relatively broad (Suryanto et al. concentrations used in this study. However, peak
2014; Nam et al. 2016). For this reason, this peak is intensities at 2h * 22.2° increased with chemical
labelled as (1 1 0) ? (1 - 1 0) in Fig. 8 (Bonarski and treatment. To ascertain the effect of chemical treat-
Olek 2011). The two peaks occurring at 2h * 22.2° ment on crystallite size of the cellulose phase, the
and 2h * 34.5° correlate to the reflections from the (2 X’Pert High Score software was used to determine the
0 0) and (0 0 4) crystallographic planes, respectively FWHM values for the (2 0 0) peaks of the untreated
(Bonarski and Olek 2011; Sathitsuksanoh et al. 2011; and treated RPFs (see Table 6). It is noted that the
French 2014; Du et al. 2018). diffraction peak 2h * 22.2° became sharper (i.e. the
The presence of these peaks consistently at prac- FWHM value reduced) with chemical treatment. The
tically the same 2h values shows that the structure of crystallite size for the (2 0 0) peak of each of the tested
the natural cellulose in the tested RPFs, which is of the

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 Cellulose

Table 6 Crystallite size and crystallinity index obtained for hydrolyze the amorphous fraction of cellulose con-
untreated and treated raffia palm fibers tained in NF, thereby leaving a higher fraction of
Material K k (Å) b (°) h (°) D (Å) CI (%) crystalline cellulose (Zafeiropoulos et al. 2002; Le
Troedec et al. 2008; Kaushik et al. 2012; Cai et al.
Cellulose 0.90 1.54056 4.00 22.9 21.56 59.1 2016).
Untreated 0.90 1.54056 2.83 22.2 30.32 54.4
fiber
Thermal analysis
NaOH treated 0.90 1.54056 1.42 22.4 60.51 68.2
H2SO4 0.90 1.54056 1.57 22.4 54.73 72.4
treated
Figures 9 shows the typical DSC curves obtained for
both the untreated and chemically treated RPFs, while
Table 7 summarizes the key reaction peak tempera-
material was determined using the Scherrer Eq. (3) tures. The untreated and chemically treated RPFs
(Nam et al. 2016). exhibit similar DSC profiles. For each fiber sample,
are three main peaks: one endothermic peak and two
Kk exothermic peaks. The broad endotherm is due to
D¼ ð3Þ
b cos h evaporation of water molecules in the fiber (Sara-
where D is the crystallite size, while K, k, b and h are vanakumar et al. 2013). Its enthalpy value and peak
the correction factor, wavelength, FWHM (in rad) and temperature changed with treatment. The two exother-
Bragg angle (i.e. 2h 7 2), respectively. The results are mic peaks are characteristics of natural fibers. Two
summarized in Table 6. The crystallite size calculated exothermic reactions at approximately 340 °C and
using the theoretical FWHM value of 4.0° is added for 475 °C were observed in the DSC thermogram of
comparison. It is seen that crystallite sizes of fibers Akamatsu wood (Tsujiyama and Miyamori 2000). The
treated with NaOH and H2SO4 are greater than that of transition occurring at 340 °C was attributed to
the untreated fiber. The increase in the crystallite size polysaccharides, while that at 475 °C was attributed
of the treated fibers was reported to be the reason for to lignin. In a DSC study of different types of wood
the sharpness of the peaks after chemical treatments biomass, three exothermic peaks were observed at
(Suryanto et al. 2014; Nam et al. 2016). about 280–310 °C, 355–365 °C, and 410–430 °C
The crystallinity index (CI) of the fibers was (Bryś et al. 2016), which were respectively attributed
estimated using Eq. (4) (Segal et al. 1959). to the decomposition of hemicellulose, cellulose, and
lignin. DSC analysis of pure hemicellulose, cellulose
It  Ia and lignin showed peak decomposition temperature at
CI ð%Þ ¼  100 ð4Þ
It approximately 275 °C, 355 °C and 365 °C, respec-
where It is the total intensity at (2 0 0) (located at tively (Yang et al. 2007). In the present study,
2h * 22.2°) and Ia is attributed to the amorphous exothermic reaction peak temperatures occurred at
fraction (i.e. the minimum intensity between (1 1 0) about 275 °C and 352 °C in the untreated, both of
and (2 0 0) peaks) which is located at 2h * 18.5° in which increased to higher values with chemical
the present study. CI values estimated for the tested treatment as shown in Table 6. On the basis of the
materials are shown in Table 6. mentioned previous DSC studies (Tsujiyama and
The apparent crystallinity index (CI) of untreated Miyamori 2000; Yang et al. 2007; Bryś et al. 2016),
RPF is estimated to be 54.4%, which is lower than CI the first exothermic peak is attributed to hemicellulose
values of 66.3% obtained for curaua fiber (Tomczak decomposition while the second peak is pyrolysis of
et al. 2007) and 64% reported for Raffia textilis fiber cellulose.
(Elenga et al. 2009). However, after alkaline and acid It is believed that the removal of non-cellulosic
treatments, the CI values obtained increased to 62.8% components and the resulting increase in cellulose
and 72.4%, respectively. The increase in the crys- content after chemical treatments made the observed
tallinity index of treated RPF can be attributed to the increase in the reaction peak temperatures possible.
observed increase in cellulose content as shown in Removal of non-cellulosic materials resulted in high
Table 1. Alkaline and acid treatments are known to degree of crystalline structural order which, in turn,
imparted high resistance to thermal degradation to the

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Cellulose

Fig. 9 Typical differential scanning calorimetry thermograms obtained for a untreated b alkaline treated and c acid treated raffia palm
fibers

Table 7 Thermal properties of untreated and treated raffia palm fibers obtained from differential scanning calorimetry analysis
Sample Endothermic peak (°C) First exothermic peak (°C) Second exothermic peak (°C)

Untreated fiber 131.5 275.2 352.1

NaOH treated fiber 141.9 294.4 361.7
H2SO4 treated fiber 95.8 302.6 363.8

fibers (Ouajai and Shanks 2005). Hao (Hao 2013) alkaline and acid treated RPFs. The degradation
reported an increase in decomposition temperature of profile of untreated RPFs is characterized by three
cellulose from 357 to 367 °C for hemp fibers after distinct peaks, which is consistent with results
chemical treatment, while Aziz and Ansell (Aziz and reported for other natural fibers (Arias et al. 2013;
Ansell 2004) reported that alkalization treatment Elenga et al. 2013; Dong et al. 2014; Oliveira and
increased the thermal stability of both kenaf and hemp D’Almeida 2014). The first peak at * 66 °C in the
fibers. DTG curve (Fig. 10b) is due to evaporation of
Figure 10 shows TGA results (both weight loss in absorbed water and corresponds to roughly a mass
% and DTG in wt%/°C) obtained for untreated, loss of 5% (Fig. 10a) (Tomczak et al. 2007; Elenga

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 Cellulose

alkaline treatment, there is an increase in the mass loss

of water (27%) as well as in degradation temperatures
of hemicellulose and cellulose. The maximum mass
loss associated with hemicellulose occurred at *
312 °C, while that associated with cellulose degra-
dation occurred at * 353 °C. However, as shown in
Table 1, acid treatment of RPFs considerably reduced
the hemicellulose content of the fibers thereby result-
ing in no mass loss peak temperature for this
component. Similar results of disappearance of the
hemicellulose peak was reported by Dong et al. (Dong
et al. 2014) and Rosa et al. (Rosa et al. 2009) after
alkaline treatment of coir fibers while Elenga et al.
(Elenga et al. 2013) reported similar results for fibers
of Raffia textilis treated with 2.5 wt%, 5 wt% and 10
wt% NaOH. Mass loss due to water evaporation in
acid treated fibers increased to roughly 14%. A
decrease in the degradation temperature of cellulose
can be observed in Fig. 10b.

Conclusions

The effect of alkaline and acid treatments on RPFs

sourced from Nigeria were investigated using different
material characterization techniques. The following
conclusions can be drawn within the scope of this
Fig. 10 Thermal profiles obtained for untreated, alkaline and
study:
acid treated raffia palm fibers. a TGA curves and b DTG curves
1. Chemical treatment with 10 wt% NaOH and
et al. 2013). As temperature increased, the mass loss 0.6 M H2SO4 solutions changed morphological,
rate increased also. The second peak at * 295 °C in thermal and chemical properties of RPFs. It
the untreated fiber is attributed to degradation of removed surface impurities on the fiber. Both
hemicellulose and it accounts for approximately 50% cellulose content and crystallinity index of RPFs
of the total mass loss. A maximum degradation rate increased with treatment.
(mass loss rate) for pure hemicellulose was reported to 2. Alkaline treatment under the conditions used in
be 268 °C (Yang et al. 2007). For tururi fibers, the this study did not mercerize or delignify raffia
maximum mass loss rate occurring at 299 °C was palm fibers. The sulphuric acid treatment used
attributed to degradation of hemicellulose (Oliveira removed hemicellulose substantially, but failed to
and D’Almeida 2014). The third thermal event that remove lignin.
peaked at * 345 °C in the untreated fiber is associ- 3. Structural changes occurred in the non-cellulosic
ated with pyrolysis of cellulose (Yang et al. 2007; components of RPFs after alkaline and acid
Martins et al. 2008; Oliveira and D’Almeida 2014). treatments. Certain chemical groups were
The maximum mass loss reported for pure cellulose removed upon treatments, thus reducing the water
was at 355 °C (Yang et al. 2007), while that reported absorption capacity of the treated fibers.
for tururi fibers occurred at 379 °C (Oliveira and 4. Tensile strength and percent elongation at break of
D’Almeida 2014). RPFs reduced after chemical treatments.
Chemical treatment of raffia palm fibers yielded
mixed results with respect to thermal stability. After

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Cellulose

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technical assistance received from Mr. Jason Maley and Dr.
searching the Cambridge structural database and visualiz-
Jianfeng Zhu of the Saskatchewan Structural Sciences Centre
ing crystal structures. Acta Crystallogr Sect B 58:389–397
(SSSC), University of Saskatchewan, Saskatoon with respect to
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Conflict of interest The authors declare that they have no
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