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Industrial Crops and Products 44 (2013) 192 199
Contents lists available at SciVerse ScienceDirect
Industrial Crops and Products
journa l h o me pag e: www.elsev ier .com
Fabrica s areinfor
Dasong DCivil Engineerin bridge
a r t i c l
Article history:Received 12 SeReceived in reAccepted 6 No
Keywords:Natural bersHemp bersNanocelluloseMechanical
propertyInterface property
ed toed asles (nidatio011ningat thtly. T
by 3diffractogram (XRD) were used to reveal the mechanism of
nanocellulose reinforcement on natural bers.FEG-SEM illustrated
that the nanocellulose treatment had resulted in an effective
distribution of nanocel-lulose along the stria on the surface of
bers, giving rise to a signicant increase in the tensile strengthof
the treated hemp bers. The XRD analysis also showed that the
crystallinity index of the treated bershad increased from 55.17% to
76.39%. X-ray photoelectron spectroscopy (XPS) has been used to
charac-
1. Introdu
Natural available ansteadily risiapplicationand Gassancritical
discrecycling hawith the focincrease in arose muchpublicatione.g.
pulp (Guand compo
The use posite mate2001). Combased bio-c
CorresponE-mail add
0926-6690/$ http://dx.doi.oterize the surface of bers and
attenuated total reectance-fourier transform infrared (ATR-FTIR)
wascarried out to determine the surface chemical reaction in order
to elucidate the interface properties andself-modication mechanisms
of the hemp bers.
2012 Published by Elsevier B.V.
ction
bers (hemp), which are rich in cellulose are abundantlyd easy to
handle and process. Due to low prices and theng performance of
technical and standard plastics, the
of natural bers came to a near-halt from 1940s (Bledzki, 1999;
Mohanty et al., 2005). However, from 1990s, theussion about the
preservation of natural resources ands led to a renewed interest
concerning natural materialsus on renewable raw materials. More
recently, with anenvironmental awareness, exploiting natural bers
has
interest and become of importance. To date, numerouss have
reported about the applications of natural bers,tirrez and del Ro,
2005), ethanol (Kreuger et al., 2011)
site (Ramires et al., 2010).of natural bers to make low cost and
eco-friendly com-rials is a subject of great importance (Bismarck
et al.,pared with glass ber-based composites, natural ber-omposites
display several excellent advantages, e.g. low
ding author.ress: [email protected] (M. Fan).
density, renewable and low cost. However, these natural bers
dis-play their drawbacks, e.g. higher polar and hydrophilic, which
makenatural bers both poorly compatible with polymer and resultin
the loss of mechanical properties upon atmospheric
moistureadsorption (Belgacem and Gandini, 2005). Various treatments
(e.g.physical treatments (Ragoubi et al., 2010), chemical
treatments (Liuet al., 2007), biological treatments (Li et al.,
2009)) on the nat-ural bers have been investigated by researchers
to improve themechanical properties of bers.
New technologies (e.g. nanotechnology, biological
technology)have also recently been employed by researchers to
modify nat-ural bers and can be grouped into three approaches,
namely, (1)soaking; (2) layer-by-layer deposition; and (3)
sonochemical depo-sition. These approaches were mainly developed to
immobilizenanoparticles on the surface of natural bers, which were
used fortextiles in the nishing process. The nanotechnology-based
nishtechniques give rise to new properties, e.g. anti-bacteria (Lee
et al.,2003; Tarimala et al., 2006; Ilic et al., 2009),
self-cleaning (Qi et al.,2007; Uddin et al., 2008; Veronovski et
al., 2009), water repellent(Yu et al., 2007; Tomsic et al., 2008;
Bae et al., 2009) and UV lightblocking (Wang et al., 2005; Mondal
and Hu, 2007; Becheri et al.,2008) to the natural bers and enhance
the performance of nalclothing product (Pasta et al., 2010). The
hemp bers treated with
see front matter 2012 Published by Elsevier
B.V.rg/10.1016/j.indcrop.2012.11.010tion of nanocelluloses from
hemp bercement of hemp bers
ai, Mizi Fan , Philip Collinsg Department, School of Engineering
and Design, Brunel University, Kingston Lane, Ux
e i n f o
ptember 2012vised form 4 November 2012vember 2012
a b s t r a c t
A novel fabrication has been employdeveloped nanocellulose was
then us
The size distribution of nano-particsis (NTA). Results showed
that the ox(29281 nm) and the average size (10ference under eld
emission gun-scan(AFM). Mechanical testing showed thproperties of
natural bers signicanmodied hemp bers were increased/ locate /
indcrop
nd their application for the
, Middlesex UB8 3PH, UK
produce nanocelluloses from natural bers (hemp) and the coupling
agent to modify hemp bers themselves.anocellulose) was measured by
nanoparticle tracking analy-nsonication developed nanocellulose had
wider size range2 nm). Morphologies of nanocellulose displayed a
slight dif-
electron microscopy (FEG-SEM) and atomic force microscopye
nanocellulose modication could improve the mechanicalhe modulus,
tensile stress and tensile strain of nanocellulose6.13%, 72.80% and
67.89%, respectively. FEG-SEM and X-ray
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D. Dai et al. / Industrial Crops and Products 44 (2013) 192 199
193
Table 1Experimental levels of NaOH and NaClO.
Experiment Addition of NaOH (%) Addition of NaClO (%)
Std 1 14 60Std 2Std 3
fungus Ophteristics anthat the ehemp bersrespectively2008)
usedto modify nbiological tcessfully debers to ren
The prefabricate nalulose was distributionphologies oAFM.
Mechied naturawere perfoincrease ofATR-FTIR wof natural to reveal
thmechanism
2. Materia
2.1. Materi
Hemp yaHemp berLtd., UK. Dene diaminhypochloritUnsaturated
2.2. Fabrica
Hemp yaby scissors. of chopped out at 65 Cvarious sodTable 1.
Yieequation:
Yield % = WW
where Wf isand Wn is th
2.3. Modic
2.3.1. DTABHemp
tained 30 mwith pH valand supporhemp bers
hemp bers were dried with vacuum oven at 70 C for 24 h
andconditioned at 20 2 C and 65 2% relative humidity before
uses.
2.3.2. Nanocellulose modication DTA), whraturwere
at 20
nsile
coning c
on . Su
556lengt
1 mNent a
sin a
aturyrenariouanocf dil
weie botin, t
and t, the
ers w
M
AFMf the ry in
oscopA) ws imaent
an ra
R-FT
-FTIometd wied wwas uions:
G-SE
ut 5iamet 60smal10 708 65
iostoma ulmi showed an improved acidbase charac-d resistance to
moisture (Gulati and Sain, 2006); andxural strength and exural
modulus of the modiedpolyester composites were improved by 21% and
12%,. Bismarck et al. (Juntaro et al., 2007; Pommet et al.,
the bacteria Gluconacetobacter xylinus strain BPR 2001atural
bers (hemp bers and sisal bers). By using
echnology, nanosized bacterial cellulose has been suc-posited
around natural bers, and such the adhesion ofewable polymers
improved.sent work employed oxidation/ultrasonication tonocellulose
from hemp bers at rst. Then, the nanocel-used as coupling agent to
treat hemp bers. Size
of nanocellulose was characterized by NTA, and mor-f
nanocellulose were characterized by FEG-SEM andanical properties
and interfacial properties of the mod-l bers were investigated
chiey. FEG-SEM and XRDrmed to reveal the mechanism of tensile
strength
the bers with nanocellulose modication. XPS andere carried out
to investigate the surface propertiesbers coated with unsaturated
polyester with the aime mechanism of interface change and
self-modications.
ls and methods
als
rns were obtained from Shanxi Greenland Textile Ltd.s were
supplied by a Hemp Farm & Fiber Companyodecyltrimethylammonium
bromide (DTAB), ethyl-e tetraacetic acid (EDTA), sodium hydroxide,
sodiume and sodium sulde were supplied by SigmaAldrich.
polyester was obtained from CFS.
tion of nanocellulose
rns were chopped into short bers (length: 0.51 cm)Nanocellulose
was prepared by the oxidation hydrolysisshort hemp bers. The
oxidation hydrolysis was carried, 4 h under continuous agitation
and sonication withium hydroxide and sodium hypochlorite, as shown
inld of nanocellulose was worked out by the following
n
f 100 (1)
the weight of the shorted hemp yarns before hydrolysise weight
of nanocellulose after oxidation.
ation of natural bers
modicationbers (1 g) were soaked in beaker (50 ml), which
con-
The(30 mltempebers tioned
2.4. Te
Themountappliedof cardInstrongauge tion oftreatm
2.5. Re
Unswith stwith vtion; n20 ml o(on theinto thfor 5 m80 C,
coolingthe b
2.6. AF
Thedrop oleft to dA NanCA, USple wainstrum1 Hz sc
2.7. AT
ATRSpectrout anequippof 45
condit20 C.
2.8. FE
Abodish (doven aing. A l DTAB solution 0.05% (by the weight of
dried bers)ue 11. The beaker was then loosely covered with a
glassted in an ultrasonic bath at 60 C for 1 h. After that, the
were washed with distilled water. Finally, the modied
a Zeiss Sup(FEG-SEM).on the surfatrical conduB modied hemp (0.5
g) bers were soaked in beakerich contained 2% nanocellulose
suspension in roome for 10 min. Then, the nanocellulose modied
hemp
dried with vacuum oven at 70 C for 24 h and condi- 2 C and 65 2%
relative humidity before uses.
testing
ditioned individual ber was temporarily xed on theard (Fig. 1)
with adhesive tape. A droplet of glue wasthe center of both sides
of the hole along the lengthbject the test pieces to tensile
strength test by using6 at a crosshead speed of 3 mm/min and with
25 mmh with screw grips (the capacity is 100 N with a resolu-).
About 20 samples were tested for untreatment, DTABnd nanocellulose
treatment.
dsorption measurements
ated polyester, which was ordered from CFS was dilutede until
the volatile content was 95%. Hemp bers (0.5 g)s treatments
(without modication; DTAB modica-ellulose modication) were,
respectively, immersed inuted unsaturated polyester in a glass
bottle. 2% catalystght of unsaturated polyester) of catalyst was
then addedtle. After degassing the compounds with ultrasonic bathhe
temperature was raised from room temperature tohe compounds were
treated for 15 min at 80 C. After
bers were washed with distilled water, and nally,ere dried with
vacuum oven at 60 C for 24 h.
was used to examine the surface of nanocellulose. Asuspension
was deposited onto freshly cleaved mica and
a desiccating capsule with silica gel for a period of 12 h.e
IIIa microscope (Digital Instruments, Santabarbara,
ith a multimode head was used for measurement. Sam-ged in
tapping mode. Height images were recorded. The
was operated with a resonance frequency of 155 kHz,te and a
spring constant of 12103 N m1.
IR
R spectra were recorded on a PerkinElmer Spectrum oneer. After
resin adsorption experiment, the bers with-th nanocellulose
treatment were mounted on an ATRith 3 bounce diamond crystal and an
incident anglesed. The instrument was operated under the
following
4000650 cm1 range; 4 cm1 resolution; 16 scans and
M
0 ml nanocellulose suspension was dropped into petriter 55 mm).
Then, the suspension was dried in vacuumC. A thin nanocellulose lm
was obtained after dry-l piece of the nanocellulose lm was examined
withra 35 VP eld emission scanning electron microscopy
The test pieces were coated with thin layer platinumce in an
Edwards S150B sputter coater to provide elec-ctivity. Following
coating, samples were observed and
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194 D. Dai et al. / Industrial Crops and Products 44 (2013) 192
199
men m
operated atcollected di
FEG-SEMlulose treatwith thin laobserved un
2.9. NTA
Nanoparformed usiSalisbury, Uwas introdnanocelluloscope.
TheBrownian mimage analyover 22 s. Tmaximum pat 10 in the
2.10. XPS
XPS wasaluminum backgroundscans were high-resoluanalyzer paface
normal10 nm. The from their n
O
C= IO
IC S
S
where IO anoxygen andsensitivity f
2.11. XRD
Raw hemlulose mod
tion dvante msed. 42 nmand 4ystal
emp
(I0 0 2I
I0 0 2 peakoth cactioetw
licate
ults
ze disFig. 1. Set-up of single ber test: (a) specimen mount and
(b) test speci
10 kV using the secondary electron mode with imagesgitally.
images of hemp bers without treatment and nanocel-ment were also
been taken. The test pieces were coatedyer platinum according to
the above protocol and thender the same conditions as
previously.
ticle tracking analysis (NTA) experiments were per-ng a digital
microscope LM10 System (NanoSight,K). 1 ml of the diluted sample
(concentration 0.001%)
uced into the chamber by a syringe. The particles ofse in the
sample were observed using the digital micro-
video images of the movement of particles underotion were
analyzed by the NTA, version 1.3 (B196)sis software (NanoSight).
Each video clip was capturedhe detection threshold was xed at 100,
whereas thearticle jump and minimum track length were both set
NTA software.
performed using a VG Escalab 210 system with an
diffraca D8 agraphiwere uof 0.1540 kV The cr(1959)
CI% =
wherelatticesents bof diffrangle b10 rep
3. Res
3.1. Sianode (AlK = 1486.6 eV) operating at 150 W with a
pressure of 5 109 mbar. The low-resolution surveytaken with a 1 eV
step and 50 eV analyzer pass energy;tion spectra were taken with a
0.1 eV step and 50 eVss energy. The angle between X-ray beam and
the sur-
was kept at 0 and the depth of analysis was practicallyatomic
ratio of oxygen-to-carbon (O/C) was calculatedormalized peak areas
as:
C
O(2)
d IC are the normalized integrated area of the peaks for carbon,
respectively SC/SO is the corrected term for theactor.
p bers, DTAB modied hemp bers and nanocel-ied hemp bers were
subjected to a powder X-ray
Fig. 2 plose with vof nanocelluand 29321std 1, std 2Compared
lose fabrica(the acid hacid hydrolthat oxidatThe yield o34.31%
andacterized bFEG-SEM c45.45 nm todifference ticles can bcan be
fouof samples.ounted on the mount (dimensions in mm).
method analysis (PXRD) respectively. For this analysis,ced
Bruker AXS diffractometer, Cu point focus source,onochromator and
2D-area detector GADDS systemThe diffracted intensity of CuK
radiation (wavelength) was recorded between 5 and 40 (2 angle
range) at0 mA. Samples were analyzed in transmission mode.linity
index (CI) was evaluated by using Segal et al.irical method as
follow:
Iam)0 0 2
100 (3)
is the maximum intensity of diffraction of the (0 0 2) at a 2
angle of between 21 and 23, which repre-rystalline and amorphous
materials. Iam is the intensityn of the amorphous material, which
is taken at a 2een 18 and 20 where the intensity is at a minimum.s
were used.
and discussion
tribution and morphologies of nanocelluloseresents the results
of size distribution of nanocellu-arious treatments. According the
NTA, the size rangelose for std 1, std 2 and std 3 is 31281 nm,
38278 nm
nm respectively, the average size of nanocellulose for and std 3
is 100 nm, 112 nm and 103 nm, respectively.with acid hydrolysis
(Morn et al., 2008), nanocellu-ted by oxidationsonication shows
wider size rangeydrolysis gives 560 nm) and higher average size
(theysis gives 30.90 nm). However the NTA results
discloseionsonication also can fabricate nano-scale cellulose.f
nanocellulose for std 1, std 2 and std 3 are 10.72%,
42.02%, respectively (Fig. 2). Std 3 was further char-y FEG-SEM
(Fig. 3(a)) and AFM (Fig. 3(b)). According toharacterization, the
size of nanocellulose ranges from
168 nm. AFM image of nanocellulose shows a slightwith FEG-SEM,
as shown in Fig. 3(b), not only par-e observed in this image but
also rod like of bril
nd. This may be due to the difference of preparation
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D. Dai et al. / Industrial Crops and Products 44 (2013) 192 199
195
nocel
3.2. Mechanbers
3.2.1. MechMechan
were summnanocelluloural bers, raw bers, tlulose
modirespectivelyral bers (O
re w to th
FEG-S natubserrilla
b) cleFEG-
of tFig. 2. Size distribution and picture from NTA video of
na
ical properties of nanocellulose modied natural
anical propertiesical properties of hemp bers with various
treatmentsarized in Table 2. It is apparent that both DTAB andse
treatment enhance the mechanical properties of nat-especially for
nanocellulose treatment, compared withhe modulus, tensile stress
and tensile strain of nanocel-ed hemp bers increase by 36.13%,
72.80% and 67.89%,
therefobe due
3.2.2. The
were ointerbFig. 4(bers. surface. As reported, dislocation is
the weakest link in natu-uajai et al., 2004; Eder et al., 2007; Dai
and Fan, 2011),
and (2) boCompared w
Fig. 3. Morphology of nanocellulose (a) by FEG-SEM (100,000)
lulose (std 1, std 2 and std 3).
e conjecture the increase of mechanical properties maye repair
of dislocation in the bers.
EMral bers before and after nanocellulose modication
ved with FEG-SEM. As shown in Fig. 4(a), impurity andr gap can
be found on the surface of raw hemp bers.arly shows the presence of
nanocellulose around theSEM micrograph shows that nanocellulose
covers thehe bers with two ways, namely, (1) lling in the stria
nding the inter-bril on the surface of hemp bers.ith macro-bers
from nature, nanocellulose possesses
and (b) by AFM (height image).
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196 D. Dai et al. / Industrial Crops and Products 44 (2013) 192
199
Table 2Mechanical properties of modied hemp bers.
Experiment Diameter(m)
C.V. ofdiameter (%)
Modulus(GPa)
C.V. ofmodulus (%)
Tensile stressat break (MPa)
C.V. ofstress (%)
Tensile strainat break (%)
C.V. ofstrain (%)
Unmodied 696.68 9.07 2.29 5.31DTAB modi 735.29 7.65 2.47
9.98Nanocellulo 1203.85 9.25 3.84 5.92
emp bers (magnication: (a) 20,000; (b) 48,000).
higher spec2005; Stensit has a relatfor a singleWang, 2008lulose
on thbers. The hand may leatage of highhydroxyl grril through
elastic modcal perform(2006), lamtion could modicatiolayer,
theseties of S2 laof bers.
3.2.3. XRDX-ray di
of unmodibers. An ehemp bersummarizemajor crystoccurs
fromtallographicbetween 0 crystallinitylulose modis
apparentincreased sion the ber
000
000
000
I002
Hemp fibers
DTAB Modified
Hemp fibers
Nanocellulose
Modified Hemp fibersCI
DTAB modified=65.95%
CIHemp fibers
=55.17%
CINanocellulose modified
=76.39% 46.76 6.75 28.29 9.39 cation 45.10 9.65 29.83 7.95 se
modication 51.39 7.05 38.51 8.44
Fig. 4. FEG-SEM morphologies of untreated (a) and nanocellulose
modied h
ic surface area (up to 170 m2 g1) (Samir et al., 2004,tad et
al., 2008; Wagberg et al., 2008; Habibi et al., 2010),ively high
elastic modulus of 78150 GPa as determined
nanocellulose bril (Guhados et al., 2005; Cheng and; Iwamoto et
al., 2009). Therefore, covering of nanocel-e surface of bers will
introduce new properties ontoigher specic surface area will rough
the bers surfaced to a stronger interface with resin. The second
advan-
3
4
5
ten
sity
(a.
u.) specic surface area is based on the high density ofoups
(Stenstad et al., 2008), which will bond interb-hydrogen bonding.
Moreover, the attaching of higherulus of nanocellulose may lead to
a better mechani-ance for natural bers. As described by Thygesen et
al.ellae with 100 nm thick existed in S2 layer, delamina-be
observed in this layer. Therefore, in the process ofn,
nanocellulose might penetrate into the lamellae in S2
lling will give rise to increase the mechanical proper-yer and
might contribute to the dislocations reparation
ffractogram was used to investigate the crystallinityed, DTAB
modied and nanocellulose modied hempxample of X-ray powder
diffraction spectra from theses is given in Fig. 5. Crystallinity
index analysis wasd in Table 3. It can be seen from Table 3 that
thealline peak of the hemp bers with various treatments
21.77 to 22.63, which represents the cellulose crys- plane (0 0
2, Bragg reection). The minimum intensity
0 2 and 1 0 1 peaks (Iam) is from 18.52 to 19.11. The index for
raw bers, DTAB modication and nanocel-ication is 55.17%, 65.95% and
76.39%, respectively. It
that after modication, crystallinity of hemp bersgnicantly. This
may be due to the removal of impuritys or attributed directly to
attaching nanocellulose.
1
1000
2000In
Fig. 5. X-ray dbers.
3.3. Interfa
Interfacimines the Various me
Table 3Intensity and
Samples
Raw bers DTAB modiNanocellulo
modied 0 20 30 402
I004
I101
I101
Iam
iffractogram of unmodied, DTAB and nanocellulose modied hemp
ce property of nanocellulose modied natural bers
al property of bers is the main factor, which deter-nal
performance of the bers-based composites.
thods (e.g. micro-mechanical techniques (Mandell et al.,
crystallinity of modied hemp bers.
2 () Intensity(a.u)
Crystallinityindex (%)
Iam I0 0 2 Iam I0 0 2
19.11 22.63 1822 4064 55.17ed bers 18.52 21.77 1529 4491
65.95sebers
18.58 21.94 1307 5538 76.39
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D. Dai et al. / Industrial Crops and Products 44 (2013) 192 199
197
Table 4Absorbed resins of raw hemp bers and modied bers.
Samples Absorbed resin (mg/0.5 g bers)
Raw bers 52.05DTAB 33.65Nanocellulose modication 72.35
1980; Gaur and Miller, 1989; Yue et al., 1995), spectroscopic
tech-niques (Zadorecki and Rnnhult, 1986; Hua et al., 1987;
Takaseand Shiraishi, 1989; Felix and Gatenholm, 1991), surface
charac-terization (Gassan et al., 2000; Montes-Morn et al., 2001;
Parket al., 2006)) have been developed for assessing interfacial
property.Especially, for spectroscopic techniques, researchers
always useSoxhlet extraction as pretreatment before FTIR or XPS
characteriza-tion (Park and Kim, 2000; Matuana et al., 2001). In
the present work,we develop a novel method without Soxhlet
extraction pretreat-ment for the measurement of polyester
adsorption on the surfaceof bers and the characterization of ber
surface by FTIR and XPS.The adsorbed unsaturated polyester on the
surface of bers withvarious treaafter nanocfrom 52.05treatment,
bers to 33modicatioresult is in apaper. Namwith resins
XPS is allosic and poFig. 6 showunsaturatedvarious metelements
onand C1s wefrom this gthe O/C atobers/unsaThis value indicating
twith the resis 0.356 anwith the reresults of XPdeveloped cproperty
of
600
O1
Fig. 6. XPS widDTAB and nan
535 530 2922902882862842822800
1000
2000
3000
4000
5000
6000
7000
8000
3 DTAB fibers/Unsaturated
polyester
C1sO1s
2 DTAB-Nanocellulose fibers
/Unsaturated polyester
1 Unsaturated polyester
4 Raw fibers/ Unsaturated
polyester
Inte
nsi
ty /
cps
Binding Energy /eV
Atomic ratio of O/C
1 0.245
2 0.272
3 0.356
4 0.349
Fig. 7. O1s and C1s narrow spectra of unsaturated polyester and
bers with untreat-ment, DTAB and nanocellulose modication immersed
with unsaturated polyester.
ATR-FTIR has been used extensively to investigate the surfaceof
bers as well as the resin adhesion, and spectra subtraction is
in variety of situations, such as an inspection of
incomingaterials, comparison of batches or samples, evaluation ofc
reactionllulo
with wit
attr ATRolyew betai
can anceepord C6ver, nad emay nd Cter. T(a)) wala em1
supned 1 is
0
2
4
6
8
0
2
4
3345Region 1
a
b
of nanocellulose modified fibers
c Unsaturatted polyesteer from surface
of raw fibers
c
b
a
Region 2
360 0tments was summarized in Table 4. Table 4 shows
thatellulose treatment the resin adsorption was increased
mg/0.5 g bers to 72.35 mg/0.5 g bers, but for DTABthe adsorbed
resin was decreased from 52.05 mg/0.5 g.65 mg/0.5 g bers. This
indicates that nanocellulosen can improve the interfacial
properties of bers. Thisgreement with those discussed in 3.2.2 in
this presentely, nanocellulose can increase the interface of
bers.ways used to study the chemical compositions of cellu-lymeric
materials as well as their chemical interactions.s XPS wide scans
spectra for unsaturated polyester,
polyester coated bers, which were pretreated withhods. It can be
seen that oxygen and carbon are the main
the surface of bers. High resolution of spectra at O1sre shown
in Fig. 7. Atomic ratio of O/C also is calculatedure. Nanocellulose
modication results in a decrease inmic ratio, which is 0.272
compared to O/C ratio for rawturated polyester or DTAB
bers/unsaturated polyester.is similar with unsaturated polyester
which is 0.245,hat almost all of the surface of the bers were
coveredin. For DTAB treatment and raw bers, O/C atomic ratiod
0.349, respectively. These results are in agreementsin absorption
measurement as illustrated above. TheS characterization indicates
that the method that havean be used as novel assessment way for the
interface
bers.
532.3 eV
531.5 eV
532.1 eV
531.9 eV
284.7 eV
284.8 eV
284.9 eV
284.5 eVs
Raw fiber s/U nsaturated poly este r
DTAB fibers /Unsatu rated polyes ter
DTAB-Nan ocellu lose fib ers /unsatura tedp olyese r
Unsaturate d po lyester
C1s
useful raw morganisubtrananocecoatedspectramay be
Thetra of pand raMore d(b). Asabsorbvious r(C2
anmoreo(StenstFig. 8 at C2 apolyes(Fig. 9(Tarim1380 cfurtheris
assig989 cm
0.0
0.0
0.0
0.0
0.0
0.1
0.1
0.1
Ab
sorb
ance500 40 0 30 0 20 0 100 0
Binding Energy /eV
e scans spectra of unsaturated polyester and bers with
untreatment,ocellulose modication immersed with unsaturated
polyester.
4000
Fig. 8. ATR-FTlulose modiections, and so on. This present work
employs spectra to subtract unsaturated polyester spectrum from
these modied and un-modied hemps bers which are
unsaturated polyester, then compare these subtractingh raw
unsaturated polyester. The differences spectrumibuted to the effect
of nanocellulose.-FTIR spectra of pure unsaturated polyester (a),
spec-ster subtraction from nanocellulose modied bers (b)ers (c)
after resin coating were presented in Fig. 8.
ls about regions 2 and 3 were shown in Fig. 9(a) andbe seen, the
subtracted spectrum b appears negative
in region 1 (from 3600 to 3345 cm1). According to pre-ts (Kondo,
1997; Singh et al., 2000), free hydroxyl groups) in cellulose were
assigned around 35613358 cm1;anocellulose possesses high density of
hydroxyl groupst al., 2008). The negative absorbance in spectrum
(b) ofbe due to the esterication between hydroxyl groups6 of
nanocellulose and carboxyl groups of unsaturatedhis can be further
proved from the peak at 1426 cm1
hich is assigned with the H C H bending vibrationt al., 2006).
Moreover, the appearance of peak aroundcan be clearly observed in
spectrum a in Fig. 9(a) alsoport this observation. Generally, the
peak at 912 cm1
with C H (in CH CH) out-of-plane bending of styrene, assigned
with C H (in CH CH) out-of-plane bending
Pure unsaturated polyester
Unsaturatedpolyester from surface
Reg ion 33500 3000 2500 2000 1500 1000
Wavenumber /cm-1
IR spectra of pure unsaturated polyester, subtraction from
nanocel-d bers and raw bers.
-
198 D. Dai et al. / Industrial Crops and Products 44 (2013) 192
199
1380
a
a Pure unsaturated polyester
b Unsaturatedpolyester from
surface of nanocellulose
modified fibers
c Unsaturatted polyesteer from
surface of raw fibers
1200
a Pure unsaturated polyester
b Unsaturatedpolyester from
surface of nanocellulose
modified fibers
c Unsaturatted polyesteer from surface of raw fibers
a
Fig. 9. ATR ed b
of unsatura2009), the less styrenepeak appeamodicatioof
modiedtrum b andpolyester is
4. Conclus
Oxidatioduce nanocNTA, FEG-Scomes. Theused as coucation
procconcluded a
(1) The momodierespecti
(2) Nanoceon the inter-b
(3) The cry55.17% of nano
(4) The resi50%, indicationand car
Acknowled
This reseBoard, DepaTP/5/SUS/6
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Fabrication of nanocelluloses from hemp fibers and their
application for the reinforcement of hemp fibers1 Introduction2
Materials and methods2.1 Materials2.2 Fabrication of
nanocellulose2.3 Modification of natural fibers2.3.1 DTAB
modification2.3.2 Nanocellulose modification
2.4 Tensile testing2.5 Resin adsorption measurements2.6 AFM2.7
ATR-FTIR2.8 FEG-SEM2.9 NTA2.10 XPS2.11 XRD
3 Results and discussion3.1 Size distribution and morphologies
of nanocellulose3.2 Mechanical properties of nanocellulose modified
natural fibers3.2.1 Mechanical properties3.2.2 FEG-SEM3.2.3 XRD
3.3 Interface property of nanocellulose modified natural
fibers
4 ConclusionsAcknowledgementReferences