polymers

Article
Low Density Wood-Based Particleboards Bonded
with Foamable Sour Cassava Starch:
Preliminary Studies
Sandra Monteiro 1 , Jorge Martins 1,2 , Fernão D. Magalhães 1 and Luísa Carvalho 1,2, *
1 LEPABE—Faculdade de Engenharia, Universidade do Porto, rua Dr. Roberto Frias, 4200-465 Porto, Portugal;
sandram@fe.up.pt (S.M.); jmmartins@estgv.ipv.pt (J.M.); fdmagalh@fe.up.pt (F.D.M.)
2 DEMAD—Department of Wood Engineering, Polytechnic Institute of Viseu, Campus Politécnico de Repeses,
3504-510 Viseu, Portugal
* Correspondence: lhcarvalho@estv.ipv.pt; Tel.: +351-919-905-176

Academic Editor: Antonio Pizzi

Received: 29 June 2016; Accepted: 29 September 2016; Published: 8 October 2016

Abstract: This work investigates the feasibility of producing low density particleboards using an
adhesive system based on sour cassava starch, taking advantage of its adhesive and self-expansion
properties. Relevant properties of the produced particleboards were evaluated according to European
Standards including: density, internal bond, moisture content and thickness swelling. Low density
particleboards were produced with densities between 207 kg/m3 and 407 kg/m3 . The best
performance corresponded to particleboard with a density of 318 kg/m3 , an internal bond strength
of 0.67 N/mm2 , and a thickness swelling of 8.7%. These values meet the standard requirements of
general purpose lightweight boards for use in dry conditions. Heat post-treatment (24 h at 80 ◦ C) led
to lower internal bond strength, due to retrogradation (recrystallization of amylose and amylopectin
chains upon cooling) causing higher rigidity of the starch binder. However, it showed to have a
significant effect on decreasing the thickness swelling.

Keywords: lightweight; particleboards; sour cassava starch; foam

1. Introduction
According to Mohanty, “sustainability, industrial ecology, eco-efficiency, and green chemistry are
guiding the development of the next generation of materials, products, and processes.” There is a vital
need for development of innovative bio-based products and technologies that are not dependent on
fossil fuel [1]. Biomaterials, obtained partially or entirely from biomass sources, play a relevant role in
this context [2]. European standard EN 309 defines particleboard as a “panel material manufactured
under pressure and heat from particles of wood (wood flakes, chips, shavings, saw-dust and similar)
and/or other lignocellulosic material in particle form (flax shives, hemp shives, bagasse fragments and
similar), with the addition of an adhesive” [3]. Lately, special attention has been given to lightweight
particleboards, in an effort to facilitate handling and transportation. Furthermore, there is a current
trend in furniture design to use high-thickness components, further increasing the demand for materials
with reduced weight. Panels with a density below 600 kg/m3 are defined as lightweight particleboard
(CEN/TS 16368) [4]. One way to decrease the weight of panels is by incorporating low density particles
in the core layer [5]. However, this comes along with decreases in mechanical performance (flexural
strength, internal bond strength, and resistance to axial withdrawal of screws), in the quality of the
finish (coating, edge lamination), and in machinability.
Synthetic formaldehyde-based resins are currently used to produce wood-based particleboards,
due to their low cost and good binder performance. Natural-based alternatives have been reported,

Polymers 2016, 8, 354; doi:10.3390/polym8100354 www.mdpi.com/journal/polymers

Polymers 2016, 8, 354 2 of 11
Polymers 2016, 8, 354 2 of 11

such as
as adhesives
adhesivesbased
basedonontannins, lignin
tannins, andand
lignin their combinations
their [6–8],[6–8],
combinations soy protein [9–12][9–12]
soy protein and starch
and
[13,14].[13,14].
starch Unlike tannins, the otherthe
Unlike tannins, natural
otheradhesives must be combined
natural adhesives must be with a synthetic
combined with acompound,
synthetic
such as phenol-formaldehyde
compound, resin orresin
such as phenol-formaldehyde PMDI (polymeric
or PMDI isocyanate),
(polymeric in order
isocyanate), in ordertotosatisfy
satisfy the
requirements of
requirements of relevant
relevant standards
standards[15].
[15].
Starch is
Starch is one
one of the most abundant
abundant natural
natural polymers
polymers and
and is relatively
relatively inexpensive.
inexpensive. Cereal
Cereal grains
grains
(such as corn and wheat), tubers (such as potato), and roots (such as cassava) are some
(such as corn and wheat), tubers (such as potato), and roots (such as cassava) are some of the commercial of the
commercial
sources sources
of starch for of starch for
industrial industrial exploitation.
exploitation. Starch
Starch consists consists
of two majorof two major
molecular molecular
components,
components, amylose and amylopectin (Figure 1), which can be differentiated
amylose and amylopectin (Figure 1), which can be differentiated by their chemical structure. Theby their chemical
linear
structure.
α-(1 The linear
→4) linked glucanα-(1→4) linked
is called glucan
amylase is called
while amylase
an α-(1 whileglucan
→4) linked an α-(1→4) linked glucan
with 4.2%–5.9% α-(1with
→6)
4.2%–5.9%
branch α-(1→6)
linkages branch linkages is amylopectin.
is amylopectin.

(a) amylose
Figure 1. Molecular structure of (a) amylose and
and (b)
(b) amylopectin.
amylopectin.

Starch has
Starch has excellent
excellent affinity
affinity towards
towards polar polar materials
materials such such as as cellulose,
cellulose, because
because of of the
the many
many
hydroxyl groups,
hydroxyl groups, forming
forming strong
strong adhesive
adhesive bonds bonds [16].
[16]. It is extensively
It is extensively used used in in the form of
the form of binders,
binders,
sizing materials, glues, and pastes [17]. Its current use in particleboard production involves aa
sizing materials, glues, and pastes [17]. Its current use in particleboard production involves
combination with
combination with synthetic
synthetic adhesives,
adhesives, suchsuch as as isocyanates
isocyanates and and urea-formaldehyde
urea-formaldehyderesins resins[18].
[18].
Cassava sour starch is a traditional food ingredient made
Cassava sour starch is a traditional food ingredient made by fermentation and sun drying by fermentation and sun drying ofof
native cassava starch. It shows good expansion upon heating, which
native cassava starch. It shows good expansion upon heating, which makes it widely used in baking. makes it widely used in baking.
Expansion occurs
Expansion occurs after
after starch
starch gelatinization,
gelatinization, as as aa consequence
consequence of of water
water vaporization
vaporization combined
combined with with
appropriate paste fluidity, swelling and solubilization. Presence
appropriate paste fluidity, swelling and solubilization. Presence of carboxylate functional groups, of carboxylate functional groups,
formed during
formed duringfermentation/sun
fermentation/sun drying,
drying, hashasbeen correlated
been correlated withwith
expansion
expansionperformance
performance [19]. Some
[19].
authors
Some studied
authors the production
studied the productionof biodegradable
of biodegradable foam foam
trays trays
basedbasedon cassava starchstarch
on cassava blended with
blended
chitosan
with and Kraft
chitosan and Kraftfiberfiber
[20] [20]
or with sunflower
or with sunflower protein
proteinandand cellulose fiber
cellulose [21].
fiber Cassava
[21]. Cassava starch, in
starch,
combination
in combination withwitha small percentage
a small percentage of urea-formaldehyde
of urea-formaldehyde resin,resin,
has been
has used
been as useda binder in wood-
as a binder in
based particleboards with densities of 650 and
wood-based particleboards with densities of 650 and 750 kg/m [22]. 750 kg/m 3 [22].
3
The world’s
The world’s largest
largest producers
producers of of cassava
cassava are are Africa
Africa with
with 57%57% and and Asia
Asia with
with 31%.
31%. Latin
Latin America
America
and the
and the Caribbean
Caribbean provide
provide 12% 12% ofof the
the world’s
world’s supplysupply [23].
[23]. Approximately
Approximately 60% 60% of of the
the production
production is is
used for human consumption, about 33% for animal feed and 7%
used for human consumption, about 33% for animal feed and 7% for different industries such as textile, for different industries such as
textile,food
paper, paper,andfood and adhesives
adhesives [24]. The[24].usesThe uses ofvary
of cassava cassava vary depending
depending on the continent.
on the continent. While in Asia Whileit
inused
is Asia mostly
it is used mostly ininindustry,
in industry, Africa itsinmain
Africa its main
purpose purposeconsumption.
is human is human consumption.
Even thoughEven though
the cassava
the cassava
world trade world
growstradeaboutgrows36% per aboutyear,36%its per
price year,
has its price has
remained remained
stable and can stable and can
actually actually be
be considered
considered
low low whentocompared
when compared other crops. to It
other
can be crops.
arguedIt can becassava
that arguedcan thatbecassava
used oncan be used
a large scaleonasaalarge
raw
scale as a raw material for different products without compromising
material for different products without compromising its consumption as food or the local ecosystems. its consumption as food or the
local
An ecosystems.
important factorAn thatimportant
contributes factor
to thisthat contributes
observation to this
is that observation
cassava is that cassava
can be produced can be
in low fertility
produced
soils and wherein lowthe fertility
drainagesoilsisand where the
insufficient drainage
[25], unlike is insufficient
corn or potato.[25],
This unlike
allows corn or potato.
taking advantage This
allows taking advantage of currently deteriorated and unused land
of currently deteriorated and unused land for cassava production [23]. In addition, cassava can be for cassava production [23]. In
addition, cassava can be stored for long periods of time [26]. According
stored for long periods of time [26]. According to the report of the United Nations, in some African to the report of the United
Nations, in
countries some
there is aAfrican
political countries
interest inthere
makingis a political
cassava ainterest
drivinginforcemaking cassava
of local a driving
economic growth force of
[27].
local economic growth [27]. Agriculture must be viewed not only
Agriculture must be viewed not only as a means of subsistence but also as a foundation for the as a means of subsistence but also
as a foundation
integrated for the integrated
and sustainable industrial and sustainable
production industrial
of food, energy production
and biosourced of food, energy
materials and
[23,28].
biosourced materials [23,28]. The present work studies the feasibility
The present work studies the feasibility of producing low density particleboards using sour cassava of producing low density
particleboards using sour cassava starch as the main binder, taking advantage of its adhesive and
expansion properties. The resulting 100% natural products were characterized in terms of their
physico-mechanical properties.
Polymers 2016, 8, 354 3 of 11

starch as the main binder, taking advantage of its adhesive and expansion properties. The resulting
100% natural products were characterized in terms of their physico-mechanical properties.

2. Materials and Methods

2.1. Materials
Native and sour cassava starch was purchased at a local supermarket in Porto, Portugal. Chitosan
(molecular weight around 300 kDa, degree of deacetylation > 85%) was supplied by Golden-Shell
Pharmaceutical Co. Ltd (Zhejiang, China). Populus L. fibers, commonly used in medium density
fiber panels (MDF) production, was provided by Valbopan-Fibras de Madeira S.A (Nazaré, Portugal).
Glycerol (≥95%) was supplied by Sigma-Aldrich (Steinheim, Germany). Wood particles with a
moisture content of 4% used for the production of particleboards were supplied by Sonae Indústria
PCDM (Oliveira do Hospital, Portugal).

2.2. Determination of Amylose Content

The amylose content determination was performed by Eurofins (Madrid, Spain). Sample was first
defatted with dichloromethane/methanol and 75% of propanol, and then the starch was solubilized in
2 M sodium hydroxide solution. The amylose content was determined by potentiometric titration with
in-situ formed I2 (from iodate). This procedure is based on the method described by Banks et al. [29].

2.3. Scanning Electron Microscopy

The interior morphology of particleboards was observed by scanning electron microscopy, using
a high resolution (Schottky) Environmental Scanning Electron Microscope with X-ray Microanalysis
and Electron Backscattered Diffraction analysis: Quanta 400 FEG ESEM/EDAX Genesis X4M
(FEI, Hillsboro, OR, USA). Samples were coated with a Au/Pd thin film, by sputtering, using the SPI
Module Sputter Coater equipment. The analysis were performed at CEMUP (Centro de Materiais da
Universidade do Porto, Porto, Portugal).

2.4. Fourier Transform Infrared (FTIR) Spectroscopy

FTIR spectra of the native and sour cassava starch were recorder with a Vertex 70 spectrometer
(Bruker, Karlsruhe, Germany). The absorbance spectra were computed between 4000 and 500 cm−1 at
4 cm−1 resolution. Symmetrical interferograms on 66 scans were co-added for each spectrum.

2.5. Preparation of Binder System

The formulation of the adhesive system is shown in Table 1. Sour cassava starch and distilled
water were mixed first. Chitosan solution, at 5 wt % concentration, was prepared by adding chitosan
to propionic acid solution (6 wt %), and then mixing for 3 h at 60 ◦ C. This solution was then added
to the binder adhesive in the proportion shown in Table 1. Finally, Populus fibers and glycerol were
added and stirring was maintained for 5 min. The adhesive system is a brownish viscous liquid with a
solid content of 38%.

Table 1. Formulation of the adhesive system.

Component Quantity (wt %)

Sour cassava starch 30.5
Distilled water 30.5
Chitosan solution 33.4
Populus fibers 2.8
Glycerol 2.8
Polymers 2016, 8, 354 4 of 11

2.6. Foamability of Sour and Native Cassava Starch

Two formulations were prepared with each starch, as described in Section 2.5. The same amount of
mixture (20 g) was placed in a glass beaker, and heated in an oven at 190 ◦ C during 40 min. The volume
of expansion was measured.

2.7. Particleboard Production

Wood particles were manually blended with the adhesive. The adhesive/wood ratio was 1:1,
based on weight of solid adhesive content and oven dry wood. Single layer mats were hand formed
in square aluminum foil deformable containers (Lusoforma, Mem Martins, Portugal), with initial
dimensions of 220 × 220 × 80 mm3 . A computer-controlled laboratory scale hot-press (homemade at
our laboratory), equipped with a linear variable displacement transducer (LVDT), a pressure transducer
and thermocouples, was used for producing the panels. The platen temperature was set to 190 ◦ C.
The adhesive/wood mixture was placed on the bottom platen, and the top platen was positioned at
25 mm height, during 30 min. Afterwards the top platen was slowly lifted until 28 mm thickness, over
a 6 min period, and the final position maintained for 5 min.
About 12 h after production, part of the particleboards were subjected to heat post-treatment (HPT)
in an oven, at 80 ◦ C for 24 h. The remaining boards were not subjected to any kind of post-treatment.
All boards were conditioned at 20 ◦ C and a relative humidity of 65% until testing. The mass of
wood/binder mixture used to produce the panels with different densities was between 276 g and 725 g.

2.8. Particleboard Characterization

The boards were tested according to the European standards for density (D) (EN 323), internal
bond strength (IB) (EN 319), moisture content (MC) (EN 322) and thickness swelling (TS) (EN 317).
In order to evaluate the variability of the measurements, 5 particleboards were produced from the same
binder formulation and their properties measured. The coefficient of variation (ratio between standard
variation and average value of measurement) obtained for each property were: density—4.0%, internal
bond strength—2.7%, thickness swelling—10.7%, moisture content—7.5%.

3. Results and Discussion

3.1. Foamability of Sour Cassava Starch

The ability of native and sour cassava starches to expand during baking was compared.
The formulation containing sour cassava starch increased about 700% in volume (Figure 2), while
the one containing native starch increased about 200%. Water vaporization combined with good
swellability and paste fluidity of sour cassava starch led to the formation of a foam with good a
expansion ability upon heating, without the need for the addition of expansion agents [19].
Polymers 2016, 8, 354 5 of 11
Polymers 2016, 8, 354 5 of 11

Polymers 2016, 8, 354 5 of 11

Figure
Figure 2. 2. Expansionbehavior
Expansion behaviorofofdifferent
differenttypes
types of
of cassava
cassava starches.
starches.(a,b)
(a,b)Native
Nativecassava starch
cassava starchbefore
before
and after heating, respectively; (c,d) sour cassava starch before and after heating, respectively.
and after heating, respectively; (c,d) sour cassava starch before and after heating, respectively.
Figure 2. Expansion behavior of different types of cassava starches. (a,b) Native cassava starch before
3.2. FTIR andSpectroscopy
after heating,Analysis
respectively; (c,d) sour cassava starch before and after heating, respectively.
3.2. FTIR Spectroscopy Analysis
3.2.Figure
FigureFTIR 3 representsAnalysis
Spectroscopy
3 represents
the FTIR spectra of native and sour cassava starches. The two spectra are
the FTIR spectra of native and sour cassava starches. The two spectra are very
very similar. The absorption peaks at 3291.2 cm−1 and 2930.7 −1cm
−1 can be attributed to O–H and C–H
similar. The absorption
Figure peaks
3 represents theatFTIR
3291.2 cm−1ofand
spectra 2930.7
native andcmsour can
cassavabe attributed
starches. The to O–H and C–H
two spectra arebond
bond stretching, respectively [30]. The absorption at 1645.0 −1 was
cm−1 was assigned as C–O–C stretching
very similar.
stretching, The absorption
respectively [30]. The peaks at−13291.2atcm
absorption −1 and 2930.7
1645.0 cm cm−1assigned
can be attributed
as C–O–C to O–H and C–H
stretching and the
and the absorption peak at 1455.4 cm was attributed to C–H bending.
bond
absorption stretching, respectively − 1 [30]. The absorption at 1645.0 cm −1 was assigned as C–O–C stretching
The peak at 1455.4
absorbances at cm
1149.4was cm−1attributed
and 1077.2tocm C–H bending.
−1 are both assigned as the coupling of C–O, C–C
and the
The absorptionat
absorbances peak at 1455.4
1149.4 cm −1cmand
−1 was attributed
1077.2 cm −1 to
areC–H
both bending.
assigned as the couplingbridge
of C–O, C–C
and O-H bond stretching, bending −1and asymmetric−1 stretching of the C–O–C glycosidic [31].
The absorbances at 1149.4 cm and 1077.2 cm are both assigned as the coupling of C–O, C–C
andTheO-H bond stretching,
absorbance peak at 997.2 bending
cm−1 canand beasymmetric
attributed to stretching
the C–O–Hof the C–O–C
bending and H–C–Hglycosidic bridge
related modes. [31].
and O-H bond stretching, bending −1 canand asymmetric stretching of the C–O–C glycosidic bridge [31].
TheThe
absorbance
peak at peak
860.1 cm at
−1 997.2
can be cm
assigned be
to attributed
C–O–C to the
symmetrical C–O–H
stretchingbending
and and
C-H H–C–H
deformation related
[32]. modes.
The absorbance peak at 997.2 cm−1 can be attributed to the C–O–H bending and H–C–H related modes.
−1 can be assigned to C–O–C symmetrical stretching and C-H deformation [32].
The peak
TheSourat 860.1
peak starch cm
was
at 860.1 cmexpected to showtohigher
−1 can be assigned C–O–Ccarbonyl andstretching
symmetrical carboxyland content than native [32].
C-H deformation starch, as a
SourofSour
result starch
oxidationwas
starch wasexpected
during to showhigher
the fermentation/sun
expected to show higher carbonyl
drying
carbonyl andand
production carboxyl
carboxyl process
contentcontent
[19].
thanSuch than
native native
differences
starch, as starch,
aare,
as however,
a result
result of oxidation
ofnot
oxidation during
visible,during
in thethe
particular fermentation/sun
in terms of thedrying
fermentation/sun drying
expected production
carbonyl
production bandprocess
process at 1735
[19]. [19].
cm
Such −1. Such
Similar
differencesdifferences
results
are,
were
are, obtained
however,
however, not by visible,
not Demiate
visible, inet particular
in particularal. [33] andinof
in terms may
termsbe due
of the
the expected to aexpected
low concentration
carbonyl at 1735 cmof
bandcarbonyl bandsaidatgroups
−1. Similar 1735 not−1 .
resultscm
allowing
were
Similar detection.
obtained
results werebyobtained
Demiate et byal. [33] andetmay
Demiate be due
al. [33] andtomaya low beconcentration
due to a lowofconcentration
said groups not of said
groups The
allowing amylose content
detection.
not allowing detection. of native and sour cassava starches was determined by potentiometric
The The
titration, andamylose
amylose a value content
of 18%
content of of native
(w/w)
native was
andand sour cassava
obtained
sour cassava starches
starcheswas
for both. wasdetermined
determined by by
potentiometric
potentiometric
titration, and a value of 18% (w/w) was obtained for both.
titration, and a value of 18% (w/w) was obtained for both.

Figure 3. 3.
FTIR spectra −1)−1−
) 1spectral
Figure
Figure 3. FTIR FTIR
spectra ofofnative
spectra ofnative
nativeand
and sour
andsour cassava starch
sourcassava starchin
starch inthe (4000–500
the(4000–500
(4000–500 cm
cmcm spectral region.
region.
) spectral region.
Polymers 2016, 8, 354 6 of 11

Polymers 2016, 8, 354 6 of 11

3.3. Physico-Mechanical Properties of Particleboards
3.3. Physico-Mechanical Properties of Particleboards
Figure 4 depicts the particleboards produced with sour cassava starch–based binder. The boards,
shown Figure 4 depicts
in Figure the particleboards
4a, appear rigid and produced
strong when with handled,
sour cassava andstarch–based binder. Thesmell
have no noticeable boards,
after
shown in Figure 4a, appear rigid and strong when handled, and have
cooling. The wood particles show good cohesion and cannot be easily detached. Figure 4b shows no noticeable smell after
cooling.
that The wood
the particles are particles
surrounded show bygood cohesion and cannot
a heterogeneous foam-likebe easily detached.
material, createdFigure 4b shows
by starch that
expansion.
Thethe particles
internal are surrounded
morphology by apanel
of the heterogeneous
is seen morefoam-like
clearlymaterial, created
in the SEM by starch
image expansion.
depicted The 4c.
in Figure
internal morphology of the panel is seen more clearly in the SEM image depicted
The foam fills the voids between the particles and seems to be well adhered to the wood particle in Figure 4c. The
foam fills the voids between the particles and seems to be well adhered to the wood
surfaces. Wood fibers, present in the adhesive formulation, are visible within the foam cell walls. particle surfaces.
TheWood fibers,
binder’s present ability
foaming in the adhesive formulation,
causes separation ofare
thevisible
woodwithin the foam
particles, cell walls.
allowing Thepanel’s
for the binder’slow
foaming ability causes separation of the wood particles, allowing for the panel’s low density,
density, hopefully maintaining good cohesion and therefore guaranteeing acceptable mechanical
hopefully maintaining good cohesion and therefore guaranteeing acceptable mechanical properties.
properties. Chitosan and wood fiber were added to the sour cassava starch formulation in order to
Chitosan and wood fiber were added to the sour cassava starch formulation in order to improve the
improve the foam properties, based on previous evidence found in the literature [20]. In addition to
foam properties, based on previous evidence found in the literature [20]. In addition to the reinforcing
the reinforcing role of wood fiber, highly compatible with the starch matrix, the interaction between the
role of wood fiber, highly compatible with the starch matrix, the interaction between the amino
amino groups
groups of chitosan
of chitosan and the andhydroxyl
the hydroxyl
groups groups of starch
of starch may provide
may provide mechanical
mechanical strengthening
strengthening and
and decreased
decreased water
water solubility.
solubility. TheThe formulation
formulation has yet
has not notbeen
yet been
fully fully optimized
optimized forapplication,
for this this application,
the
thepurpose
purposeofofthethepresent
presentworkworkbeingbeingtotodemonstrate
demonstratethe thefeasibility
feasibility and
and potential
potential of of
lowlow density
density
particleboards
particleboards produced
producedusing usingthis
thistype
typeofofbinder.
binder.

Figure 4. Particleboards produced with sour cassava starch–based binder. (a) Outside appearance; (b)
Figure 4. Particleboards produced with sour cassava starch–based binder. (a) Outside appearance;
close-up detail; (c) SEM image showing wood particles and surrounding foam, 100× magnification.
(b) close-up detail; (c) SEM image showing wood particles and surrounding foam, 100× magnification.
Polymers 2016, 8, 354 7 of 11
Polymers 2016, 8, 354 7 of 11
Polymers 2016, 8, 354 7 of 11
The particleboards were produced from different starting masses of wood/binder mixture, in
The
orderThe to particleboards
particleboards were
were produced
identify an optimal combination
produced from
fromofdifferent
composite
different starting masses
properties.
starting ofofwood/binder
The
masses effect of the mixture,
wood/binder heat in
post-
mixture,
order
treatment
in orderto identify
(HPT
to of an
identify optimal
80 an
°C for 24combination
optimalh) after of composite
production
combination of was alsoproperties.
composite evaluated. The
The effect
properties. resultsofofthe
The effect ofheat
the the post-
density of
heat
post-treatment (HPT of 80 C for 24 h) after production was also evaluated. The results of of
treatment
the final (HPT
dry of 80 °C
particleboardsfor ◦24
are h) after
shown production
in Figure 5, was
as a also evaluated.
function of the The results
expected of
density the density
(ratio of the
the final
dry
density dry
mixture
of theparticleboards
mass
finalto are shown
theparticleboards
dry volume in
areFigure
shown5,to
corresponding asthe
in a function
5, asofadefined
thickness
Figure the expected
function by density
ofthe
the final (ratio
press
expected of the
platen
density
dry mixture
separation
(ratio of theof mass to themass
28 mixture
dry mm). volume corresponding
to the to the thickness
volume corresponding defined defined
to the thickness by the final
by thepress
finalplaten
press
separation of 28 mm).
platen separation of 28 mm).

Figure 5. Density of dry particleboards bonded with sour cassava starch foam. White circles: without
Figure
HPT; 5. Density
5.
FigureblackDensity of
of dry
circles: withparticleboards
dry HPT. Dashedbonded
particleboards bonded with
with sour
line shows sour cassava
cassava starch
coincidence starch foam.
foam.
between White
White circles:
measured circles: without
without
and expected
HPT; black circles: with HPT. Dashed line shows coincidence between measured and expected
HPT; black circles: with HPT. Dashed line shows coincidence between measured and expected
densities. densities.
densities.
minimum value
The minimum value of of the
the density
density obtained
obtained was was215 kg/m33.. Initially
215kg/m Initially the
the densities
densities of the
The minimum
particleboards increase valuewithofthe
theincrease
densityofobtained totalwas
the total mass
mass 215 kg/m
of mixture
of mixture3. Initially the densities of the
used, independent
used, independent of being
particleboards
subjected or notincrease
to the heat with the increase ofThe
post-treatment. themixture
total mass of mixture
expands used, independent
until reaching the top pressofplaten,
being
subjected or not
defines the
which defines to the
the maximum heat post-treatment.
maximum height height of of the The mixture
the particleboard. expands until reaching the
particleboard. The measured values coincide with the top press platen,
which defines
expected
expected ones: the
ones:Greater maximum
Greater mixture
mixture height
mass mass of placed
placedthebetween
particleboard.
between the
the press The measured
press
platen platen values
implies impliescoincide
higher with
higherHowever,
density. the
density.
expected
However,
for expected ones: Greaterabove
fordensities
expected mixture
densities
about mass
above about3 ,350
placed
350 kg/m between
thekg/m 3,the
measured thepress
measuredplaten
densities implies
densities
show higher
show
a negative density.
adeviation.
negative
However,
deviation.
This for expected
This
is a consequence ofdensities
the highofabove
is a consequence amount about
the high 350 kg/m
ofamount
water vapor 3, the measured densities show a negative
of water thatvapor that is within
is retained retainedthewithin
panelthe panel
while it
deviation.
while
stays it stays
inside This is
theinside a consequence
press. the
Afterpress. of the
After
removal, high
removal,
this amount
internal this of water
internal
pressure vapor
pressure
results inthat is retained
a results
springback within
in a effect,
springbackthe effect,
causing panel
the
while it the
causing stays
particleboard inside
particleboard
to expand,the thus
press. Afterthus
to expand,
decreasing removal, this For
decreasing
its density. internal pressure
its density.
expected For results
expected
densities in aaround
springback
densities
above above
550 around
kg/m 3,
effect,
causing
550
this kg/m the
3
actually particleboard
, this actually
tends to cause to expand,
tends to causethus
internal decreasing
internal
bursting, since its
bursting,thedensity.
since theFor
cohesive expected
cohesive
strength ofdensities
strength above
of the
the binder, stillaround
binder, still
warm
550 kg/m
warm
and withand3, this actually tends to cause internal bursting, since the cohesive strength of the binder, still
withmoisture
high high moisture
content,content, is not sufficient
is not sufficient to balance to balance
the internalthe internal stressby
stress caused caused
trapped by
warm and
trappedFigure
vapor. with
vapor.6Figure high moisture
shows6 close-up content,
shows close-up is
imagesimages not sufficient
of twoofboards,
two boards, to balance the
one produced
one produced internal
with with stress
a lowa low caused
initial
initial mass massby
(a),
trapped
(a), vapor.
showing
showing uniform Figure
uniform 6internal
internal shows close-up
morphology,
morphology, images
and and
another of another
two has
that boards,
that one
visiblyhas produced with
visibly delaminated
delaminated a low
due to initial
due tomass
the phenomena the
(a), showing
phenomena
described uniform
described
above (b). aboveinternal(b).morphology, and another that has visibly delaminated due to the
phenomena described above (b).

Figure 6.
Figure 6. Detail of internal
Detail of internal morphology
morphology ofof particleboards:
particleboards:(a)
(a)expected
expecteddensity
densityof
of313
313kg/m
kg/m33,, showing
showing
Figure 6.internal
uniform
uniform Detail ofstructure;
internal internal morphology
structure; expected of
(b) expected
(b) particleboards:
density
density of 550
of (a)3,expected
550 kg/m
kg/m 3
showingdensity
,showing internalofdelamination.
internal 313 kg/m3, showing
delamination.
uniform internal structure; (b) expected density of 550 kg/m3, showing internal delamination.
Polymers 2016, 8, 354 8 of 11

No Polymers 2016, 8, 354

significant difference was found in the equilibrium moisture content of the particleboards. 8 of 11

This was in the range of 10.4% to 12.3% for non-heat-treated boards, and of 8.4% to 11.6% for
No significant difference was found in the equilibrium moisture content of the particleboards.
heat-treated boards.
This was in the range of 10.4% to 12.3% for non-heat-treated boards, and of 8.4% to 11.6% for heat-
The internal
treated boards. bond strength (IB) provides an overall evaluation of the board’s mechanical integrity,
indicating how well
The internal the bond
core material
strength is(IB)bonded together.
provides The IB
an overall values ofof
evaluation thethe
particleboards produced
board’s mechanical
are given in Figure
integrity, 7. Particleboards
indicating how wellnot thesubjected to HPTisshow
core material bonded an initial increase
together. The inIBthe IB, asofexpected
values the
from theparticleboards producedas
increased density, areit given in Figure
promotes more 7. Particleboards
effective internal not subjected
cohesion. to A
HPT show an initial
maximum value of
increase
0.67 N/mm 2 was
in the IB, as expected
attained, correspondingfrom the to aincreased
density of density,
318 kg/m as it 3promotes
. Note thatmore effectivetointernal
according European
cohesion. A maximum value of 0.67 N/mm 2 was attained, corresponding to a density of 318 kg/m3.
Technical Specification CEN/TS 16368, for lightweight particleboards type LP2 (the most demanding)
Note that according to European Technical Specification CEN/TS 16368, for lightweight
with thicknesses between 20 and 25 mm, the minimum requirement for the IB is 0.30 N/mm2 [4].
particleboards type LP2 (the most demanding) with thicknesses between 20 and 25 mm, the
For expected densities above 313 kg/m3 , the IB decreases, due to the higher board density causing
minimum requirement for the IB is 0.30 N/mm2 [4].
vapor entrapment and, densities
For expected as a consequence
above 313 kg/mof the3, resulting internal
the IB decreases, due stress,
to therupture of inter-particle
higher board density causingbonds.
For thevapor
highest expected densities, this ends up leading to full delamination,
entrapment and, as a consequence of the resulting internal stress, rupture of inter-particle as discussed before,
and a virtually
bonds. Fornull the IB. Heatexpected
highest post-treatment
densities,hasthistwo
endsdistinct
up leading effects on delamination,
to full the IB of the as particleboards.
discussed
For expected
before, densities up to 313
and a virtually nullkg/mIB. 3Heat
, it leads to a lower IB.
post-treatment hasHeattwo treatments are used
distinct effects on theforIB
theofphysical
the
particleboards. For expected densities up to 313 kg/m 3, it leads to a lower IB. Heat treatments are used
modification of starch granules, inducing crystalline rearrangement and promoting intramolecular
bonds for
[34].the physical modification of starch granules, inducing crystalline rearrangement and promoting
intramolecular
The actual outcomes bonds of [34].
the treatment are highly dependent on the starch’s botanical origin [35].
The actual outcomes of the treatment are highly dependent on the starch’s botanical origin [35].
In the work presented here, HPT causes some degree of modification in the sour cassava starch that
In the work presented here, HPT causes some degree of modification in the sour cassava starch that
yields a weaker foam structure, probably due to increased brittleness. The heat treatment may be
yields a weaker foam structure, probably due to increased brittleness. The heat treatment may be
inducing retrogradation,
inducing i.e., recrystallization
retrogradation, due to the
i.e., recrystallization duerearrangement
to the rearrangement and intramolecular interactions
and intramolecular
duringinteractions
the expulsion of water. This is observed in the aging of thermoplastic
during the expulsion of water. This is observed in the aging of thermoplastic starch, starch, which is known
to result in increased brittleness [36]. Interestingly, for the higher expected densities,
which is known to result in increased brittleness [36]. Interestingly, for the higher expected densities, the IB obtained
for thetheheat-treated
IB obtained particleboards
for the heat-treated is actually higher
particleboards than forhigher
is actually the non-treated ones. The ones.
than for the non-treated reasons
for thisThe reasons for this
strengthening arestrengthening
not yet clear, are but
not yet
may clear,
be but may be
related to related
the higherto themoisture
higher moisture
content content
of these
boards,ofshortly
these boards, shortly after resulting
after production, production, in resulting
a different in physical
a differentrearrangement
physical rearrangement
of starchofduring
starch the
during
heat treatment. the heat treatment.

FigureFigure 7. Internal
7. Internal bond ofbond of particleboards
particleboards bondedbonded withcassava
with sour sour cassava
starch starch
foam. foam.
WhiteWhite
circles:circles:
Without
Without HPT; black circles:
HPT; black circles: With HPT. With HPT.

The thickness swelling (TS) results are shown in Figure 8. The TS tends to increase with the
The thickness
expected swelling
density, due to(TS) results
higher arecausing
density shownhigher
in Figure 8. absorption.
water The TS tends to increase
However, withis the
this effect
expected density, due to higher density causing higher water absorption. However, this
counterbalanced by the improvement in the internal bond strength, resulting in the dip in TSeffect
for is
counterbalanced by the improvement in the internal bond strength, resulting in the dip in TS for
expected densities between 300 and 350 kg/m3 , where the IB shows a maximum value. Since the
 Polymers 2016, 8, 354 9 of 11

expected densities between 300 and 350 kg/m3, where the IB shows a maximum value. Since the IB
decreases
Polymers 2016, 8, 354 for higher densities, thickness swelling increases again. It must be noted that the values 9 of 11
obtained for the TS can be considered quite low. According to European Standard EN 312, for non-
load-bearing boards for use in humid conditions with thicknesses between 20 and 25 mm, the
maximum
IB decreases acceptable
for higher value for TS
densities, is 13% [37].
thickness For the panel
swelling produced
increases with It
again. a density
must beof 318 kg/mthat
noted 3,
the
which displayed the best IB result, the measured TS is 8.7%. It is important to
values obtained for the TS can be considered quite low. According to European Standard EN 312, note that these boards
are intended for furniture use in dry conditions (standard value not specified).
for non-load-bearing boards for use in humid conditions with thicknesses between 20 and 25 mm,
The heat post-treatment consistently causes a significant decrease in TS. Once again, this may be
the maximum
relatedacceptable value
to the physical for TS is 13%
modifications [37].
that are For the
known panel
to occur produced
in starches withtoaheating
subject density of 318 kg/m3 ,
(increased
which displayed thereduced
crystallinity, best IBhydration,
result, the measured
increased TS is 8.7%.
intramolecular It is important
interaction), to note into
which translate thatreduced
these boards
are intended for power
swelling furniture
[34]. use in dry conditions (standard value not specified).

Figure 8.Figure 8. Thickness

Thickness swelling
swelling of particleboards
of particleboards bonded with
bonded with sour
sourcassava
cassavastarch foam.
starch WhiteWhite
foam. circles:circles:
Without HPT; black circles: With HPT.
Without HPT; black circles: With HPT.
4. Conclusions
The heatLightweight
post-treatment consistently causes a significant decrease in TS. Once again, this may be
particleboards, bonded with an adhesive system, based on sour cassava starch with
related toadded
the physical
chitosan and wood fibers,that
modifications wereare knownwith
produced to occur in starches
densities subject
between 207 kg/mto heating
3 and (increased
407 kg/m 3.

crystallinity,
Thesereduced hydration,
low density increased
values were intramolecular
obtained thanks interaction),
to the good self-foaming whichoftranslate
property the starch,into reduced
which
swelling allows
powerfor the separation of wood particles and the creation of low density domains while
[34].
maintaining good cohesion. Very good internal bond strength and thickness swelling values were
obtained. The best overall performance corresponded to a panel with a density of 318 kg/m3, an IB of
4. Conclusions
0.67 N/mm2, and a TS of 8.7%. Heat post-treatment revealed to not be beneficial in terms of internal
Lightweight
bond strength,particleboards, bondedinwith
but led to a decrease an adhesive
the thickness system, based on sour cassava starch with
swelling.
added chitosan The and
use ofwood fibers,
this 100% wereadhesive
natural produced with
system densities
allows between
for producing low207 kg/m
density 3 and 407 kg/m3 .
particleboards
These lowwith excellentvalues
density performance. Optimization
were obtained of theto
thanks adhesive
the goodformulation and production
self-foaming property conditions
of the starch,
will be the subject of future studies.
which allows for the separation of wood particles and the creation of low density domains while
Acknowledgments:
maintaining good cohesion. This work
Verywas financially
good supported
internal bond by:strength
Project POCI-01-0145-FEDER-006939
and thickness swelling (Laboratory
values were
for Process Engineering, Environment, Biotechnology and Energy—LEPABE) funded by FEDER funds through
obtained. The best overall performance corresponded to a panel with a density of 318 kg/m3 , an IB of
COMPETE2020—Programa Operacional Competitividade e Internacionalização (POCI)—and by national funds
0.67 N/mm 2 , and a TS of 8.7%. Heat post-treatment revealed to not be beneficial in terms of internal
through FCT—Fundação para a Ciência e a Tecnologia. The authors acknowledge to João Pereira for the support
bond strength, but led to atesting.
in physico-mechanical decrease in the thickness swelling.
TheAuthor
use ofContributions:
this 100% natural adhesive
Sandra Monteiro system
conceived andallows forthe
performed producing
experiments,low density
analyzed data particleboards
and wrote
the paper.
with excellent Jorge Martins,Optimization
performance. Fernão D. Magalhães
of theand Luísa Carvalho
adhesive supervised
formulation andtheproduction
experimental conditions
work and will
reviewed the paper.
be the subject of future studies.

Acknowledgments: This work was financially supported by: Project POCI-01-0145-FEDER-006939 (Laboratory
for Process Engineering, Environment, Biotechnology and Energy—LEPABE) funded by FEDER funds through
COMPETE2020—Programa Operacional Competitividade e Internacionalização (POCI)—and by national funds
through FCT—Fundação para a Ciência e a Tecnologia. The authors acknowledge to João Pereira for the support
in physico-mechanical testing.
Author Contributions: Sandra Monteiro conceived and performed the experiments, analyzed data and wrote the
paper. Jorge Martins, Fernão D. Magalhães and Luísa Carvalho supervised the experimental work and reviewed
the paper.
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2016, 8, 354 10 of 11

References and Notes

1. Mohanty, A.K.; Misra, M.; Drzal, T. Sustainable Bio-Composites from renewable resources: Opportunities
and challenges in the green materials world. J. Polym. Environ. 2002, 10, 19–26. [CrossRef]
2. Weiss, M.; Haufe, J.; Carus, M.; Brandão, M.; Bringezu, S.; Hermann, B.; Patel, M.K. A Review of the
Environmental Impacts of Biobased Materials. J. Ind. Ecol. 2012, 16, 169–181. [CrossRef]
3. European Committee for Standardization. Particleboards—Definition and Classification. EN 309, 2005.
4. European Committee for Standardization. Lightweight Particleboards—Specifications. CEN/TS 16368, 2014.
5. Monteiro, S.; Dias, Â.; Martins, J.; Carvalho, L. Synthesis of Multihollow Polyester Particles in Supra- and
Infra-Millimeter Size Ranges by Double Emulsion Process. Polym. Eng. Sci. 2016, 56, 590–597. [CrossRef]
6. Ballerini, A.; Despres, A.; Pizzi, A. Non-Toxic, zero emission tannin-glyoxal adhesives for wood panels.
Eur. J. Wood Wood Prod. 2005, 63, 477–478. [CrossRef]
7. Valenzuela, J.; Leyser, E.V.; Pizzi, A.; Westermeyer, C.; Gorrini, B. Industrial production of pine tannin-bonded
particleboard and MDF. Eur. J. Wood Wood Prod. 2012, 70, 735–740. [CrossRef]
8. Mansouri, N.E.; Pizzi, A.; Salvado, J. Lignin-Based polycondensation resins for wood adhesives. J. Appl.
Polym. Sci. 2007, 103, 1690–1699. [CrossRef]
9. Liu, Y.; Li, K. Chemical modification of soy protein for wood adhesives. Macromol. Rapid Commun. 2002, 23,
739–742. [CrossRef]
10. Liu, Y.; Li, K. Development and characterization of adhesives from soy protein for bonding wood.
Int. J. Adhes Adhes. 2007, 27, 59–67. [CrossRef]
11. Wescott, J.M.; Frihart, C.R.; Traska, E. High-Soy-Containing water-durable adhesives. J. Adhes. Sci. Technol.
2006, 20, 859–873. [CrossRef]
12. Lorenz, L.; Frihart, C.R.; Wescott, J.M. Chromatographic analysis of the reaction of soy flour with
formaldehyde and phenol for wood adhesives. J. Am. Oil Chem. Soc. 2007, 84, 769–776. [CrossRef]
13. Amini, M.H.M.; Hashim, R.; Hiziroglu, S.; Sulaiman, N.S.; Sulaiman, O. Properties of particleboard made
from rubberwood using modified starch as binder. Compos. Part B Eng. 2013, 50, 259–264. [CrossRef]
14. Belgacem, M.; Gandini, A. Monomers, Polymers and Composites from Renewable Resources, 1st ed.; Elsevier:
Oxford, UK, 2008; pp. 321–342.
15. Mansouri, H.R.; Navarrete, P.; Pizzi, A.; Tapin-Lingua, S.; Benjelloun-Mlayah, B.; Pasch, H.; Rigolet, S.
Synthetic-Resin-Free wood panel adhesives from mixed low molecular mass lignin and tannin. Eur. J. Wood
Wood Prod. 2011, 69, 221–229. [CrossRef]
16. Imam, S.H.; Mao, L.; Chen, L.; Greene, R.V. Wood Adhesive from Crosslinked Poly(Vinyl Alcohol) and
Partially Gelatinized Starch: Preparation and Properties. Starch/Stärke 1999, 51, 225–229. [CrossRef]
17. Tharanathan, R.N. Starch—Value addition by modification. Crit. Rev. Food Sci. Nutr. 2005, 45, 371–384.
[CrossRef] [PubMed]
18. Tondi, G.; Wieland, S.; Wimmer, T.; Schnabel, T.; Petutschnigg, A. Starch-Sugar synergy in wood adhesion
science: Basic studies and particleboard production. Eur. J. Wood Wood Prod. 2012, 70, 271–278. [CrossRef]
19. Zhu, F. Composition, structure, physicochemical properties, and modifications of cassava starch.
Carbohydr. Polym. 2015, 122, 456–480. [CrossRef] [PubMed]
20. Kaisangsri, N.; Kerdchoechuen, O.; Laohakunjit, N. Biodegradable foam tray from cassava starch blended
with natural fiber and chitosan. Ind. Crop. Prod. 2012, 37, 542–546. [CrossRef]
21. Salgado, P.R.; Schmidt, V.C.; Ortiz, S.E.; Mauri, A.N.; Laurindo, J.B. Biodegradable foams based on cassava
starch, sunflower proteins and cellulose fibers obtained by a baking process. J. Food Eng. 2008, 85, 435–443.
[CrossRef]
22. Fueangvivat, V.; Jarusombuti, S.; Hiziroglu, S.; Bauchongkol, P. Properties of Sandwich-Type Particleboard
Panels Made from Rubberwood and Eastern Redcedar. For. Prod. J. 2014, 64, 72–76. [CrossRef]
23. Okudoh, V.; Trois, C.; Workneh, T.; Schmidt, S. The potential of cassava biomass and applicable technologies
for sustainable biogas production in South Africa: A review. Renew. Sustain. Energy Rev. 2014, 39, 1035–1052.
[CrossRef]
24. Pandey, A.; Soccol, C.; Nigam, P.; Soccol, V.; Vandenberghe, L.; Mohan, R. Biotechnological potential of
agro-industrial residues. I: Sugarcane bagasse. Bioresour. Technol. 2000, 74, 69–80. [CrossRef]
25. Nassar, N.; Ortiz, R. Cassava improvement: Challenges and impacts. J. Agric. Sci. 2007, 145, 163. [CrossRef]
Polymers 2016, 8, 354 11 of 11

26. Taiwo, K. Utilization Potentials of Cassava in Nigeria: The Domestic and Industrial Products. Food Rev. Int.
2006, 22, 29–42. [CrossRef]
27. Sanginga, M. Root and Tuber Crops (Cassava, Yam, Potato and Sweet Potato). Available
online: http://www.afdb.org/fileadmin/uploads/afdb/Documents/Events/DakAgri2015/Root_and_
Tuber_Crops__Cassava__Yam__Potato_and_Sweet_Potato_.pdf (accessed on 30 September 2016).
28. Tilman, D.; Socolow, R.; Foley, J.; Hill, J.; Larson, E.; Lynd, L.; Pacala, S.; Reilly, J.; Searchinger, T.;
Somerville, C.; et al. Beneficial biofuels-the food, energy, and environment trilemma. Science 2009, 325,
270–271. [CrossRef] [PubMed]
29. Banks, W.; Greenwood, C.T.; Muir, D.D. The characterization of starch and its components. Part 3:
The technique of semi-micro, differentail, potentiometric, iodine titration and the factors affecting it.
Starch/Stärke 1971, 21, 118–124. [CrossRef]
30. Zhang, Y.R.; Wang, X.L.; Zhao, G.M.; Wang, Y.Z. Preparation and properties of oxidized starch with high
degree of oxidation. Carbohydr. Polym. 2012, 87, 2554–2562. [CrossRef]
31. Klein, B.; Vanier, N.L.; Moomand, K.; Pinto, V.Z.; Colussi, R.; Zavareze, E.; Dias, A.R.G. Ozone oxidation of
cassava starch in aqueous solution at different pH. Food Chem. 2014, 155, 167–173. [CrossRef] [PubMed]
32. Van Soest, J.J.G.; Tournois, H.; Wit, D.; Vliegenthart, J.F.G. Short-Range structure in (partially) crystalline
potato starch determined with attenuated total reflectance Fourier-transform IR spectroscopy. Carbohydr. Res.
1995, 279, 201–214. [CrossRef]
33. Demiate, I.M.; Dupuy, N.; Huvenne, J.P.; Cereda, M.P.; Wosiacki, G. Relationship between baking behavior of
modified cassava starches and starch chemical structure determined by FTIR spectroscopy. Carbohydr. Polym.
2000, 42, 149–158. [CrossRef]
34. Zavareze, E.D.R.; Dias, A.R.G. Impact of heat-moisture treatment and annealing in starches: A review.
Carbohydr. Polym. 2011, 83, 317–328. [CrossRef]
35. Gunaratne, A.; Hoover, R. Effect of heat-moisture treatment on the structure and physicochemical properties
of tuber and root starches. Carbohydr. Polym. 2002, 49, 425–437. [CrossRef]
36. Nafchi, A.M.; Moradpour, M.; Saeidi, M.; Alias, A.K. Thermoplastic starches: Properties, challenges,
and prospects. Starch/Stärke 2013, 65, 61–72. [CrossRef]
37. European Committee for Standardization. Particleboards—Specifications. EN 312, 2010.

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