European Polymer Journal 67 (2015) 483–493

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European Polymer Journal

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Xylan – A green binder for wood adhesives

Emelie Norström a, Linda Fogelström a, Petra Nordqvist b, Farideh Khabbaz b, Eva Malmström a,⇑
a
KTH Royal Institute of Technology, School of Chemical Science and Engineering, Department of Fibre and Polymer Technology,
Teknikringen 56-58, SE-100 44 Stockholm, Sweden
b
AkzoNobel, Casco Adhesives AB, P.O. Box 115 38, SE-100 61 Stockholm, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: Wood adhesives are mainly prepared from polymers derived from petroleum-based
Received 30 September 2014 resources. With the increasing concern for the environment, it is necessary to find alterna-
Received in revised form 13 February 2015 tives derived from bio-based resources that can replace petroleum-based polymers. To
Accepted 14 February 2015
enable this transition it is important that the adhesive properties in terms of bond strength,
Available online 23 February 2015
water resistance and heat resistance are similar, and that the alternative can compete in
terms of cost. Hemicelluloses are a byproduct from the pulp industry. From environmental
Keywords:
and economic perspectives it is preferable to utilize all components from wood and
Wood adhesive
Polysaccharide
decrease the amount of low-value byproducts. In this study, hemicelluloses are suggested
Hemicellulose to be used as binders in wood adhesives, why water dispersions of xylan have been pre-
Xylan pared and evaluated. However, xylan itself cannot be used as a wood adhesive due to its
Tensile shear strength limited bonding performance, especially regarding the water resistance. With the addition
Water resistance of dispersing agents, poly(vinyl alcohol) or poly(vinyl amine), and crosslinkers, such as gly-
oxal or hexa(methoxymethyl) melamine, the xylan dispersions demonstrate promising
results. Wood veneers bonded with xylan dispersions and evaluated with ABES,
Automated Bonding Evaluation System, demonstrate a good bond strength and surprising-
ly good water resistance. Several xylan dispersions fulfill the D1 and WATT 91 require-
ments for wood adhesives according to European Standards EN 204 and EN 14257,
exhibiting good bond strength and heat resistance. Xylan dispersed in a poly(vinyl amine)
solution also shows remarkable water resistance and reaches the threshold for the D2 cri-
terion according to European Standard EN 204.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction too expensive. However, petroleum resources are both lim-

Wood adhesives of today are mainly produced from
petroleum-based polymers. These perform very well with
respect to mechanical properties and are not considered
Abbreviations: PVA, poly(vinyl alcohol); PVAm, poly(vinyl amine);
HMMM, hexa(methoxymethyl) melamine; AATMP, trimethylolpropane
triacetoacetate; CA, citric acid; BTCA, butanetetracarboxylic acid; PVAc,
poly(vinyl acetate); pTSA, toluene-4-sulfonic acid monohydrate; ABES,
Automated Bonding Evaluation System; RH, relative humidity.
⇑ Corresponding author. Tel.: +46 8 790 72 25.
E-mail address: mavem@kth.se (E. Malmström).
ited and non-renewable, and with the increasing concern
for the environment, it is necessary to find alternatives
derived from bio-based sources. Furthermore, some of
the petroleum-based adhesives used today contain haz-
ardous chemicals, e.g., formaldehyde, that have a negative
impact on the environment and human health. To enable
the replacement of petroleum-based adhesives with bio-
based alternatives the properties have to be similar, or bet-
ter, and the cost should not be increased. A typical wood
adhesive binder (poly(vinyl acetate), PVAc) cost
approximately 1.5–2 €/kg. Wood adhesives have to possess

http://dx.doi.org/10.1016/j.eurpolymj.2015.02.021
0014-3057/Ó 2015 Elsevier Ltd. All rights reserved.
484 E. Norström et al. / European Polymer Journal 67 (2015) 483–493
sufficient bonding performance as monitored through
determination of bond strength, water resistance and heat
resistance.
Bio-based polymers such as protein from milk, blood
and soy beans have been used as adhesives for centuries
but were replaced by petroleum-based polymers due to
cost and durability [8]. Bio-based polymers such as pro-
teins, tannins, lignins and polysaccharides are today being
explored as possible adhesives due to their relative abun-
dance and promising properties [33]. It has proven difficult
to produce wood adhesives consisting of solely bio-based
polymers, mostly due to their insufficient water resistance
[8]. Therefore, it might be necessary to add small amounts
of additives derived from petroleum to obtain the neces-
sary properties. Another challenge when using bio-based
polymers for commercial applications is their natural var-
iations in characteristics, emanating from locus and
growth conditions, giving rise to differences between
batches due to the type of tree, growth, season, extraction
process, etc. [40]. Proteins extracted from soy bean and
wheat gluten have been studied thoroughly for their adhe-
sive properties [2,4,11,15–21,27–30,39]. Protein adhesives
have shown promising results, but further work is being
conducted to improve the bond strength and water resis-
tance. Another group of polymers, interesting for adhesive
applications, are polysaccharides. Starch is a polysaccha-
ride that is used in paper bonding, especially for packaging
applications, but generally starch does not have sufficient
properties to be used for wood bonding [8]. Modifications
of starch are therefore necessary to obtain the properties
required for wood adhesives. An adhesive with promising
properties was obtained by crosslinking starch and poly
(vinyl alcohol), PVA, with hexa(methoxymethyl)melamine,
HMMM [12,13,38]. The bonded veneers demonstrated
good bond strength but a long press time (15 min), and a
high press temperature (175 °C) was necessary.
Starch has been combined with tannins, resulting in a
wood adhesive with properties similar to commercial
wood adhesives, interesting for plywood applications
[25,26]. Starch has also shown promising results to be used
in particleboard production [41]. Furthermore, vinyl acet-
ate has been grafted from starch using ammonium persul-
fate as initiator [43–45] and further blended with silica
nanoparticles [43] to improve the bond strength and the
water resistance. Wheat flour, containing starch and pro-
teins, has also been studied as a wood adhesive [1].
Gums are another type of polysaccharide that have
shown potential to be used as wood adhesives. Gum dis-
persions such as locust bean gum, guar gum, and tamarind
gum show remarkable results with good bond strength and
heat resistance without any modifications. Locust bean
gum also exhibits very good water resistance. The bonding
performance is comparable with a commercial poly(vinyl
acetate) D2 wood adhesive and it is possible to perform
the bonding with hot-pressing as well as pressing at room
temperature [31].
Hemicelluloses are, after cellulose, the most abundant
polysaccharides on earth. The industrial utilization of
hemicelluloses has so far been modest, compared with
other abundant polysaccharides such as cellulose and
starch. In the pulp industry, significant amounts of
hemicelluloses and lignin are obtained and combusted at
the mill to recover energy. From an environmental and
economic perspective it would be desirable to exploit the
biomass more effectively by utilizing all components in
wood. There is an increasing interest in the biorefinery
concept, where all components in wood are used, and not
only the cellulosic part [34]. Hemicelluloses have a lower
energy value than lignin, it would therefore be more
rational to separate hemicelluloses from lignin prior to
combustion and utilize hemicelluloses for more valuable
applications [7]. It has proven difficult with today’s process
techniques to isolate hemicelluloses in larger quantities,
since its withdrawal affects the overall mass-balance at
the mill. Recently, long-term strategies for the pulp indus-
try have shifted toward an increased awareness of the
potential of the byproducts. If valuable material applica-
tions will be realized, thereby increasing the economic
incentive to isolate hemicelluloses, alterations of the pre-
sent pulp process can be envisioned, such that extraction
of hemicelluloses would be technically and economically
viable [14,32].
Hemicelluloses have received significant interest during
the last decades due to their potential for packaging, such
as barrier films and coatings for food [10,24]. However, the
research on using hemicelluloses as binders in wood adhe-
sives is minor. It has shown to be difficult to form free-
standing films of hemicelluloses without any modifica-
tions, due to poor film-forming ability. An adhesive should
be able to wet, flow and penetrate the wood surface to
some extent in order to form a proper bond [8]. The film-
forming ability is therefore important also for adhesives.
Plasticizers such as sorbitol and glycerol can be used to
enhance the film-forming properties [23]. However, the
addition of a plasticizer will also result in a more hydrophi-
lic film, which could be detrimental for wood-adhesive
applications. Hemicelluloses are hydrophilic by nature,
due to their abundance of hydroxyl groups, and thereby
hygroscopic, which will limit the adhesive properties and
result in a poor water resistance. Interestingly, the numer-
ous hydroxyl groups also gives the possibility for chemical
functionalization. Research efforts to increase the
hydrophobicity of hemicellulose have focused on chemical
modifications such as esterification, etherification, grafting
procedures and crosslinking [10]. Crosslinkers, including
citric acid [35,42], butanetetracarboxylic acid [9,46] and
glyoxal [22], have been used to crosslink hemicelluloses
for applications such as films and foams.
Among hemicelluloses, xylan is the most common, and
it is also the main hemicellulose in hardwood. Potential
sources of xylan are agricultural crops (such as straw, sor-
ghum, sugar cane, corn stalks and cobs), hulls and husks
from starch production as well as forest and pulping waste
products from softwood and hardwood [3].
The aim of this study was to investigate the use of
hemicelluloses as green binders in wood adhesives. In
order to circumvent the difficulties of obtaining industri-
al-grade hemicelluloses, beechwood xylan purchased from
Sigma Aldrich was used. Another reason for choosing a
commercial source of hemicelluloses for this exploratory
research work was to minimize natural variations between
batches. Such variations complicate the evaluation and
 E. Norström et al. / European Polymer Journal 67 (2015) 483–493
render it difficult to draw unambiguous conclusions.
However, it must be taken into account that the beech-
wood xylan purchased from Sigma Aldrich probably has
different properties compared with xylans/hemicelluloses
extracted from pulping processes. The approach in this
study was to disperse xylan in water and evaluate the bond
strength, water resistance and heat resistance. To improve
the adhesion properties, poly(vinyl alcohol) and poly(vinyl
amine) were evaluated as dispersing agents and citric acid,
butanetetracarboxylic acid, glyoxal, hexa(methoxymethyl)
melamine and trimethylolpropane triacetoacetate were
assessed as crosslinkers. A commercial poly(vinyl acetate)-
based wood adhesive, PVAc, was used to benchmark the
experimental results obtained for the dispersions, even
though it is based on a latex system.
2. Experimental
2.1. Materials
Xylan (P90% HPLC) from beechwood; 1,2,3,4-butanete-
tracarboxylic acid, BTCA, toluene-4-sulfonic acid monohy-
drate, pTSA, and citric acid, CA, were purchased from Sigma
Aldrich. Wood veneers and beech-wood panels were kind-
ly supplied by Akzo Nobel, Casco Adhesives AB. Poly(vinyl
alcohol), Poval 217, PVA, was obtained from Kuraray.
LupaminÒ 9095, 20 wt% solution of poly(vinyl amine),
PVAm, with a molar mass of 340,000 g/mol was supplied
by BASF. Glyoxal, 40% w/w aq. soln. was purchased from
Alfa Aesar. Hexa(methoxymethyl)melamine, HMMM, was
kindly supplied by Becker Industrial Coatings AB.
Trimethylolpropane triacetoacetate, AATMP was pur-
chased from Lonza. Hydrochloric acid, for analysis, fuming,
37% solution in water, ACROS Organics™ was purchased
from Fisher Scientific. CascolÒ 3304, a poly(vinyl acet-
ate)-based (PVAc-based) wood adhesive was kindly sup-
plied by Akzo Nobel, Casco Adhesives AB and used as a
reference. Cascol is a thermoplastic wood adhesive, suit-
able for indoor applications.
2.2. Preparation of xylan dispersions
2.2.1. Small-scale dispersions for bonding wood veneers
Xylan from beechwood (1 g) was dispersed in water
(4 ml) to obtain a dispersion with 20 wt% solid content,
X20. The dispersion was stirred with a vortex (genie 2
lab dancer) from Scientific Industries and with a spoon
for approximately 2 min. Xylan dispersions (5 g total) were
prepared with dispersing agents (0.8, 2.4, 4 or 5.6 wt%)
and/or crosslinker (0.8 or 4 wt%). All dispersions contain
20 wt% xylan but have different total solid contents. The
dispersing agent was dissolved (for PVA) or diluted (for
PVAm) in water, where after xylan (1 g) was added to the
solution. Finally, the crosslinker was added when all other
components had been added. All xylan dispersions are pre-
sented in Table S1 in supplementary data. The sample
names are abbreviations of the components in the disper-
sions. Abbreviations in sample name: X = xylan,
G = glyoxal, H = HMMM, C = CA, B = BTCA, A = AATMP. The
number following each abbreviation is the weight% of each
485
component in the final dispersion, exemplified by X20-
PVA4 – where X20 means 20 wt% xylan and PVA4 means
4 wt% PVA and 76 wt% water.
Reference dispersions were also prepared with dispers-
ing agents and crosslinkers but without any addition of
xylan, Table S1 in supplementary data.
The pH of two xylan dispersions was adjusted from 4 to
2 in an attempt to increase the reactivity of the system
with the addition of HCl (0.3 ml, 2 M), yielding the X20-
G4-HCl and X20-G4-PVA4-HCl dispersions. Two xylan dis-
persions, X20-H4-pTSA and X20-H4-PVA4-pTSA, were pre-
pared with 2 wt% pTSA (based on the amount of xylan) in a
similar attempt. The pH decreased from approximately 5 to
4. More details in supplementary data.
A few xylan dispersions containing PVAm and glyoxal
or HMMM as crosslinker were prepared with 15 wt% xylan
content instead of 20 wt% to evaluate if the bonding per-
formance could be improved by decreasing the viscosity.
The proportions of xylan, PVAm and crosslinker were the
same but more water was added to the dispersion. More
details in supplementary data.
2.2.2. Large-scale dispersions for bonding wood panels
Xylan dispersions that were found to have promising
results were further studied in larger scale. Xylan disper-
sions (60 g total) were prepared with dispersing agents
(PVA or PVAm) and crosslinkers (glyoxal, HMMM or
AATMP). The dispersing agent was dissolved (PVA) or
diluted (PVAm) first, and xylan (12 g) was then added to
the solution. All dispersions contain 20 wt% xylan but have
different total solid contents. The crosslinker was added
when all other components had been added. The disper-
sions were stirred with an overhead stirrer at 60 rpm for
15 min at room temperature. The dispersions that were
prepared in large scale are presented in bold text in
Table S1 in supplementary data.
2.3. pH-measurements
The pH of dispersions prepared in small scale were
measured with a pH glass electrode (JENWAY) connected
to a pH meter (3510 pH meter JENWAY). The measure-
ments were performed directly after preparation.
2.4. Xylan composition
The content of the xylan from beechwood purchased
from Sigma Aldrich was determined by ion-exchange chro-
matography. Prior to the analysis, the samples were acid–
hydrolyzed using a two-step technique according to SCAN–
CM 71:09 [36]. Approximately 200 mg xylan was mixed
with 3 ml H2SO4 (72% w/w) and kept in a vacuum desicca-
tor for an hour. Deionized water (84 ml) was added and the
mixture was kept in an autoclave for 60 min at 125 °C. The
obtained solution was filtered through a glass-fiber filter,
yielding a condensate of lignin residue (Klason lignin)
and monosaccharide solution filtrates. The filtrate was
diluted and analyzed with high-performance anion-ex-
change chromatography (Dionex, Sunnyvale, CA, USA)
equipped with pulsed amperometric detector (HPAEC–
PAD) using a CarboPac PA-1 column. The system was
486 E. Norström et al. / European Polymer Journal 67 (2015) 483–493
equilibrated for 7 min with 260 mM sodium hydroxide and
170 mM sodium acetate followed by 100% ultrapure water
for 6 min. Only ultrapure water was used as eluent during
the sample injection at a flow rate of 1 ml/min. A solution
of 300 mM NaOH was added to the column effluent before
the PAD cell at a flow rate of 0.5 ml/min. Five calibration
standards with several concentrations were prepared using
six monosaccharides: xylose, galactose, rhamnose, man-
nose, arabinose, and glucose. Data was processed with
Chromeleon 7.1 software. The Klason-lignin residue was
dried at 105 °C for 12 h and gravimetrically determined.
2.5. Size exclusion chromatography
The xylan from beechwood samples were analyzed
using size exclusion chromatography SEC, (SECcurity
1260, Polymer Standard Services, PSS, Mainz, Germany)
coupled to a refractive index detector (SECcurity 1260,
Polymer Standard Services, Mainz, Germany) thermostated
at 45 °C. Separations were performed using a combined
column set-up with a GRAM pre-column, and two GRAM
1000 analytical columns in series (Polymer Standard
Services, Mainz, Germany) with 0.5 ml/min of dimethyl
sulfoxide, DMSO, (LiBr 0.5% w/w) as mobile phase at
60 °C. The samples (100 ll) were injected with a 65 min
interval. Calibration of the detectors and the column set-
up was performed by injection of pullulan standards
(Polymer Standard Services, Mainz, Germany). Prior to ana-
lysis, all samples were dissolved in DMSO at 70 °C for 48 h.
Data collection and analysis from SEC separations with
light scattering detection was performed using WinGPC
software (Polymer Standard Services, Mainz, Germany).
2.6. Fourier transform infrared spectroscopy (FTIR)
Dispersions were applied on glass substrates using an
applicator (700 lm) and allowed to dry at either 120 °C
for 10 min and further conditioned at 23 °C and 50% relative
humidity or directly at 23 °C and 50% relative humidity pri-
or to analysis. Fourier transform infrared spectroscopy
(FTIR) spectra were recorded on a Perkin–Elmer Spectrum
2000 FT-IR instrument (Norwalk, CT) equipped with a single
reflection (ATR: attenuate total reflection) accessory unit
having a diamond ATR crystal (Golden Gate) from Gaseby
Specac Ltd. (Kent, England). All spectra were normalized
against the specific ATR-crystal adsorption.
2.7. Specimen preparation
2.7.1. Application method 1: veneers
Beech-wood veneers were conditioned at 20 °C and 65%
relative humidity for at least one week before gluing. Veneer
strips (0.6 mm in thickness) were punched with the dimen-
sions (117 mm  20 mm). The extremities of two veneer
strips (5 mm overlap) were bonded with a thin glue line
(360 g adhesive/m2) approximately 2 h after dispersion
preparation. The bonded veneer strips were hot pressed at
120 °C and 0.7 MPa, for 2.5 min in an Automated Bonding
Evaluation System device, ABES II from Adhesive
Evaluation Systems. Ten samples were prepared with each
adhesive. Adhesives that showed excellent bonding
performance were further tested by pressing veneers bond-
ed with the adhesive at lower temperatures, 70 °C or room
temperature. A press temperature of 150 °C was also tested
for the xylan dispersions containing HMMM and PVAm,
more details in supplementary data.
The dispersions containing PVAm and glyoxal or
HMMM were further evaluated as 2-component adhesives.
Three different types of 2-component adhesives (a–c) were
prepared with the same components as in the 1-compo-
nent adhesive, Table S1 in supplementary data. The 2a-
component adhesives were prepared by mixing xylan with
the crosslinker in one vial, and just prior to bonding of the
veneers, PVAm was added. The 2b-component adhesives
were prepared by mixing xylan with PVAm in one vial
and just prior to bonding the veneers, the crosslinker was
added. The 2c-component adhesives were prepared by
mixing xylan and PVAm and applying that mixture on
one side of the veneer and applying the crosslinker on
the other side, before pressing the veneers together.
More details in supplementary data.
A poly(vinyl acetate)-based wood adhesive (PVAc) used
for indoor applications was used as a benchmark.
2.7.2. Application method 2: panels
Wood panels (400 mm  135 mm  5 mm) were condi-
tioned at 20 °C and 65% relative humidity for at least one
week before gluing. The panels were bonded approximate-
ly 2 h after the dispersion preparation. On one side of each
wood panel, adhesive (180 g/m2) was applied. The bonded
wood panels were hot-pressed at 120 °C for 10 min.
2.8. Tensile shear strength measurements
2.8.1. Method 1: veneers
The tensile shear strength of the veneer pieces was
measured using the ABES apparatus. All test pieces were
conditioned for one week at 20 °C and 65% relative humid-
ity. Five pieces were further immersed in water for 3 h at
20 ± 5 °C and allowed to dry again at 20 °C and 65% relative
humidity for a week before tensile shear strength
measurements.
2.8.2. Method 2: panels
All bonded wood panels were conditioned at 20 °C and
65% relative humidity for seven days and cut into test
pieces according to the European Standard EN 204 [5]
and WATT 91 [6] for classification of thermoplastic wood
Table 1
Conditioning methods and the minimum tensile shear strength values to
fulfill the criteria of the durability classes [5,6].
Conditioning method Tensile shear Durability
strength (MPa) class
7 days in standard atmospherea P10 D1
7 days in standard atmospherea, 3 h P8 D2
in water at 20 ± 5 °C, 7 days in
standard atmospherea
7 days in standard atmospherea, 1 h P7 WATT 91
in oven at 80 °C
a
Standard atmosphere means 20 ± 2 °C and 65 ± 5% RH.
 E. Norström et al. / European Polymer Journal 67 (2015) 483–493
adhesives for non-structural applications. The test pieces
were conditioned according to the conditioning method
shown in Table 1. An Alwetron tensile testing machine
(model TCT 50, Lorentzen and Wettre, Sweden) was used to
measure the tensile shear strength. A speed of 50 mm/min
was used and the maximum force was recorded. Five test
pieces were tested for each conditioning method. The
minimum values of tensile shear strength that must be
reached for the classification of thermoplastic adhesives
into the durability classes D1 and D2, according to EN
204 [5] and the strength at elevated temperature WATT
91 [6], are presented in Table 1.
3. Results and discussion
The scope of the present study was to investigate the
possibility of using wood hemicelluloses as binders in
wood adhesives. Even though pulp manufacturers have
expressed significant interest for the use of hemicellulose
in wood adhesives it has not been possible to obtain real-
istic samples in sufficient amounts. Xylan, as a model sub-
stance for hemicelluloses, has therefore been purchased
from Sigma–Aldrich.
The xylan was characterized with respect to sugar con-
tent using ion-exchange chromatography; it was found to
contain mainly xylose (P96%) [37] but traces of arabinose,
galactose, glucose and rhamnose were also found. The lign-
in content, determined by the Klason method, was
approximately 1% by weight. The molar mass was
approximately 10,000 g/mol according to size exclusion
chromatography.
Xylan-water dispersions were prepared and evaluated
as binders in wood adhesives. A dispersion with as high
solid content as possible is preferred in order to obtain
an adhesive joint with sufficient bond strength, while
minimizing the total volume of the dispersion and water
evaporation during hot pressing. However, an adhesive
with too high solid content may be too viscous to spread
Fig. 1. The tensile shear strength measurements of veneers, bonded with xylan dispersed in glyoxal and/or PVA, using the ABES device. The substrates were
conditioned for a week at 20 ± 2 °C and 65 ± 5% RH (dry) and further immersed in water for 3 h at 20 ± 5 °C and allowed to dry at 20 °C and 65% RH (redried)
prior to analysis.
487
efficiently. A water dispersion containing 20 wt% xylan,
denoted X20, has a suitable viscosity and can easily be
spread on wood surfaces, and was selected as the base dis-
persion in this study. Noteworthy, this work does not
entail a thorough study of the dispersion process or the
physical properties of the dispersion, even though they will
also affect the adhesion properties. The bonding perfor-
mance of X20 was evaluated by bonding wood veneers
together using ABES, and after conditioning the tensile
shear strength of the adhesive joint was measured. The
bonded veneers held together under dry conditions and
displayed a low tensile shear strength (2.2 MPa), Fig. 1.
However, all samples delaminated when immersed in
water, demonstrating the anticipated poor water resis-
tance. The bond strength of an adhesive can be enhanced
by improving the film-forming ability and/or by crosslink-
ing the adhesive. In an attempt to improve the bonding
performance of xylan, dispersing agents, PVA or PVAm,
and/or one of the following crosslinkers; glyoxal, HMMM,
AATMP, CA and BTCA were added. Keeping in mind that
none of these compounds originate as side streams from
the forest industry, the ambition is to maintain the xylan
as the main constituent, thus using low amounts of
additives.
Reference dispersions containing either PVA or PVAm
and the crosslinkers, but without xylan, were also prepared
to rule out that the positive effects emanated from the dis-
persing agent and/or crosslinker as such. These reference
dispersions were evaluated with the same method as the
xylan dispersions, but have different solid contents,
Table S1. Wood veneers bonded with the reference disper-
sions exhibited significantly lower bond strengths and
poor water resistances compared with the dispersions con-
taining xylan. Many samples delaminated directly after
hot-pressing. It could be concluded that xylan is a neces-
sary component for these adhesive systems to obtain suffi-
cient adhesion strength.
The addition of 4 wt% PVA to X20 resulted in a smooth
dispersion that was easily spread on the wood surface. The
488 E. Norström et al. / European Polymer Journal 67 (2015) 483–493
Fig. 2. The tensile shear strength measurements of veneers, bonded with xylan dispersed in HMMM and/or PVA, using the ABES device. The substrates were
conditioned for a week at 20 ± 2 °C and 65 ± 5% RH (dry) and further immersed in water for 3 h at 20 ± 5 °C and allowed to dry at 20 °C and 65% RH (redried)
prior to analysis. ⁄ Only one sample was obtained in the press, the rest delaminated.
dry strength of the adhesive joint was slightly improved
but the water resistance was still poor and all wood sub-
strates delaminated in water (X20-PVA4 in Fig. 1).
The effect of crosslinking xylan was also evaluated by
the addition of a typical crosslinker: glyoxal, HMMM, CA
or BTCA to X20. Glyoxal is a dialdehyde that can react with
hydroxyl groups to form hemiacetal groups. By adding gly-
oxal (denoted G in the sample name) to X20, a dispersion
was obtained and readily applied onto wood veneers.
However, no effect on the bonding performance was
observed, X20-G4 in Fig. 1. To evaluate the combined effect
of dispersing agent and crosslinker, PVA as a dispersing
agent and glyoxal as a crosslinker were added to X20 to
afford heterogeneous dispersions, easily applied onto
veneers. The strength of the adhesive was found to
increase substantially. The dry strength of the veneers
bonded with X20-G0.8-PVA2.4 is twice as high compared
with those bonded with X20, (Fig. 1). However, the adhe-
sive still had poor water resistance and all veneers
delaminated in water. A higher concentration of glyoxal
did not change the bonding performance, whereas a higher
concentration of PVA had a large impact on bond strength.
The dry strength improved to 7.5 MPa for X20-G0.8-
PVA5.6, which is even higher than for the commercial,
PVAc-based, wood adhesive. The water resistance was also
significantly improved in the xylan dispersion containing
4 wt% glyoxal with increasing amount of PVA. A bond
strength of 2.7 MPa was obtained after the samples bonded
with X20-G4-PVA5.6 had been immersed in water and
allowed to dry again.
Inspired by the positive effect of the glyoxal crosslinker
we also investigated the effect of HMMM (denoted H in the
sample name), which can react with hydroxyl groups
through methanolysis. The addition of 4 wt% HMMM to
X20 resulted in a dispersion that was easy to apply to the
veneer. However, X20-H4 did not show sufficient bonding
performance, Fig. 2, as many samples delaminated directly
after hot-pressing and only two samples adhered together.
The combined effect of PVA and HMMM is also presented
in Fig. 2. It was found that the bonding performance was
improved; the dry strength increased and the veneers held
together when immersed in water, demonstrating an
enhanced water resistance for all X20-dispersions contain-
ing both HMMM and PVA. The bonding performance could
be further improved by increasing the amount of PVA.
However, an increased amount of HMMM did not give rise
to improved bonding performance.
The addition of CA or BTCA, respectively, to the xylan
dispersions containing PVA did not result in sufficient
bonding performance. The dry strength was only slightly
improved and all samples delaminated when immersed
in water, Figs. S1 and S2 in supplementary data.
Motivated by the positive effects obtained when adding
PVA, we decided to also evaluate the corresponding effect
of PVAm as a dispersing agent for X20. X20-dispersions
becomes gel-like, with a very high viscosity when PVAm
is added, possibly owing to attractive interactions.
Consequently, it is rather difficult to apply and spread
the adhesive on the wood veneer. Surprisingly, even
though the dispersions were heterogeneously applied, the
adhesion strength was improved significantly, Fig. 3.
X20-dispersions containing 0.8, 2.4, 4.0 and 5.6 wt% of
PVAm were studied. A small amount of PVAm, X20-
PVAm0.8 increased the dry strength of the adhesive from
approximately 2 to 3 MPa. The bonding performance was
further improved when the amount of PVAm was
increased. The dispersion X20-PVAm2.4 has a dry strength
of approximately 4 MPa. The veneers held together when
immersed in water and demonstrated a tensile shear
strength of 1.5 MPa in redried state. A larger addition of
PVAm resulted in a very thick dispersion, but the bonding
performance was further improved; X20-PVAm4 showed
similar bonding performance as the commercial PVAc
wood adhesive. Wood veneers bonded with X20-
PVAm5.6 demonstrated tensile shear strength of 8.2 MPa
in dry state and 4.5 MPa after immersion in water and sub-
sequent redrying. The adhesive joint was stronger than the
wood and even resulted in wood failure. This is superior
 E. Norström et al. / European Polymer Journal 67 (2015) 483–493
Fig. 3. The tensile shear strength measurements of veneers, bonded with xylan dispersed PVAm, using the ABES device. The substrates were conditioned for
a week at 20 ± 2 °C and 65 ± 5% RH (dry) and further immersed in water for 3 h at 20 ± 5 °C and allowed to dry at 20 °C and 65% RH (redried) prior to
analysis.
bonding performance compared with the commercial PVAc
adhesive. To rule out that the positive effect was originat-
ing from PVAm only, veneers were bonded with the 20 wt%
solution of PVAm, without xylan. The dry strength was
lower than for the dispersion containing only xylan,
whereas the bond strength of the samples that had been
immersed in water and redried, was higher. Conclusively,
it is the combination of xylan and PVAm that gives rise
to superior adhesion properties.
The promising results using PVAm as dispersing agent
challenged us to investigate, from an environmental point
of view, if it was possible to reduce the press temperature.
The X20-PVAm2.4 and X20-PVAm5.6 dispersions were
evaluated by pressing the veneers at lower temperatures,
70 °C and room temperature (RT). A press temperature of
120 °C was necessary to obtain sufficient bond strength
and water resistance using X20-PVAm2.4. The bond
strength of the veneers bonded with X20-PVAm5.6 and
pressed at room temperature was reduced but was still
as high as the samples bonded at 120 °C with X20-
PVAm2.4. When the samples were pressed at 70 °C the
bond strengths of the dry veneers were similar to the com-
mercial PVAc adhesive. The bond strengths of the redried
samples were, however, slightly lower than those pressed
at room temperature but significantly lower than PVAc.
X20-PVAm was further studied with the addition of
crosslinker: glyoxal, HMMM or AATMP. The addition of
glyoxal and PVAm to the xylan dispersion resulted in even
thicker dispersions. The dispersions containing 2.4 wt%
PVAm, were gel-like, but rather easy to spread on the wood
surface, whereas the dispersions containing 5.6 wt% PVAm
contained lumps and were therefore more difficult to apply
to the wood surface. The tensile shear strengths of the
wood veneers that were bonded with xylan dispersions
containing glyoxal and PVAm are presented in Fig. 4. The
addition of glyoxal to X20-PVAm2.4 did not have a sig-
nificant effect. The addition of glyoxal to X20-PVAm5.6
deteriorated the bonding performance severely in both
the dry state and redried state.
489
The xylan dispersion containing PVAm was further
evaluated with the addition of HMMM as a crosslinker.
The addition of HMMM results in highly viscous, heteroge-
neous, dispersions which makes them difficult to apply to
the wood surface. The tensile shear strengths of the
veneers bonded with xylan dispersions containing
HMMM and PVAm are presented in Fig. 5. The addition
of a small amount of HMMM had a minor effect on the
bonding performance of the xylan dispersion containing
2.4 wt% PVAm. A larger addition of HMMM, results in
improved water resistance with an increased bond
strength in the redried state, from 1.5 MPa to 2.5 MPa.
Surprisingly, the addition of HMMM to the xylan disper-
sion containing 5.6 wt% PVAm slightly reduced the dry
strength of the bonded veneers. The water resistance of
the xylan dispersion with 5.6 wt% PVAm was unchanged
with the addition of HMMM.
AATMP is an acetyl acetonate trimer used for the
modification of adhesives, sealants, and coatings. It can
act as a crosslinker and reacts with amines such as those
of PVAm to form a crosslinked material. Khosravi et al.
used AATMP to crosslink wheat gluten to improve the
bonding performance of a wood adhesive for particleboard
application [17]. An addition of AATMP (denoted A in the
sample name) to the xylan-PVAm dispersions gave highly
viscous heterogeneous dispersions, but they were still pos-
sible to spread on the veneers. The tensile shear strengths
of the wood veneers that were bonded with xylan disper-
sions containing AATMP and PVAm are presented in
Fig. 6. By adding AATMP to the xylan dispersion with
2.4 wt% PVAm, the bonding performance was considerably
improved. The tensile shear strength of the veneers bonded
with X20-A0.8-PVAm2.4 was above 6 MPa, compared with
approximately 4 MPa for X20-PVAm2.4. The bond strength
of the veneers that were redried after water immersion
increased from approximately 1.5 MPa to approximately
4 MPa with the addition of 0.8 wt% AATMP. The water
resistance was further improved by increasing the amount
of AATMP to 4 wt% (X20-A4-PVAm5.6). The bonding
490 E. Norström et al. / European Polymer Journal 67 (2015) 483–493

Fig. 4. The tensile shear strength measurements of veneers, bonded with xylan dispersed in glyoxal and/or PVAm, using the ABES device. The substrates
were conditioned for a week at 20 ± 2 °C and 65 ± 5% RH (dry) and further immersed in water for 3 h in water at 20 ± 5 °C and allowed to dry at 20 °C and
65% RH (redried) prior to analysis.

Fig. 5. The tensile shear strength measurements of veneers, bonded with xylan dispersed in HMMM and/or PVAm, using the ABES device. The substrates
were conditioned for a week at 20 ± 2 °C and 65 ± 5% RH (dry) and further immersed in water for 3 h at 20 ± 5 °C and allowed to dry at 20 °C and 65% RH
(redried) prior to analysis. ⁄ Only one sample was obtained in the press, the rest delaminated.

performance deteriorated when veneers were bonded with
X20-A0.8-PVAm5.6 and X20-A4-PVAm5.6 instead of X20-
PVAm5.6.
In conclusion, the addition of PVAm to the xylan disper-
sion remarkably improves the tensile shear strength of the
adhesive. The addition of glyoxal reduces the bond
strength and water resistance of the adhesives whereas
HMMM and AATMP can improve the bonding performance
for the dispersions containing 2.4 wt% PVAm. However,
HMMM and AATMP does not have any positive effect on
the bonding performance on the dispersions with 5.6 wt%
PVAm.
PVAm probably forms very strong attractive inter-
molecular interactions with xylan and the wood surface.
The addition of a covalent crosslinker may interrupt or
weaken these interactions, thereby reducing the bonding
performance of the dispersion. Another possibility is
pre-curing; the reaction with the crosslinker proceeds too
fast and reacts before the adhesive system is applied onto
the wood surface.
In an attempt to study the crosslinking of the xylan dis-
persions in more detail, dispersions were applied on glass
substrates and dried in an oven at 120 °C for 10 min and
at room temperature overnight. The dried material was
further analyzed with FTIR. The dispersions, however, were
shown to be difficult to analyze using FTIR. The films were
complex and different spectra were obtained on different
spots. The dispersions are not homogeneous and do not
react homogeneously. One example of a FTIR spectrum is
shown in Fig. S9 in supplementary data.
The xylan dispersions that showed promising results in
the tensile shear strength evaluation using ABES were pre-
pared in larger scale and used to bond wood panels togeth-
er that were further evaluated according to European
 E. Norström et al. / European Polymer Journal 67 (2015) 483–493 491

Fig. 6. The tensile shear strength measurements of veneers, bonded with xylan dispersed in AATMP and/or PVAm, using the ABES device. The substrates
were conditioned for a week at 20 ± 2 °C and 65 ± 5% RH (dry) and further immersed in water for 3 h at 20 ± 5 °C and allowed to dry at 20 °C and 65% RH
(redried) prior to analysis.

Standards EN204 and EN14257 [5,6]. The tensile shear
strengths of the wood panels bonded with different X20-
based dispersions are presented in Fig. 7. All wood panels
bonded and conditioned for a week have higher tensile
shear strength than 10 MPa, thereby fulfilling the D1 crite-
rion, except X20-H0.8-PVAm2.4 and X20-PVAm5.6. The
X20-PVAm5.6 dispersion was highly viscous and rather
difficult to spread out over the wood panel which may
explain the poor result.
To be classified as a D2 wood adhesive the tensile shear
strength has to be 8 MPa or higher. Some wood specimens
demonstrate poor water resistance and delaminate in
water; especially those that had the lowest concentration
(2.4 wt%) of dispersing agents (PVA or PVAm) as well as
all specimens bonded with X20-G0.8-PVAm5.6, Fig. 7.
Increasing the amount of dispersing agent improves the
water resistance. However, most of the adhesives were
sensitive toward water and the bond strengths were dras-
tically reduced compared with the dry samples. The wood
specimens bonded with X20-PVAm5.6 demonstrated a
remarkable water resistance and the adhesive fulfill the
D2 criterion even though the dispersion was thick and dif-
ficult to spread.
None of the adhesives were sensitive toward elevated
temperatures, Fig. 7. All the adhesives pass the tensile
shear strength limit of 7 MPa, which means that they fulfill
the WATT 91 criterion. The insensitivity of xylan toward
elevated temperatures is hypothesized being due to its
cyclic structure and the formation of hydrogen bonding.
The two techniques of bonding wood veneers (ABES)
and bonding wood panels (EN204 and EN14257) together
rely on different methodologies. The bonded areas are
not the same; wood veneers are bonded on an area of
1 cm2 compared with wood panels that are bonded on an

Fig. 7. Tensile shear strength of wood panels bonded with different xylan-based wood adhesives. The dotted lines show the limits to pass the D1, D2 and
WATT 91 criteria. [5,6] The wood specimens bonded with X20-G0.8-PVAm5.6 were not heat treated since too few specimens were obtained after the
pressing due to delamination of the wood panel.
492 E. Norström et al. / European Polymer Journal 67 (2015) 483–493
area of 540 cm2. Therefore, the adhesives’ spreadability is
more important when bonding larger wood panels.
Bonding of wood veneers and evaluation using ABES is an
efficient and rapid screening of the adhesive performance,
whereas the method using wood panels is much more rele-
vant when assessing the industrial applicability of disper-
sions. To conclude, the two methods complement each
other and address different properties, i.e., spreadability
with wood panels and adhesion performance with ABES.
Taking this into account it is not unexpected that the same
dispersion gave rise to different results with the two
techniques.
4. Conclusions
Xylan has been successfully dispersed and evaluated as
a wood adhesive. The xylan-based dispersion, X20, itself
cannot be used as a wood adhesive due to its limited bond-
ing performance, especially regarding water resistance.
Dispersing agents (PVA and PVAm) and crosslinkers (gly-
oxal, HMMM, AATMP, CA and BTCA) have been added with
the aim to improve the dispersibility and the bonding per-
formance. It was shown that the addition of PVA slightly
improves dry strength but has no effect on water resis-
tance. The addition of both PVA and a crosslinker; glyoxal
or HMMM, improves water resistance. HMMM improves
both the dry strength and the water resistance of the adhe-
sives. The bonding performance of the xylan dispersion
was remarkably improved when PVAm was used as dis-
persing agent. The bonding performance was further
improved by the addition of HMMM or AATMP as
crosslinkers. Xylan dispersed in 5.6 wt% PVAm demon-
strates surprisingly good results regarding water and heat
resistance. The xylan in combination with dispersing agent
and crosslinker demonstrates a very good bond strength,
water resistance and heat resistance. Almost all X20-based
dispersions evaluated according to European Standard, can
successfully be classified as D1 and WATT 91 adhesives. In
conclusion, xylan can be used as the major component in
wood adhesives. However, the spreadability of the adhe-
sives has to be improved to obtain further enhanced bond-
ing performance when larger areas, such as wood panels,
are bonded.
Acknowledgements
Wobama, WoodWisdom – Net ERA-NET/Formas are
acknowledged for financial support.
Appendix A. Supplementary material
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.eurpolymj.2015.02.021.
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