polymers

Article
Exploring Fully Biobased Adhesives: Sustainable Kraft Lignin
and 5-HMF Adhesive for Particleboards
Liam Dorn , Arthur Thirion, Masoumeh Ghorbani, Luis M. Olaechea and Ingo Mayer *

Institute for Materials and Wood Technology, Bern University of Applied Sciences (BFH),
CH-2500 Biel, Switzerland; dornl1@bfh.ch (L.D.); tia2@bfh.ch (A.T.); ohl1@bfh.ch (L.M.O.)
* Correspondence: ingo.mayer@bfh.ch

Abstract: Most adhesives used in the wood-based panel (WBP) industry are petroleum-based and
are associated with environmental impact and price fluctuations. Furthermore, most have potential
adverse health impacts, such as formaldehyde emissions. This has led to interest from the WBP
industry in developing adhesives with bio-based and/or non-hazardous components. This research
focuses on the replacement of phenol-formaldehyde resins by Kraft lignin for phenol substitution
and 5-hydroxymethylfurfural (5-HMF) for formaldehyde substitution. Resin development and op-
timization was carried out regarding varying parameters such as molar ratio, temperature or pH.
The adhesive properties were analyzed using a rheometer, gel timer and a differential scanning
calorimeter (DSC). The bonding performances were evaluated using an Automated Bonding Eval-
uation System (ABES). Particleboards were produced using a hot press, and their internal bond
strength (IB) was evaluated according to SN EN 319. Hardening of the adhesive could be achieved
at low temperatures by increasing or decreasing the pH. The most promising results were obtained
at pH 13.7. The adhesive performances were improved by adding filler and extender (up to 28.6%
based on dry resin) and several boards were produced reaching P1 requirements. A particleboard
achieved a mean IB of 0.29 N/mm2 , almost reaching almost P2 requirements. However, adhesive
reactivity and strength must be improved for industrial use.

Citation: Dorn, L.; Thirion, A.; Keywords: bio-based adhesive; Kraft lignin; 5-HMF; wood-based panels; particleboards; wood-
Ghorbani, M.; Olaechea, L.M.; Mayer, based composites
I. Exploring Fully Biobased
Adhesives: Sustainable Kraft Lignin
and 5-HMF Adhesive for
Particleboards. Polymers 2023, 15,
1. Introduction
2668. https://doi.org/10.3390/
polym15122668
Globally in 2021, around 396 million m3 of wood-based panels (WBP) were pro-
duced [1]. In order of decreasing total global production volume, the main types are
Academic Editors: Oihana Gordobil, oriented strand boards, plywood, medium/high-density fiberboard, particleboards and
Stefan Beisl and René Herrera Díaz oriented strand boards [1]. WBP consists mainly of wood with 2–14% adhesive content
Received: 25 May 2023 (dry resin/dry wood mass) [2].
Revised: 9 June 2023 WBPs are mainly produced through hot pressing, where a mixture of wood, adhesive,
Accepted: 10 June 2023 and additives such as wax and emulsifiers are pressed at a specific pressing pressure of
Published: 13 June 2023 2 to 4 N/mm2 at temperatures spanning from 200 to 220 ◦ C [2,3]. The adhesives used
in the manufacturing of WBP include urea-formaldehyde (UF), phenol-formaldehyde
(PF), melamine-formaldehyde (MF), melamine-urea-formaldehyde (MUF), and resorcinol-
formaldehyde (RF), but also polyurethane adhesives based on MDI [4,5]. Among these ad-
Copyright: © 2023 by the authors. hesives, formaldehyde-based adhesives (UF, PF, MF, MUF and RF) represent approximately
Licensee MDPI, Basel, Switzerland.
95% of the adhesives used for WBP, with UF being the most widely used, representing
This article is an open access article
85% of the total production volume worldwide [5]. Formaldehyde-based adhesives have
distributed under the terms and
drawbacks, as indoor formaldehyde emissions are associated with a range of adverse
conditions of the Creative Commons
impacts on human health, including throat, nose and eye irritation [6].
Attribution (CC BY) license (https://
Moreover, formaldehyde is classified as a 1B carcinogenic, according to the European
creativecommons.org/licenses/by/
Parliament and the European Council 605/2014 [7]. Therefore, strict indoor emissions
4.0/).

Polymers 2023, 15, 2668. https://doi.org/10.3390/polym15122668 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 2668 2 of 15

standards, including EN 13986 [8], have pushed the market to reduce the amount of
formaldehyde emitted by wood-based panels. These formaldehyde-based adhesives are
also produced using petroleum-based compounds associated with higher environmental
impacts than certain bio-based alternatives [9] and lead to dependence on crude oil supply
and its associated price volatility. Within this group of formaldehyde-based adhesives, there
are differing properties. UF is low cost, rapid curing and possesses good dry bond strength
but has low water resistance, restricting it to indoor use [10]. This means that UF resins
are modified via partial or full urea replacement for high-humidity applications of more
expensive compounds, such as melamine, phenol or resorcinol [11,12]. PF resins are the
preferred adhesives for producing exterior-grade panels and represent the second most con-
sumed type of wood adhesive after UF [13]. As an alternative to UF resins, polyurethanes
can also be used, as they possess higher dimensional stability and increased moisture resis-
tance compared to UF [12]. Usually, such polyurethanes are based on methylene diphenyl
diisocyanate (MDI) and display a better VOC profile [12] but they remain a hazard at the
production site and require a high level of health protection [14]. Moreover, it remains
petroleum-based and suffers from technical issues due to its propensity to generate sticky
build-up on the press surface and its slower curing time when compared to formaldehyde-
based resins [15]. The issues with the current adhesive systems described above have led
to much interest in the wood industry regarding substituting formaldehyde and other
fossil-derived components in WBP adhesives. In this body of work, we concentrate on
phenol and formaldehyde substitution in PF resins.
Lignin has excellent potential for phenol substitution due to its phenolic structure,
and low price [16]. Technical lignin refers to Lignin that is isolated from by-streams in
lignocellulosic refiners. These included Kraft, soda, organosolv and hydrolysis Lignin
and lignosulphonates [17]. These have different properties, including molecular weight,
polydispersity, homogeneity and the presence of certain functional groups [17]. Currently,
Kraft and lignosulfonate represent the largest by volume, making them the most interesting
for high-volume applications, such as in adhesives for wood-based panels. Especially,
Kraft lignin, with a high availability potential and further improvement in extraction
technology [18], is a suitable candidate to replace such large volume resin as PF resin,
with a worldwide production estimated at 5 mio tons/year. Kraft and lignosulfonate are
associated with high ash content compared to the other technical lignin, and both have
sulfur present. Kraft exhibits between 1 and 3% sulfur content in H-bonds compared to
3.5–8% in lignosulfonate [17]. Sulfur is associated with odor problems and can inhibit
catalysts [17]. Kraft lignin can be extracted from the black liquor of the Kraft pulping
processes; thus, the valorization of this by-product is currently of great interest to the pulp
and paper sector.
On a laboratory scale, 100% of phenol replacement could be achieved without a loss
of mechanical properties when compared to PF references [19]. On an industrial scale,
currently, only 50–80 wt% phenol substitution by Lignin could be achieved by BioBond
using UPM BioPiva Kraft lignin [20]. This limitation in substitution rate is partially due
to steric hindrance, reducing lignin reactivity with formaldehyde [21]. Lignin reaction
with formaldehyde is a two-step process. Firstly, there is activation by methyl-olation
at the C5 position of the guaiacol units in an alkaline medium (Figure 1A), followed by
a condensation reaction of the methylal groups previously formed [21]. In addition to
the potential of Lignin as phenol replacement, the non-toxic 5-hydroxymethylfurfural
(5-HMF) has potential as a formaldehyde replacement (Figure 1B). Moreover, 5-HMF can be
produced from biomass containing fructose or glucose. This is possible via the dehydration
of fructose under acidic conditions. For glucose, a previous isomerization into fructose
is required [22]. From a chemical point of view, 5-HMF has the advantage of bearing on
its furan ring, in addition to the aldehyde group, a hydroxy-methylene group that can
contribute to the hardening of the resin via the formation of methylene bridges.
Polymers 2023, 15, 2668 3 of 15

Figure 1. (A) Scheme of the electrophilic aromatic substitutions of coniferyl alcohol with formalde-
hyde. (B) Scheme of the proposed electrophilic aromatic substitutions of coniferyl alcohol with
5-HMF. This is based on information from literature [23]. The figure was drawn by one of this paper
authors and coniferyl alcohol is used here solely to depict the Guaiacol unit of lignin.

A phenol 5-HMF adhesive has been previously produced on a laboratory scale for
use in fiber-reinforced composites. This adhesive was synthesized by Zhang et al. using
sawdust bio-oil as phenol replacement and glucose for in situ 5-HMF formation, which
would replace formaldehyde [24]. However, full replacement of phenol by sawdust bio-oil
showed a decrease in the resulting molecular weights, indicating limitations in the poly-
condensation reaction. In this work, we aim to completely replace phenol, formaldehyde
or any other petroleum-based components.

2. Materials and Methods

2.1. Materials
Crystalline 5-Hydroxymethylfurfural (95 wt%) and in solution (aqueous 22 wt%) were
purchased from AVA Biochem AG (Zug, Switzerland).
Kraft Lignin was obtained from two European providers. Source 1 was UPM BioPiva™
395 (UPM Biochemicals, Helsinki, Finnland), with an average molecular weight of 6000 g/mol.
Source 2 was LineoTMClassic (Stora Enso, Kotka, Finnland), with an average molecular
weight of 6000–7000 g/mol.
Sodium hydroxide (aq. 50 wt%), and Calcium carbonate powder (≥99%) were sourced
from Sigma-Aldrich Chemie GmbH (Buchs, Switzerland). Wheat flour was purchased from
a local store in Switzerland. Beech veneers were supplied by Atlas Holz AG (Trübbach,
Switzerland). The particles were of core-layer dimension, consisted mainly of Norway
spruce (Picea abies), with smaller portions of recycled material, and were provided by Rauch
Spanplattenwerke GmbH (Markt Bibart, Germany).

2.2. Resin Preparation

The resin was synthesized by adding dry kraft lignin (lignin S1 and S2) (0.05 mol
C9 units) portion-wise to a solution of distilled water and sodium hydroxide (aq. 50 wt%)
and maintained at 90 ◦ C under stirring. As soon as all lignin was dissolved, a
5-HMF solution (aq. 50 wt%) was added under reflux conditions via an SPL syringe
pump (World Precision Instruments Inc., Sarasota, FL, USA). After addition, the mixture
was maintained at 90 ◦ C for a further 60 min prior to being cooled to room temperature via
the use of an ice bath. The molar ratio of the adhesive used in board production was 2:1
5-HMF to Lignin, 0.8:1 NaOH to Lignin, and the amount of water was 1.25:1 relative to the
dry mass of Lignin. A step-by-step synthesis protocol can be found in Appendix A. Solid
content was measured using a Rotavapor R-124 rotary evaporator (BUCHI Corporation,
Denver, CO, USA) with a water temperature of 50 ◦ C and pressure was progressively
reduced from atmospheric pressure to 0.035 bar until the mass remained stable.
Polymers 2023, 15, 2668 4 of 15

2.3. Viscosity Evaluation

Viscosity was measured at 20 ◦ C and 1 bar using a viscometer DV2T from Brookfield,
Middleboro, MA, USA, in a conditioned environment of 20 ± 2 ◦ C and 1.01 bar (1 atm).

2.4. Filler and Extender Content

The filler and extender used were calcium carbonate and wheat flour, respectively,
always added in a 1:1.5 ratio (calcium carbonate/wheat flour) based on weight. The
amount of both in relation to dry resin mass was varied during adhesive optimization and
particleboard production and testing and is discussed in the corresponding section.

2.5. Particleboard Preparation

The particleboard production was executed at BFH and consisted of the following
steps: drying and resination of the particles, hot pressing, sample preparation and testing.
Particle drying was carried out using a custom dryer built by Ruefli AG (Biel/Bienne,
Switzerland). The adsorption dehumidifier CR100 from COTES A/S (Aarhus, Denmark)
was run at maximum capacity with a nominal dry air flow of 100 m3 /h and 0.94 kW heating
capacity until a desired moisture content of 2–2.5% was reached. After drying, the particles
were transferred to a bag and sealed for at least one week to ensure a homogenous moisture
content level.
Particle blending was carried out using a 300-litre blender from Gebrüder Lödige
Maschinenbau GmbH (Paderborn, Germany). The particles were first added, and then the
adhesive mixture was pumped through a 6.5 mm hose, then sprayed via an air-mix nozzle
with an outlet diameter of 1.8 mm and a pressure of 2 bar. A blender rotational speed of
approximately 120 min−1 was used.
Single-layer particle boards were pressed using a HLOP 210 provided by Höfer
Presstechnik GmbH (Taiskirchen, Austria) controlled via the Pressworks software. The par-
ticleboard production process was always conducted using the 5-HMF/lignin S1 adhesives
prepared as described in Section 2.2 with a pH of 13.7. Production was carried out with
different variations in process parameters, such as press factor, moisture content or press
closing time, and variation in resin and filler/extender content. Please refer to Appendix B
for further details. The following parameters where constant among all boards produced:
press plate temperature of 200 ◦ C, final board thickness of 16 mm and target density of
650 kg/m3 . Further processing occurred once the boards had cooled overnight. The wood
to adhesive dry weight ratio was kept constant at 10 for all boards except one (Board ID 14).

2.6. Thermal Characterization of the Resin

The curing temperature was investigated using a differential scanning calorimeter
(DSC) from PerkinElmer, DSC 6000, Waltham (M.A.), USA. DSC measurements were
carried out using reusable high-pressure stainless-steel pans. Heating scans were carried
out at a rate of 10.00 ◦ C/min with the temperature range depending on the mixture’s pH,
investigated to avoid corrosion of the crucibles. These were as follows: 30–250 ◦ C for
pH >3, 30–200 ◦ C for pH 2–3, 30–180 ◦ C for pH 1.8–2, and 30–160 ◦ C for pH < 1.8.
Gel time measurements were done using a Gel timer SLIM LINE GT-S with control unit
PTC-3 from GEL INSTRUMENTE AG, Oberuzwil, Switzerland. Testing was performed
using 5 g specimens in the test tube.

2.7. Bonding Evaluation

The adhesives’ bonding strength development during pressing was determined in
accordance with ASTM D7998−15 using an Automated Bonding Evaluation System (ABES)
device (Adhesive Evaluation Systems, Inc., Corvallis, OR, USA). Two beech veneer strips
of 117 mm × 20 mm × 0.5 mm were glued together with a 5 mm overlap length (100 mm2
glue area). Therefore, a glue load of 70 g/m2 dry resin was applied. Then, the veneers were
pressed at the desired temperature and for varying durations, cooled with a set pressure of
Polymers 2023, 15, 2668 5 of 15

20 bar for 10 s and pulled apart under tensile loading. Five repetitions were performed for
each pressing time at a defined temperature.

2.8. Moisture Evaluation

The moisture contents of the veneers and particles were measured using the Moisture
Analyzer HE73 by Mettler-Toledo International Inc. (Columbus, OH, USA). The moisture
content was derived from the weight difference between moist and absolute dry mass.

2.9. Particleboard Evaluation

IB samples were cut using a circular saw and conditioned in a standard climate room
(20 ◦ C/80% R.H.) for at least one week. IB testing was carried out according to SN EN 319
using a universal material testing machine of type Z020 equipped with an Xforce K load
cell, from ZwickRoell GmbH & Co. K.G. (Ulm, Germany).

3. Results and Discussion

3.1. Adhesive Development
Firstly, the Kraft lignin from two different sources was characterized via 13 C-NMR
and yielded the following aliphatic and phenolic content (Table 1). From this, we see that
both types of Kraft lignin have similar phenolic and aliphatic content levels. The former is
more advantageous regarding reaction with 5-HMF. This work was focused on Source 1
(S1). Source 2 (S2) was exclusively used to evaluate the impact that would carry a change in
the provider/source of Kraft lignin after development of a formulation based on source 1.

Table 1. Aliphatic and phenolic content of the lignin source 1 and source 2 using 13 C-NMR [25].

Kraft Lignin Aliphatic OH mmol/g Phenolic OH mmol/g

S1 2.72 4.49
S2 2.66 4.45

To develop a 5-HMF/lignin S1 adhesive, a range of synthesis parameters were varied:

cooking time, pH, 5-HMF to lignin S1 molar ratio and Kraft lignin supplier. The starting
synthesis parameters consisted of a mixture of lignin S1 and sodium hydroxide (pH = 10)
in a molar ratio of 1:0.6. The molar ratio is based on the molar weight of the C9 units of
180 g/mol. First, to investigate a possible self-polymerization of the kraft lignin or the
5-HMF, a mixture containing lignin and another containing solely 5-HMF were cooked for
80 min at 90 ◦ C and at pH 10. In both cases, the mixtures exhibited low levels of viscosity,
thus suggesting that no self-polymerization took place or at a least at very low extents.
Then, with the addition of 5-HMF (0.5 mL/min) into the lignin S1/sodium hydroxide
mixture in a 1:1 5-HMF to lignin S1 ratio, cooking time was extended from 1 h to 1.5 h
and 2 h and the viscosity was monitored (Figure 2A). Contrary to the self-polymerization
experiments, the viscosity increased significantly during the reaction. After 1.5 h, the
viscosity reached values that begin not to be suitable for wood-based panel production.
Consequently, the reaction time was fixed at 1 h. Based on this, a range of 5-HMF to
lignin S1 molar ratios were studied. This time, it was observed that the viscosity of the
resin increased concomitantly with the 5-HMF/lignin S1 molar ratio until a ratio of 2
was achieved (Figure 2B). However, at a 5-HMF/lignin S1 molar ratio of 3, the viscosity
decreased to values similar to those obtained with a molar ratio of 0.7. At a molar ratio
of 3, the gelation time also increased to 42 min, compared to 16 min at the molar ratio of
a 0.7. This could be due to the increased amount of 5-HMF leading to a reduction in pH
from 10.8 at 0.7 to 9.6 at 3 molar ratios (Table 2). Based on those results and considering
economic factors, the molar ratio between 5-HMF and lignin S1 was maintained between 1
and 2, as 5-HMF continues to be relatively expensive.
Polymers 2023, 15, 2668 6 of 15

Figure 2. (A) Viscosity measured at room temperature (25 ◦ C) after 1 h, 1.5 h and 2 h of cooking at
90 ◦ C (B) Viscosity at room temperature of the adhesive with varying 5-HMF to lignin S1 molar ratio.

Table 2. Gel time at 100 ◦ C of the adhesive with varying 5-HMF/lignin S1 molar ratio.

5-HMF/Lignin S1
Gel Time (min) pH Solid Content
Molar Ratio
0.7 16 10.8 34.1
1 9 10.5 40.9
1.5 11 10.2 44.2
2 18 10.0 49.5
3 42 9.6 56.1

In addition to the initial characterization, a series of ABES tests were conducted to in-
vestigate the impact of 5-HMF/lignin S1 molar ratio on the resulting tensile shear strength.
The ABES results showed that the 5-HMF to lignin ratio had no impact on bond develop-
ment (Figure 3A). Moreover, the tensile shear strength was quite low. To optimize the resin
formulation in terms of performance, wheat flour was tested as potential extender, known in
the WBP industry for its low cost and biobased character [26]. Therefore, ABES testing was
performed after the addition of 10 wt% of wheat flour based on the solid content (Figure 3B).
As we can see in Figure 3B, the tensile shear strength increases significantly upon addition
of wheat flour. To conclude this ABES series, the lignin S1 was exchanged for S2 in the
preparation of the resin and ABES was measured under the same conditions. Interestingly,
we observed an improvement in the tensile shear strength when compared to 5-HMF/lignin
S1 (Figure 3C). On the other hand, neither 5-HMF/lignin S2 or 5-HMF/lignin S2 with
10 wt% of extender (Figure 3D) performed better than 5-HMF/lignin S1 with 10 wt% of
extender.
Finally, DSC measurements of the resins prepared using 1 and 2 molar ratios of
5-HMF/lignin S1 were performed and revealed a decrease in the curing temperature, when
increasing the molar ratio (Appendix C). Indeed, the maxima decreased slightly when
increasing the 5-HMF/lignin S1 molar ratio (i.e., from 183 to 178 ◦ C). This decrease is
similar independently of the source. Based on the results obtained so far, it was decided to
continue using lignin S1 solely.
Polymers 2023, 15, 2668 7 of 15

Figure 3. Adhesive strength development at 130 ◦ C of different adhesive formulations. (A) Different
5-HMF/lignin S1 molar ratio, (B) with and without wheat flour as extender, (C) source 1 and source
2, (D) Different supplier with filler.

3.2. Adhesive Optimisation

To enhance the tensile performances of the resin formulation, further optimization was
carried out focusing on the curing process at different pH. To evaluate the impact of pH
on the curing process, a series of ABES were performed. The pH was adjusted by adding
either p-toluene-sulfonic acid (pTSA) or sodium hydroxide (NaOH) to the prepared resin.
The results revealed that low curing temperatures (i.e., below 100 ◦ C) were obtained under
very acidic conditions (i.e., with a pH below 1.3) (Figure 4A). In a similar trend, the curing
temperature can also be decreased by increasing the pH, reaching the lowest values (i.e.,
115 ◦ C) at a pH near 13.8 (Figure 4B). A summary of the curing temperatures related to
the pH is illustrated in Figure 4C. When comparing the resulting tensile shear strengths at
equivalent press time, solid content and temperature in the ABES tests, it was found that
alkaline conditions exhibited higher tensile shear strengths (Figure 4D). The DSC curves
in alkaline conditions displayed a distinct peak, indicating a certain degree of curing. In
contrast, the acidic curves appeared relatively flat, as the exotherm spanned over a large
range of temperatures. Furthermore, it was observed that the resin tends to aggregate
under acidic conditions, leading to an unprocessable heterogeneous mixture, probably
because of the decrease in solubility of lignin under acidic conditions [18]. Considering
the necessity for low curing temperatures (i.e., 90–110 ◦ C) in WBP production, a pH of 13.7
was defined for further investigations and for the panel manufacturing process.
Polymers 2023, 15, 2668 8 of 15

Figure 4. Stacking of DSC chromatographs of a 5-HMF/lignin S1 resin in (A) acidic conditions using
p-toluene sulfonic acid to correct the pH and (B) under alkaline conditions using sodium hydroxide
to correct the pH. (C) Relationship between pH and curing temperature. (D) Tensile shear strength
after pressing a 130 ◦ C at pH 13.8 (blue curve) and pH 2.01 (red curve).

Further optimization was carried out on the adhesive under alkaline conditions
(pH 13.7) by means of ABES, and the relationship between bonding strength, resin, filler
and extender solid content were studied (Figure 5). Furthermore, calcium carbonate was
added to the formulation as a filler. It has been shown that this can improve important
chemical and physical characteristics in the wood-panel based industry, such as bending
strength, decrease of water absorption or thickness swelling [27]. For this series of ABES,
an experimentation space was defined where the total solid content was kept constant (i.e.,
either 45 or 60 wt%) but where the mass ratios between resin, extender and filler were
varied (Figure 5A). Considering the series with 45 wt% of solid content, similar, or even
slightly higher, tensile shear strength could be obtained after decreasing the amount of
resin content in favor of extender and filler (Figure 5B). This reduces applications cost as
less expensive 5-HMF/lignin S1 is used. The same trend could be observed in the series
with a total solid content 60 wt% (Figure 5C). On the other hand, after addition of extender
and filler in the 60 wt% series, the viscosity increased dramatically and this application,
while feasible in ABES, becomes intricate for particleboard production. In addition, even if
feasible in ABES, high viscosities could prevent absorption of the adhesive by the wood.
Because of this, additional ABES tests were conducted with a lower solid content (i.e.,
52.7 wt% of solid content) (Figure 5D). Interestingly, the tensile shear strengths displayed
was above the 45 and 60 series. Moreover, wood failure could already be observed in
some veneers after a pressing time of 30 s. This was never observed previously in our
experiments. This suggests that the bond strength becomes closer to the strength of the
veneer itself. Thus, it was chosen for initial particleboard production.
 above the 45 and 60 series. Moreover, wood failure could already be observed in
veneers after a pressing time of 30 s. This was never observed previously in our e
Polymers 2023, 15, 2668 ments. This suggests that the bond strength becomes closer to the strength
9 of 15 of the v
itself. Thus, it was chosen for initial particleboard production.

Figure 5. Impact of different adhesive solid content and filler and extender amount (based on dry
resin) on adhesive strength
Figure development.
5. Impact (A) adhesive
of different The formulations testedand
solid content andfiller
theirand
impact on adhesive
extender amount (based
resin) on
strength development adhesive
with strength
a (B) total development.
solid content (A) The
of 45 wt%, (C) formulations testedofand
total solid content their and
60 wt% impact on ad
strength
(D) differing total development with a (B) total solid content of 45 wt%, (C) total solid content of 60 wt
solid content.
(D) differing total solid content.
3.3. Particleboard Production and Testing
To trial the3.3. Particleboard
adhesive Productionproduction,
for particleboard and Testinga total of 21 combinations (Appendix B)
of parameters were tested, resulting in 14 self-standing
To trial the adhesive for particleboard boards. Their corresponding
production, a total of internal
21 combinations
bond (IB) is summarized
pendix B) in of Figure 6. From
parameters the tested,
were results, resulting
it was observed that the press boards.
in 14 self-standing factor Their
had the most significant influence,
sponding internal as no
bond self-standing
(IB) is summarized boardin could
Figurebe6.produced
From the when the
results, it was obs
press factor was below 30 s/mm. Moreover, the IB could be increased significantly
that the press factor had the most significant influence, as no self-standing board cou by
increasing the produced
press factor.whenForthe
instance, increasing
press factor the press
was below factorMoreover,
30 s/mm. from 30 (sample #12) be incr
the IB could
to 45 s/mm (sample #13) resulted in an increased IB from 0.05 to 0.27 N/mm 2 . A similar
significantly by increasing the press factor. For instance, increasing the press factor
trend was observed between
30 (sample #12)sample
to 45#15
s/mmand(sample
16, where theresulted
#13) press factor was
in an increasedIBfrom
increased from 0.05 t
30 to 37.5 s/mm. N/mm2. A similar trend was observed between sample #15 andof16,
Interestingly, the highest IB recorded with a press factor 30where
s/mmthe press
was achieved when the pressing
was increased fromwas
30 performed
to 37.5 s/mm. the day after (i.e., the
Interestingly, sample #3) rather
highest than with a
IB recorded
immediately after spraying the resin onto the wood particles (i.e., sample #2).
factor of 30 s/mm was achieved when the pressing was performed the day after (i.e.To enhance
the heat transfer plewithin the boards
#3) rather during the pressing
than immediately process,
after spraying the different
resin ontoamounts
the woodof water
particles (i.e.
were sprayed on the hot plates before pressing (i.e., sample #17 and 18) and compared
ple #2). To enhance the heat transfer within the boards during the pressing pr
to a board (i.e., sample #16) when no water was sprayed. This water spraying on the
hot plates is performed to generate additional steam that should help with heat transfer.
Unfortunately, this factory trick did not work, as all samples displayed similar IB (i.e.,
between 0.2 and 0.25 N/mm2 ). So far, the best-performing boards (i.e., sample # 3 and
13) displayed IB sufficient for P1 classification according to SN EN 312. In an attempt to
 help with heat transfer. Unfortunately, this factory trick did not work, as all samples dis-
played similar IB (i.e., between 0.2 and 0.25 N/mm2). So far, the best-performing boards
(i.e., sample # 3 and 13) displayed IB sufficient for P1 classification according to SN EN
312.2023,
Polymers In 15,
an2668
attempt to reach values related to P2 classification, two panels were 10 produced
of 15

with the same wood to a dry adhesive mass ratio of 10, but where the percentage of ex-
tender and filler wasreachincreased, keeping
values related the resintwo
to P2 classification, solid
panelscontent constant
were produced (i.e.,
with the samesample
wood #20
and 21). Interestingly,to aboard #20, mass
dry adhesive which ratiocontained lesstheadditives
of 10, but where (i.e.,
percentage of extender
extender and
and filler wasfiller)
increased, keeping the resin solid content constant (i.e., sample #20 and 21). Interestingly,
than #21 but more than #19, exhibited the highest IB and reached values close to the limit
board #20, which contained less additives (i.e., extender and filler) than #21 but more than
between P1 and P2 #19, (0.35 N/mm
exhibited the2)highest
classification.
IB and reached However,
values closefurther testing
to the limit betweenisP1required
and P2 to
2
(0.35 N/mm ) classification. However, further testing is required to ensure reproducibility
ensure reproducibility and define a significant 5% value.
and define a significant 5% value.

Figure 6. Boxplot of the IB results for all tested particleboards. P1, P2 and P3 refer to the 5% percentile
Figure 6. Boxplot of the IB results for all tested particleboards. P1, P2 and P3 refer to the 5% percen-
IB value given by SN EN 312 for the first three particleboard classes (P1–P3). The n refers to the
tile IB value given by SN ENof312
number for the
IB samples first
tested three
from particleboard
the produced board. Whiteclasses (P1–P3).toThe
circles correspond n refers to the
outliers.
number of IB samples tested from the produced board. White circles correspond to outliers.
It was also noticed during board manufacturing that moisture content seemed to
affect the IB of the particle boards. To investigate this, a series of ABES was performed
It was also noticed during
varying board
the moisture manufacturing
content that moisture
and a negative correlation content
could be observed seemed
(Appendix D) to af-
between tensile shear strength and moisture content, but additional
fect the IB of the particle boards. To investigate this, a series of ABES was performed experiments should be var-
performed to clarify this. Water could act as a plasticizer lowering the IB, suggesting that
ying the moisture content and and
water resistance a negative
or degree ofcorrelation could
crosslinking still need tobe observed
be improved (Appendix
in this system in D)
between tensile shear strength and moisture content, but additional experiments should
order to be used under humid conditions.

be performed to clarify this. Water could act as a plasticizer lowering the IB, suggesting
4. Conclusions
that water resistance and or degree
A fully bio-basedofadhesive
crosslinking still
based Kraft need
lignin and to be improved
5-HMF in thisand
has been formulated system
evaluated and applied in the production of particleboards at a lab scale. The adhesive was
in order to be used under humid conditions.
developed via varying synthesis parameters, such as lignin types, pH, cooking time and
5-HMF to lignin ratio. The adhesive reactivity could be tuned by varying the pH, reaching
4. Conclusions the requirement for hot pressing particle boards production under alkaline conditions. To

A fully bio-based adhesive based Kraft lignin and 5-HMF has been formulated and
evaluated and applied in the production of particleboards at a lab scale. The adhesive was
developed via varying synthesis parameters, such as lignin types, pH, cooking time and
Polymers 2023, 15, 2668 11 of 15

enhance the adhesive performance, formulation modifications were made, incorporating

cost-effective and bio-based additives, such as wheat flour. It could also be shown that,
in addition to the actual adhesive formulation, the setting of the adhesive (e.g., water
content) and other process parameters during panel manufacture have a major influence
on the IB of the particle boards. Utilizing this fully biobased resin, particleboards reaching
P1 classification, and nearly P2 classification, were successfully produced. However,
further improvement of the reactivity of the resin is certainly required as the current
press factor results in non-acceptable press times for current industrial applications. The
development of this fully bio-based adhesive represents an advancement in sustainable
adhesive technologies, demonstrating the potential to replace petroleum-based adhesives
in particleboard production and allowing the production of boards based fully on naturally-
derived raw materials.

5. Patents
The Patent P25109CH00—Adhesive formulation for wood panels, resulted from the
research described in this paper.

Author Contributions: Conceptualization & funding acquisition, I.M.; validation, L.M.O.; super-
vision & review, L.M.O.; investigation L.D. and M.G.; Writing—original draft preparation A.T.;
visualization L.D., A.T. and L.M.O.; Formal analysis M.G., L.D., L.M.O. and A.T. L.D. and A.T. con-
tributed equally to this paper as joint first authors. All authors have read and agreed to the published
version of the manuscript.
Funding: This study was funded by Innosuisse—Schweizerische Agentur für Innovationsförderung
Project No. 32248.1 IP-EE.
Data Availability Statement: The data presented in this study is available upon request from the
corresponding author.
Acknowledgments: The authors would also like to thank Christof Tschannen for his help in particle-
board’s manufacturing.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.

Appendix A
Sample recipe for 1500 g of wet resin.
1. Place 92.9 g of NaOH (50% solid content) and 326.6 g of distilled water in a three-neck
round-bottom flask equipped with a condenser, thermometer and stirrer.
2. Heat the three-neck round bottom flask to 90 ◦ C.
3. Add portion-wise 279.0 g of Kraft lignin (93.64% solid content) to the solution in the
three-neck round bottom flask.
4. Leave the mixture to stir for 20 min in the three-neck round bottom flask at 90 ◦ C.
5. Prepare a 5-HMF solution by adding 223.9 g of solid 5-HMF to 577.6 g of an aqueous
5-HMF solution (25 wt%) and mix the 5-HMF solution thoroughly.
6. Add the 5-HMF solution under reflux conditions via a syringe pump with an injection
rate of 13.2 mL/min to the solution in the three-neck round bottom flask at 90 ◦ C.
7. Once the addition is complete, leave the mixture at 90 ◦ C for 60 min under stirring.
8. Cool the resin immediately via insertion into an ice bath.
The resin pH would then be varied via the addition of further NaOH.
Polymers 2023, 15, 2668 12 of 15

Appendix B

Table A1. Board production press parameters.

Adhesive’s Adhesive on
Dry Resin Extender Target Mat
Days Since Filler Content Total Solid Wood Water Spray Press Closing Press Factor Produced
Board ID Content Content Moisture
Blending (d) (wt%) Content Particles (g/m2 ) Time (s) (s/mm) Viable Board
(wt%) (wt%) Content (%)
(wt%) (wt%)
1 0 35 7 10.5 52.5 10 12 0 15 15 No
2 0 35 7 10.5 52.5 10 12 0 15 30 Yes
3 1 35 7 10.5 52.5 10 12 0 15 30 Yes
4 1 35 7 10.5 52.5 10 12 0 15 15 No
5 1 35 7 10.5 52.5 10 12 0 15 22.5 No
6 0 35 7 10.5 52.5 10 12 0 15 22.5 No
7 0 35 7 10.5 52.5 10 12 0 5 30 No
8 0 35 7 10.5 52.5 10 12 0 5 22.5 No
9 0 35 7 10.5 52.5 10 12 0 5 30 No
10 0 35 7 10.5 52.5 10 12 0 5 30 Yes
11 0 35 7 10.5 52.5 10 12 0 15 30 Yes
12 0 35 7 10.5 52.5 10 12 0 5 37.5 Yes
13 0 35 7 10.5 52.5 10 12 0 5 45 Yes
14 0 35 7 10.5 52.5 13 12 0 15 30 Yes
15 0 35 7 10.5 52.5 10 10 0 15 30 Yes
16 0 35 7 10.5 52.5 10 10 0 15 37.5 Yes
17 0 35 7 10.5 52.5 10 10 25 15 37.5 Yes
18 0 35 7 10.5 52.5 10 10 50 15 37.5 Yes
19 0 35 7 10.5 52.5 10 10 0 5 37.5 Yes
20 0 35 9 13.5 57.5 10 9.5 * 0 5 37.5 Yes
21 0 35 10 15 60 10 9.1 * 0 5 37.5 Yes
* mat moisture content as was measured.
35 7 10.5 52.5 10 10 0 15 37.5 Yes
35 7 10.5 52.5 10 10 25 15 37.5 Yes
35 7 10.5 52.5 10 10 50 15 37.5 Yes
35 7 10.5 52.5 10 10 0 5 37.5 Yes
35 9 15, 2668 13.5
Polymers 2023, 57.5 10 9.5 * 0 5 37.5 Yes 13 of 15
35 10 15 60 10 9.1 * 0 5 37.5 Yes
* mat moisture content as was measured.

Appendix C
Appendix C

13 of 15
Figure A1. DSC curves for 1:1
Figure 5-HMF/Kraft
A1. DSC lignin
curves for 1:1 S1 at a pH
5-HMF/Kraft of S1
lignin 10.5,
at a exothermic up. 13.3up.
pH of 10.5, exothermic mg13.3
of mg
a of a
40.9 wt% resin (dry mass 5.44resin
40.9 wt% mg).(dry mass 5.44 mg).

Figure A2. DSC curves for 2:1

Figure A2. 5-HMF/Kraft lignin
DSC curves for 2:1 S1 at a pH
5-HMF/Kraft of S1
lignin 10.0,
at a exothermic up. 11.5 up.
pH of 10.0, exothermic mg11.5
of mg
a of a
49.45s% resin (dry mass 5.68 resin
49.45s% mg).(dry mass 5.68 mg).
Polymers 2023, 15, 2668 14 of 15
Figure A2. DSC curves for 2:1 5-HMF/Kraft lignin S1 at a pH of 10.0, exothermic up. 11.5 mg of a
49.45s% resin (dry mass 5.68 mg).

Figure A3. DSC curves for 1:1 5-HMF/Kraft lignin S2 at a pH of 10.4, exothermic up. 18.6 mg of a
Polymers 2023, 15, x Figure A3. DSC curves for 1:1 5-HMF/Kraft lignin S2 at a pH of 10.4, exothermic
14 of up.
15 18.6 mg of a
39.83 wt% resin (dry mass 7.4 mg).
39.83 wt% resin (dry mass 7.4 mg).

Figure A4. DSC curves for 2:1 5-HMF/Kraft lignin S2 at a pH of 10.0, exothermic up 10.5 mg of a
Figure A4. DSC curves for 2:1 5-HMF/Kraft lignin S2 at a pH of 10.0, exothermic up 10.5 mg of a
49.68 wt% resin (dry mass 5.21 mg).
49.68 wt% resin (dry mass 5.21 mg).
Appendix D
Appendix D

Figure A5. Impact of veneer moisture content on adhesive strength development at 100 °C with a
press time of (A) 120 s and (B) 180 s.
Figure A5. Impact of veneer moisture content on adhesive strength development at 100 ◦ C with a
References
press time of (A) 120 s and (B) 180 s.
1. FAOSTAT. Available online: https://www.fao.org/faostat/en/#data/FO (accessed on 5 May 2023).
2. Irle, M.; Barbu, M.; Niemz, P.; Carvalho, L.; Martins, J.; Costa, C.; Muszyski, L.; Launey, M.; Sernek, M.; Dunky, M.; et al.
Wood-Based Panels an Introduction for Specialists; Thoemen, H., Irle, M., Sernek, M., Eds.; Brunel University Press: London, UK,
2010; ISBN 978-1-902316-82-6.
3. Wong, E.D.; Zhang, M.; Wang, Q.; Kawai, S. Formation of the density profile and its effects on the properties of fiberboard. J.
Wood Sci. 2000, 46, 202–209.
Polymers 2023, 15, 2668 15 of 15

References
1. FAOSTAT. Available online: https://www.fao.org/faostat/en/#data/FO (accessed on 5 May 2023).
2. Irle, M.; Barbu, M.; Niemz, P.; Carvalho, L.; Martins, J.; Costa, C.; Muszyski, L.; Launey, M.; Sernek, M.; Dunky, M.; et al.
Wood-Based Panels an Introduction for Specialists; Thoemen, H., Irle, M., Sernek, M., Eds.; Brunel University Press: London, UK,
2010; ISBN 978-1-902316-82-6.
3. Wong, E.D.; Zhang, M.; Wang, Q.; Kawai, S. Formation of the density profile and its effects on the properties of fiberboard. J.
Wood Sci. 2000, 46, 202–209. [CrossRef]
4. Dunky, M. Adhesives in the Wood Industry in Handbook of Adhesive Technology, Second Edition, Revised and Expanded, 2nd ed.; Pizzi,
A., Mittal, K.L., Eds.; CRC Press: Boca Raton, FL, USA, 2003; pp. 872–941. ISBN 0-8247-0986-1.
5. Papadopoulou, E.; Nakos, P.; Tsiantzi, S.; Athanassiadou, E.; Chimar Hellas, S.A. The challenges of Bio-adhesives for the wood
composite industries. In Proceedings of the 9th Pacific Rim Bio-Based Composites Symposium, Rotorua, New Zealand, 5–8
November 2008.
6. WHO. WHO Guidelines for Indoor Air Quality: Selected Pollutants; WHO Regional Office for Europe: Copenhagen, Denmark, 2010.
7. The European Commission. Commission Regulation (EU) No 605/2014; Official Journal of the European Union: Luxembourg, 2014.
8. Deutsches Institut für Normung. Holzwerkstoffe zur Verwendung im Bauwesen-Eigenschaften, Bewertung der Konformität und
Kennzeichnung; EN 13986:2004+A1:2015; Beuth Verlag GmbH: Berlin, Germany, 2015.
9. Arias, A.; González-García, S.; González-Rodríguez, S.; Feijoo, G.; Moreira, M.T. Cradle-to-gate Life Cycle Assessment of
bio-adhesives for the wood panel industry. A comparison with petrochemical alternatives. Sci. Total Environ. 2020, 738, 140357.
[CrossRef] [PubMed]
10. Kristak, L.; Antov, P.; Bekhta, P.; Lubis, M.A.; Iswanto, A.H.; Reh, R.; Sedliacik, J.; Savov, V.; Taghiyari, H.R.; Papadopoulos, A.N.;
et al. Recent progress in ultra-low formaldehyde emitting adhesive systems and formaldehyde scavengers in wood-based panels:
A review. Wood Mater. Sci. Eng. 2022, 18, 763–782. [CrossRef]
11. Solt, P.; Konnerth, J.; Gindl-Altmutter, W.; Kantner, W.; Moser, J.; Mitter, R.; van Herwijnen, H.W. Technological performance of
formaldehyde-free adhesive alternatives for particleboard industry. Int. J. Adhes. Adhes. 2019, 94, 99–131. [CrossRef]
12. Pizzi, A.; Kumar, R.N. Adhesives for Wood and Lignocellulosic Materials; Scrivener Publishing LLC: Beverly, MA, USA, 2019.
13. Hussin, M.H.; Abd Latif, N.H.; Hamidon, T.S.; Idris, N.N.; Hashim, R.; Appaturi, J.N.; Brosse, N.; Ziegler-Devin, I.; Chrusiel, L.;
Fatriasari, W.; et al. Latest advancements in high-performance bio-based wood adhesives: A critical review. J. Mater. Res. Technol.
2022, 21, 3909–3946. [CrossRef]
14. Stubdrup, K.; Karlis, P.; Roudier, S.; Delgado Sancho, L. Best Available Techniques (BAT) Reference Document for the Production of
Wood based Panels; JRC Science for Policy Report; Publications Office of the European Union: Luxembourg, 2016.
15. McCracken, T.S. PMDI Prepolymers for Enhanced Curing for Production of Wood Composite Panels; Coatings World: Columbia, MD,
USA, 2019.
16. Ghorbani, M.; Liebner, F.; Van Herwijnen, H.W.; Pfungen, L.; Krahofer, M.; Budjav, E.; Konnerth, J. Lignin phenol formaldehyde
resoles: The impact of lignin types on adhesive properties. BioResources 2016, 11, 6727–6741. [CrossRef]
17. Vishtal, A.; Kraslawski, A. Challenges in industrial applications of technical lignins. BioResources 2011, 6, 3547–3568. [CrossRef]
18. Demuner, I.F.; Colodette, J.L.; Demuner, A.J.; Jardim, C.M. Biorefinery review: Wide-reaching products through kraft lignin.
BioResources 2019, 14, 7543–7581. [CrossRef]
19. Kalami, S.; Arefmanesh, M.; Master, E.; Nejad, M. Replacing 100% of phenol in phenolic adhesive formulations with lignin. J.
Appl. Polym. Sci. 2017, 134, 45124. [CrossRef]
20. Wisa-Biobond. Available online: https://www.wisaplywood.com/wisa-biobond/ (accessed on 15 May 2023).
21. Laurichesse, S.; Avérous, L. Chemical modification of lignins: Towards biobased polymers. Prog. Polym. Sci. 2014, 39, 1266–1290.
[CrossRef]
22. Menegazzo, F.; Ghedini, E.; Signoretto, M. 5-Hydroxymethylfurfural (HMF) Production from Real Biomasses. Molecules 2018, 23,
2201. [CrossRef] [PubMed]
23. Fabbri, F.; Bischof, S.; Mayr, S.; Gritsch, S.; Jimenez Bartolome, M.; Schwaiger, N.; Guebitz, G.M.; Weiss, R. The Biomodified
Lignin Platform: A Review. Polymers 2023, 15, 1694. [CrossRef] [PubMed]
24. Zhang, Y. Production and Applications of Formaldehyde-Free Phenolic Resins Using 5-Hydroxymethylfurfural Derived from
Glucose In-Situ. Ph.D. Thesis, The University of Western Ontario, London, ON, Canada, 2014.
25. Balakshin, M.; Capanema, E. On the Quantification of Lignin Hydroxyl Groups With 31P and 13C NMR Spectroscopy. J. Wood
Chem. Technol. 2015, 35, 220–237. [CrossRef]
26. Ferreira, A.M.; Pereira, J.; Almeida, M.; Ferra, J.; Paiva, N.; Martins, J.; Magalhães, F.D.; Carvalho, L.H. Biosourced Binder for
Wood Particleboards Based on Spent Sulfite Liquor and Wheat Flour. Polymers 2018, 10, 1070. [CrossRef]
27. Chen, Y.; Cai, T.; Dang, B.; Wang, H.; Xiong, Y.; Yao, Q.; Wang, C.; Sun, Q.; Jin, C. The properties of fibreboard based on
nanolignocelluloses/CaCO3 /PMMA composite synthesized through mechano-chemical method. Sci. Rep. 2018, 8, 5121.
[CrossRef] [PubMed]

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