See discussions, stats, and author profiles for this publication at: [Link]

net/publication/343448184

Water-Resistant Casein-Based Adhesives for Veneer Bonding in

Biodegradable Ski Cores

Article  in  Polymers · August 2020

DOI: 10.3390/polym12081745

CITATIONS READS

13 1,725

4 authors, including:

Ronald Schwarzenbrunner A. Petutschnigg

Fachhochschule Salzburg Fachhochschule Salzburg
4 PUBLICATIONS   24 CITATIONS    192 PUBLICATIONS   2,321 CITATIONS   

SEE PROFILE SEE PROFILE

Eugenia Mariana Tudor

Fachhochschule Salzburg
40 PUBLICATIONS   469 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Mechanical and physical properties of nutshell based particleboards View project

UTILIZAÇÃO DE TANINO CONDENSÁVEL PARA ELABORAÇÃO DE NOVOS PRODUTOS View project

All content following this page was uploaded by Eugenia Mariana Tudor on 05 August 2020.

The user has requested enhancement of the downloaded file.

 polymers
Article
Water-Resistant Casein-Based Adhesives for Veneer
Bonding in Biodegradable Ski Cores
Ronald Schwarzenbrunner 1 , Marius Catalin Barbu 1,2 , Alexander Petutschnigg 1 and
Eugenia Mariana Tudor 1,2, *
1 Forest Products Technology and Timber Construction Department, Salzburg University of Applied Sciecnces,
Markt 136a, 5431 Kuchl, Austria; [Link]-b2016@[Link] (R.S.);
[Link]@[Link] (M.C.B.); [Link]@[Link] (A.P.)
2 Faculty of Wood Engineering, Transilvania University of Brasov, B-dul. Eroilor nr. 29,
500036 Brasov, Romania
* Correspondence: [Link]@[Link]




Received: 30 June 2020; Accepted: 3 August 2020; Published: 5 August 2020


Abstract: The aim of this study is to investigate the performance of casein-based adhesives
for the bonding of ash (Fraxinus spp.) veneers for the manufacture of biodegradable skis.
Different formulations containing casein powder, water, lime, sodium silicate, and various glue
amounts were tested for shear strength after water storage, modulus of rupture and modulus of
elasticity, water absorption, and thickness swelling. Two other classic wood adhesives, namely epoxy
and polyvinyl acetate (PVAc) type D4 were used as control. The highest efficiency of both mechanical
and physical properties was recorded for the samples glued with caseins and an increased amount of
lime. There was also an affinity between casein adhesive distribution and physical and mechanical
plywood performance. Moreover, the developed casein-based glues were also used to bond the
plywood for ski cores and tested in real-life winter conditions.

Keywords: casein; veneer bonding; biodegradable gluing; ski core

1. Introduction
The main intrinsic incentives associated to the enhancement of research on alternative adhesives
for wood composites are the increased concern for bio-based glues and the health hazards resulting
from the emissions from synthetic polymers [1,2].
One of the most common adhesives for wood-based materials is urea-formaldehyde (UF) [3]. It is
used because of the high reactivity, colorlessness, rapid curing, and low cost [2,4]. UF is considered to
be probably carcinogenic to humans [5–8].
The constant interest for formaldehyde free glues has been an important driver for the comeback
of protein-based adhesives [9–11]. The overshadowed animal binders from collagen, blood, and casein
have been used for centuries. The fish glues have been used since the 1800s and the soy glues since
the 1900s [12]. Other natural adhesives are starch, tree gum, clays, cellulose, lignin, tannin, pitch,
and dextrines [13–16].
Milk proteins are classified as caseins or whey proteins, depending on the different solubilities at
a pH value of 4.6 [1], with notable adhesive properties. For thousands of years, milk proteins have
been used as main ingredients in natural adhesive formulations [13,17,18]. They were substituted by
synthetic polymers because of the cost [19], the easier processing [20], and the increased demands for
milk protein for use in the food industry [1,13].
The use of casein as a glue for wood dates back to ancient Egypt [1] or the Middle Ages,
as woodworking cement, when craftsmen employed it to bind together thin panels into thicker panels

Polymers 2020, 12, 1745; doi:10.3390/polym12081745 [Link]/journal/polymers

Polymers 2020, 12, x FOR PEER REVIEW  2 of 10 

Polymers 2020, 12, 1745 2 of 10

strength; nowadays, this protein adhesive is used for gluing bottle labels or cigarette papers [1,26] or 
is employed in high quality paper finishing, for antistatic coating of natural and synthetic fibers, and 
for indoor applications (plywood, door panels, laminates) [19]. Casein was considered a structural 
for paintings [21] or for the manufacture of Stradivari violins [22]. During the First World War,
wood adhesive and was used also in the production of glulam beams [27]. 
the plywood utilized in aircrafts was glued with casein adhesives [23–25] because of its good bond
Casein is procurable as powder [28]. To solubilize the casein, the formulation includes soaking 
strength; nowadays, this protein adhesive is used for gluing bottle labels or cigarette papers [1,26] or is
in water and, after it has swollen, blending with an alkali [1]. The sodium silicate extends the pot life 
employed in high quality paper finishing, for antistatic coating of natural and synthetic fibers, and for
and the adhesion is increased by riveting tannate or alkali tannate [19]. The viscosity can be lowered 
indoor applications (plywood, door panels, laminates) [19]. Casein was considered a structural wood
by decreasing the hydrogen bonds, adding urea and ammonia [29]. 
adhesive and was used also in the production of glulam beams [27].
The  aim  of  this  work  was  to  analyze  the  suitability  of  casein  glues  as  an  alternative  to 
Casein is procurable as powder [28]. To solubilize the casein, the formulation includes soaking in
conventional  adhesives  for  the  bonding  of  veneers  as  main  raw  material  for  biodegradable  ski 
water and, after it has swollen, blending with an alkali [1]. The sodium silicate extends the pot life and
construction. The focus of the research was set on biodegradable and nontoxic ingredients. 
the adhesion is increased by riveting tannate or alkali tannate [19]. The viscosity can be lowered by
decreasing the hydrogen bonds, adding urea and ammonia [29].
2. Materials and Methods 
The aim of this work was to analyze the suitability of casein glues as an alternative to conventional
The ash veneers (Fraxinus spp.), 1.44 mm thick, with a moisture content of 8.42%, were supplied 
adhesives for the bonding of veneers as main raw material for biodegradable ski construction. The focus
from the company J. u. A. Frischeis GmbH (Salzburg, Austria), to produce the 3‐layer plywood for 
of the research was set on biodegradable and nontoxic ingredients.
all samples (Figure 1). The veneer was glued with a casein recipe we developed on our own. The 
2. Materials and Methods
formulation for the glues consisted of casein powder (lactic‐acid precipitated), water (pH value 7), 
and  The
lime ash
(soaked 
veneers in  water  for spp.),
(Fraxinus 88  months, 
1.44 mmdry thick,
content: 
with60.9%),  both  from 
a moisture content Kremer  Pigmente 
of 8.42%, were
(Aichstetten, Germany). 
supplied from the company J. u. A. Frischeis GmbH (Salzburg, Austria), to produce the 3-layer
Two  for
plywood types 
all of  classical 
samples adhesives 
(Figure for  wood 
1). The veneergluing  were  used 
was glued with as  reference: 
a casein recipepolyvinyl  acetate 
we developed
(PVAc) D4 (Kleiberit 303) from Becker (Weingarten, Germany) and epoxy resin (Presto Epoxyharz) 
on our own. The formulation for the glues consisted of casein powder (lactic-acid precipitated),
water Motip 
from  Dupli 
(pH value 7), (Haßmersheim, 
and lime (soakedGermany).  Both 
in water for are  common 
88 months, because 
dry content: of  their 
60.9%), bothhigh 
fromresistance 
Kremer
against water, their low cost (especially PVAc), high availability, and easy processing [28]. 
Pigmente (Aichstetten, Germany).

 
Figure 1. Sample of 3-layer plywood bonded with casein-based adhesive.
Figure 1. Sample of 3‐layer plywood bonded with casein‐based adhesive. 

Two types of classical adhesives for wood gluing were used as reference: polyvinyl acetate (PVAc)
The  casein  powder  was  soaked  in  water  for  four  hours  and  subsequently  mixed  with  lime 
D4 (Kleiberit 303) from Becker (Weingarten, Germany) and epoxy resin (Presto Epoxyharz) from Motip
(Figure 2). The ingredients were mixed manually at room temperature (20 °C and 35% relative air 
Dupli (Haßmersheim, Germany). Both are common because of their high resistance against water,
humidity) until it resulted in a uniform mass. 
their low cost (especially PVAc), high availability, and easy processing [28].
Previous research [28] has shown that the formulation based on “Casein 1” achieved the best 
The casein powder was soaked in water for four hours and subsequently mixed with lime
bonding  quality  and  subsequent  appropriate  mechanical  properties  (see  Section  2.2.  Testing 
(Figure 2). The ingredients were mixed manually at room temperature (20 ◦ C and 35% relative air
Methods), compared to previous tested formulations. For this reason, “Casein 1” served as basis for 
humidity) until it resulted in a uniform mass.
the formulations studied in this research, with a glue amount of 600 g/m2. 
The sample labeling was written as follows: the capital letter after “Casein 1“ means a change in 
manufacturing  process  and  the  number  corresponds  to  a  higher  water  amount  (“Casein  2”)  and 
higher lime amount (“Casein 3“). 
The casein powder of “Casein 1C” was just soaked for 1 h before mixing all ingredients. The 
glue was applied on veneer sheets directly after mixing, except for “Casein 1B“, utilized one hour 
later after blending (Table 1).   
Polymers 2020, 12, 1745 3 of 10
Polymers 2020, 12, x FOR PEER REVIEW  3 of 10 

 
Figure 2. Preparing the adhesive based on casein powder, water, and lime.
Figure 2. Preparing the adhesive based on casein powder, water, and lime. 

Previous research [28] has shown that the formulation based on “Casein 1” achieved the best
For each type of plywood, the veneer was cut in 300 mm × 300 mm sheets, conditioned for one 
bonding quality and subsequent appropriate mechanical properties (see Section 2.2. Testing Methods),
month at 20 °C and 35% relative air humidity. The higher percentage of air humidity of 65% was not 
compared to previous tested formulations. For this reason, “Casein 1” served as basis for the
appropriate,  because  of  previous  observations  of  Schwarzenbrunner  (2019).  The  moisture  content 
formulations studied in this research, with a glue amount of 600 g/m2 .
(m.c.) of the veneers was 8.42%. This level of m.c. should improve the penetration of the glue into the 
The sample labeling was written as follows: the capital letter after “Casein 1” means a change in
wood, to strengthen the bonding. When using casein glues, it is recommended to keep the m.c. of the 
manufacturing process and the number corresponds to a higher water amount (“Casein 2”) and higher
veneers at about 8% [30]. 
lime amount (“Casein 3”).
The casein powder of “Casein 1C” was just soaked for 1 h before mixing all ingredients. The glue
Table 1. Adhesive formulations for the bonding of 3‐layer ash plywood (4 mm thickness). 
was applied on veneer sheets directly after mixing, except for “Casein 1B”, utilized one hour later after
blending (Table 1).   Casein (%)  Water (%)  Lime (%)  Glue Amount (g/m2) 
Epoxy  ‐  ‐  ‐  250 
Adhesive formulations
Table [Link]  ‐  for the bonding
‐  of 3-layer
‐  ash plywood 150 
(4 mm thickness).
Casein 1A  27.29  67.13  5.57  600 
Casein (%) Water (%) Lime (%) Glue Amount (g/m2 )
Casein 1B *  27.29  67.13  5.57  600 
Epoxy - -
Casein 1C  27.29  67.13  5.57 - 250
600 
PVAc - - - 150
Casein 1D 
Casein 1A 27.29 
27.29 67.13 
67.13 5.57 
5.57 900 
600
Casein 1E 
Casein 1B * 27.29 
27.29 67.13 
67.13 5.57 
5.57 300 
600
Casein 2 
Casein 1C 20.51 
27.29 75.30 
67.13 4.19 
5.57 600 
600
Casein 1D
Casein 3  27.29
24.01  67.13
59.07  5.57
16.92  900
600 
Casein 1E 27.29 67.13 5.57 300
*  “Casein  1B”  has  the  same  formulation  as  “Casein  1A”,  but  was  used  one  hour  later  after 
Casein 2 20.51 75.30 4.19 600
blending.  Casein 3 24.01 59.07 16.92 600
* “Casein 1B” has the same formulation as “Casein 1A”, but was used one hour later after blending.
2.1.   Manufacturing of Plywood 
For each type of
Three‐layered  plywood,
plywood  the veneer
boards  were manufactured  with ×1.44 mm 
was cut in 300 mm 300 mm ash sheets, conditionedwith 
veneer, glued  for one
the 
month at 20 ◦ C and 35% relative air humidity. The higher percentage of air humidity of 65% was not
adhesives described in Table 2, and pressed with a Höfer HLOP 280 hydraulic laboratory press (Höfer 
appropriate, because of previous observations of Schwarzenbrunner (2019). The moisture content
Presstechnik, Taiskirchen, Austria). A total number of nine boards were produced. 
(m.c.) of the veneers was 8.42%. This level of m.c. should improve the penetration of the glue into the
wood, to strengthen the bonding. When using casein glues, it is recommended to keep the m.c. of the
Table 2. Pressing parameters of reference glues. 
veneers at about 8% [30].
Pressing Temperature  Pressing   
  Pressing Time (min or h) 
2.1. Manufacturing of Plywood (°C)  Force (kN) 
Epoxy  18 h  20  (clamps) 
Three-layered plywood boards were
PVAc D4  manufactured with 1.4450 
15 min  mm ash veneer, glued
135  with the
adhesives described in
All casein samples Table 2, and pressed
16 h  with a Höfer HLOP 280
20  hydraulic laboratory
342  press
(Höfer Presstechnik, Taiskirchen, Austria). A total number of nine boards were produced.
Polymers 2020, 12, 1745 4 of 10

Table 2. Pressing parameters of reference glues.

Pressing Time (min or h) Pressing Temperature (◦ C) Pressing Force (kN)

Epoxy 18 h 20 (clamps)
PVAc D4 15 min 50 135
All casein samples
Polymers 2020, 12, x FOR PEER REVIEW 
16 h 20 342 4 of 10 

After gluing the veneers with casein, four panels were pressed simultaneously with a pressing 
After gluing the veneers with casein, four panels were pressed simultaneously with a pressing
force of 342 kN for 16 h at 20 °C and 35% relative air humidity (Tables 1 and 2). The glue application 
force of 342 kN for 16 h at 20 ◦ C and 35% relative air humidity (Tables 1 and 2). The glue application
was 600 g/m
was 600 g/m22. Only “Casein 1D” had a 50% higher glue consumption and “Casein 1E” had a 50% 
. Only “Casein 1D” had a 50% higher glue consumption and “Casein 1E” had a 50%
lower glue consumption. This unusually high value resulted from the fact that the casein glue consists 
lower glue consumption. This unusually high value resulted from the fact that the casein glue consists
of more than 60% water, which slowly evaporates during hardening. 
of more than 60% water, which slowly evaporates during hardening.
After another one‐month conditioning at 20 °C and 35% relative air humidity, the finished panels 
After another one-month conditioning at 20 ◦ C and 35% relative air humidity, the finished panels
were cut into specimens and then tested. 
were cut into specimens and then tested.

2.2. 
2.2.  Testing Methods 
Testing Methods
Physical 
Physical and 
and mechanical 
mechanical properties 
properties of 
of the 
the samples 
samples glued 
glued with 
with casein 
casein adhesive 
adhesive and 
and reference 
reference
resins were evaluated according to European norms. Prior to testing, the samples were conditioned 
resins were evaluated according to European norms. Prior to testing, the samples were conditioned at
20 ◦ C and 65% relative air humidity until constant mass was reached.
at 20 °C and 65% relative air humidity until constant mass was reached. 
The tests for mechanical properties were carried out using a Zwick Roell Z250 universal testing 
The tests for mechanical properties were carried out using a Zwick Roell Z250 universal testing
machine  (ZwickRoell, 
machine (ZwickRoell, Ulm, 
Ulm, Germany), 
Germany), with  following 
with following adjustment adjustment 
tensile oftensile 
0.973201of 
at a0.973201  at  a 
measurement
measurement range of 4000–20000 N. 
range of 4000–20,000 N.
Ten specimens from each type of plywood board with 80 mm distance between clamps, 25 ± 0.5 
Ten specimens from each type of plywood board with 80 mm distance between clamps, 25 ± 0.5 mm
mm shear width, 25 ± 0.5 mm shear length, and a saw cut width of 3 mm were cut for the tensile shear 
shear width, 25 ± 0.5 mm shear length, and a saw cut width of 3 mm were cut for the tensile shear test
test (Figure 3) according to EN 314‐1:2005‐03 [31]. The samples were cut considering that the grain 
(Figure 3) according to EN 314-1:2005-03 [31]. The samples were cut considering that the grain direction
direction  of between
of the layer the  layer the
between  the under
glue lines glue  lines 
test isunder  test  is  perpendicular 
perpendicular to the lengthto 
ofthe  length 
it. The of  it.  The 
pretreatment
included water immersion of the samples (20 ◦ C, pH value 7) for 24 h.
pretreatment included water immersion of the samples (20 °C, pH value 7) for 24 h. 

 
Figure 3. Shear strength test for 3-layer plywood with a Zwick Roell Z250 universal testing machine.
Figure 3. Shear strength test for 3‐layer plywood with a Zwick Roell Z250 universal testing machine. 

To determine the 3‐point bending strength according to EN 310:2005‐12‐01 [32], six samples with 
140, 50, and 4.5 mm length, width, and thickness were tested for each board. 
Thickness swelling and water absorption were determined for eight samples with 50 mm by 50 
mm per board (Figure 4). Their thicknesses and weight were measured at a level of accuracy of 0.1 
mm and 0.01 g, according to EN 317:2005‐12‐01 [33]. In the next step, specimens were immersed for 
Polymers 2020, 12, 1745 5 of 10

To determine the 3-point bending strength according to EN 310:2005-12-01 [32], six samples with
140, 50, and 4.5 mm length, width, and thickness were tested for each board.
Thickness swelling and water absorption were determined for eight samples with 50 mm by
50 mm per board (Figure 4). Their thicknesses and weight were measured at a level of accuracy of
0.1 mm and 0.01 g, according to EN 317:2005-12-01 [33]. In the next step, specimens were immersed
for 24 h in water at 20 ◦ C and pH level of 7. Subsequently, the samples were taken out and rinsed to
eliminate excessive water. The samples were reweighed and the thickness measured again from the
Polymers 2020, 12, x FOR PEER REVIEW 
same location prior to water soaking. 5 of 10 

 
Figure 4. Sample with 3-layer plywood after 24 h water soaking.
Figure 4. Sample with 3‐layer plywood after 24 h water soaking. 
3. Results
3. Results 
The samples bonded with epoxy resin achieved the highest tensile shear strength after water
The samples bonded with epoxy resin achieved the highest tensile shear strength after water 
storage, which is not surprising, as this is a water-resistant thermoset (Table 3). “Casein 3” had the
storage, which is not surprising, as this is a water‐resistant thermoset (Table 3). “Casein 3” had the 
second highest tensile shear strength and a low dispersion after a 24-h water bath. This casein glue
second highest tensile shear strength and a low dispersion after a 24‐h water bath. This casein glue 
formulation with 16% lime achieved a 2.7 times higher tensile shear strength than the most waterproof
formulation 
PVAc with D4).
glue (class 16% Alllime  achieved 
shear strengtha values
2.7  times  higher 1”
for “Casein tensile  shear  strength 
formulations than  the 
were relatively most 
similar,
waterproof  PVAc  glue  (class  D4).  All  shear  strength  values  for  “Casein  1”  formulations 
despite the various changes in manufacturing (“Casein 1C” soaked for 1 h in water before mixing were 
relatively similar, despite the various changes in manufacturing (“Casein 1C” soaked for 1 h in water 
with other ingredients of the formulation) and application (“Casein 1B” was utilized after one hour).
before mixing with other ingredients of the formulation) and application (“Casein 1B” was utilized 
The minimum value of shear strength for the “Casein 1” series was 0.18 MPa and the maximum value
after one hour). The minimum value of shear strength for the “Casein 1” series was 0.18 MPa and the 
0.86 MPa. “Casein 1D”, which had a higher glue amount (900 g/m2 ), achieved a 50% higher tensile
maximum value 0.86 MPa. “Casein 1D”, which had a higher glue amount (900 g/m
shear strength than “Casein 1A”. For the samples with the same formulation and different
2), achieved a 50% 
application,
higher  tensile  shear  strength  than  “Casein  1A”.  For  the  samples  with  the  same 
“Casein 1A” and “Casein 1B”, a difference of 15% of the shear strength was measured. The “Caseinformulation  and 
2”
different application, “Casein 1A” and “Casein 1B”, a difference of 15% of the shear strength was 
formulation with more water (74.53%) showed the weakest glue joint, with a minimum of 0.08 MPa
measured. The “Casein 2” formulation with more water (74.53%) showed the weakest glue joint, with 
and a maximum of 0.19 MPa.
a minimum of 0.08 MPa and a maximum of 0.19 MPa. 

Table 3. Mean, standard deviation, minimum, and maximum of the tensile shear strength of all test 
samples after water storage for 24 h, n = 10 (a, b, c, d values with the same letter are not significantly 
different: ANOVA, Post‐Hoc Tukey HSD, α = 0.05); values are significantly different to the control 
(epoxy) (ANOVA; p < 0.05). 

Tensile Shear Strength (MPa)   
Sample  Mean (Standard Deviation)  Minimum  Maximum  p 
Casein 1A  0.51 a,b (0.21)  0.22  0.83  . 
Casein 1B  0.60 a,b (0.24)  0.18  0.86  . 
Casein 1C  0.49   (0.16) 
a,b 0.26  0.75  . 
Casein 1D  0.76 b,c (0.06)  0.65  0.83  . 
Casein 1E  0.16 a (0.04)  0.13  0.24  . 
Casein 2  0.15 a (0.04)  0.08  0.19  . 
Casein 3  1.20 c (0.04)  1.12  1.24  . 
Epoxy  2.35   (0.78) 
d 1.24  3.68  ‐ 
PVAc D4  0.45 a,b (0.25)  0.16  0.76  . 
Polymers 2020, 12, 1745 6 of 10

Table 3. Mean, standard deviation, minimum, and maximum of the tensile shear strength of all test
samples after water storage for 24 h, n = 10 (a, b, c, d values with the same letter are not significantly
different: ANOVA, Post-Hoc Tukey HSD, α = 0.05); values are significantly different to the control
(epoxy) (ANOVA; p < 0.05).

Tensile Shear Strength (MPa)

Sample Mean (Standard Deviation) Minimum Maximum p
Casein 1A 0.51 a,b (0.21) 0.22 0.83 .
Casein 1B 0.60 a,b (0.24) 0.18 0.86 .
Casein 1C 0.49 a,b (0.16) 0.26 0.75 .
Casein 1D 0.76 b,c (0.06) 0.65 0.83 .
Casein 1E 0.16 a (0.04) 0.13 0.24 .
Casein 2 0.15 a (0.04) 0.08 0.19 .
Casein 3 1.20 c (0.04) 1.12 1.24 .
Epoxy 2.35 d (0.78) 1.24 3.68 -
PVAc D4 0.45 a,b (0.25) 0.16 0.76 .

The modulus of elasticity (MOE) of all tested specimens differed only slightly. If PVAc is ignored,
all formulations varied less than 20% among themselves (Table 4). The most elastic formulations were
PVAc (31.4% higher MOE than “Casein 1E”) followed by “Casein 3”, epoxy, “Casein 1C”, and “Casein
2”. The stiffest were all “Casein 1” formulations, except “Casein 1C”.

Table 4. Mean, standard deviation, minimum, and maximum of the modulus of elasticity (MOE) and
flexural strength (MOR) of all test samples, moisture content (m.c.) = 8.42%, n = 6 (a and b values with
the same letter are not significantly different: ANOVA, Post-Hoc Tukey HSD, α = 0.05), values are
significantly different to the control (epoxy) (ANOVA; p < 0.05).

MOE (GPa) MOR (MPa)

Label Mean (Standard Mean (Standard

Minimum Maximum p Minimum Maximum p
Deviation) Deviation)
Casein 1A 7.60 a,b (1.12) 5.96 9.02 . 100.91 b (9.14) 89.25 114.78 -
Casein 1B 7.32 a (0.50) 6.74 8.19 . 101.73 b (5.40) 93.20 109.39 .
Casein 1C 8.41 a,b (1.18) 6.82 9.57 - 105.47 b (11.88) 86.48 121.95 .
Casein 1D 7.68 a,b (0.35) 7.07 8.03 - 96.17 b (5.54) 88.52 102.43 .
Casein 1E 7.19 a (0.89) 6.32 8.75 - 65.10 a (18.24) 40.81 96.32 .
Casein 2 8.10 a,b (0.74) 6.86 8.76 . 96.18 b (6.08) 87.96 105.43 -
Casein 3 8.57 a,b (1.84) 6.03 11.79 . 105.78 b (19.04) 75.11 134.62 .
Epoxy 8.50 a,b (1.06) 6.47 9.37 . 105.27 b (11.57) 82.56 114.86 -
PVAc D4 9.45 b (1.29) 8.00 11.22 . 99.25 b (20.58) 62.70 126.62 .

The flexural strength (MOR) of all tested specimens differed only slightly (less than 10% without
considering “Casein 1D”) (Table 4). Following the same trend as for MOE, “Casein 1E”, the formulation
with a higher glue amount, had the lowest MOR of just 61.5% (lower than that of the specimen with
the highest value, which was “Casein 3”).
Analyzing the water absorption after 2 h water immersion (Table 5), the lowest mean was measured
for the sample glued with epoxy resin: 13.15%, with a standard deviation of 1.1%. From all the samples
manufactured with casein glue, the “Casein 1B” had the lowest mean value of 16.75%, with a standard
deviation of 0.89% (10% lower compared with the values for the samples “Casein 1A”). The highest
water absorption was reached for the samples “Casein 2”, which was 24.4% (0.98% standard deviation).
Polymers 2020, 12, 1745 7 of 10

Table 5. Mean, standard deviation, minimum, and maximum of the water absorption and thickness
swelling of all test samples after water storage for 2 h, n = 8 (a, b, c, d, e values with the same letter are
not significantly different: ANOVA, Post-Hoc Tukey HSD, α = 0.05), values are significantly different
to the control (epoxy) (ANOVA; p < 0.05).

Water Absorption (%) Thickness Swelling (%)

Mean (std. dev.) Minimum Maximum p Mean (std. dev.) Minimum Maximum p
Casein 1A b,c,d 16.52 19.83 . a
5.65 (0.73) 4.32 6.47 .
18.56 (1.10)
Casein 1B 16.75 b (0.89) 15.30 17.97 . 8.52 a (1.75) 5.15 10.02 .
Casein 1C 20.46 d (1.80) 17.17 22.66 . 8.90 a (2.34) 4.96 12.13 .
Casein 1D 17.61 b,c (0.58) 16.65 18.46 . 4.39 a (2.83) 0.16 8.06 .
Casein 1E 22.89 e (1.98) 20.14 26.06 . 10.26 a,b (1.41) 8.77 12.61 -
Casein 2 24.40 e (0.98) 23.29 25.85 . 4.88 a (2.83) 0.96 9.19 .
Casein 3 17.56 b,c (0.29) 17.26 17.92 . 9.54 a,b (4.29) 2.87 16.42 -
Epoxy 13.15 a (1.10) 11.49 14.58 - 9.96 a,b (1.64) 8.09 12.86 -
PVAc D4 19.05 c,d (0.92) 17.99 20.14 . 15.48 b (6.96) 6.65 27.24 .

The thickness swelling after 2 h (Table 5) was the lowest for the “Casein 1D” samples,
4.39% (2.83% standard deviation), “Casein 2”, 4.88% (2.83% standard deviation), and “Casein 1A”,
5.65% (0.73% standard deviation). The reference samples bonded with epoxy resin and PVAc recorded
higher means for thickness swelling, 15.48% and 9.96%, respectively.
In the case of water absorption after 24 h water storage, the samples glued with epoxy had the
lowest values, with an average of 40.24% (Table 6). Of all casein glues, “Casein 1B” (left standing for 1 h
after mixing) showed the lowest water uptake, with a minimum of 45.93%. Casein glues with a higher
glue application (“Casein 1D”) or a higher lime amount (“Casein 3”) had just about 5% higher results.
If the casein for the “Casein 1” formulation was only soaked for 1 h (“Casein 1C”), the water absorption
was 9.5% higher compared to the case when it was soaked for 4 h (“Casein 1A”). The highest water
absorption was measured for the samples with a lower glue application (“Casein 1E”) and with a higher
water amount (“Casein 2”). Results of PVAc showed approximately the mean value of all results.

Table 6. Mean, standard deviation, minimum, and maximum of the water absorption and thickness
swelling of all test samples after water storage for 24 h, n = 8 (a, b, c, d, e values with the same letter are
not significantly different: ANOVA, Post-Hoc Tukey HSD, α = 0.05), values are significantly different
to the control (epoxy) (ANOVA; p < 0.05).

Water Absorption (%) Thickness Swelling (%)

Mean (std. dev.) Minimum Maximum p Mean (std. dev.) Minimum Maximum p
Casein 1A b,c,d 50.68 60.62 . a
6.01 (0.77) 4.59 6.84 .
56.74 (3.29)
Casein 1B 50.71 b (2.70) 45.93 54.14 . 9.06 a (1.84) 5.53 10.68 .
Casein 1C 62.15 d (5.62) 51.89 68.94 . 9.49 a (2.49) 5.33 13.00 .
Casein 1D 53.18 b,c (1.60) 50.67 55.64 . 4.66 a (3.03) 0.21 8.67 .
Casein 1E 69.86 e (6.20) 61.13 79.72 . 10.93 a,b (1.49) 9.37 13.38 -
Casein 2 74.00 e (3.10) 70.25 78.48 . 4.77 a (3.91) −1.72 9.91 .
Casein 3 53.50 b,c (0.85) 52.43 54.93 . 10.16 a,b (4.57) 2.98 17.43 -
Epoxy 40.24 a (3.33) 35.06 44.77 - 10.54 a,b (1.75) 8.52 13.63 -
PVAc D4 58.15 c,d (2.77) 54.74 61.45 . 16.46 b (7.41) 7.03 28.94 .

In the case of thickness swelling after 24 h water immersion (Table 6), with the exception of the
“Casein 1E” samples (with less casein adhesive amount), all the other samples glued with casein
recorded values at least 34% to 46% lower than that of epoxy and PVAc glued plywood.

4. Discussion
For all the tests, the differences between the minimum and maximum values are due to the
cutting plan. For each test, the samples were taken from different positions of the 3-layered veneers.
Polymers 2020, 12, 1745 8 of 10

The differences might be caused also by the natural inhomogeneities of the wood; hence, the glue
application may not be homogenous.
The bonding with epoxy resin offered the samples the highest tensile shear strength of 2.35 MPa.
Adding more lime in the adhesive’s formulation (17%) conferred the samples “Casein 3” the highest
values of the tensile shear strength, about two times bigger than the series “Casein 1”.
The modulus of elasticity was increased when PVAc was used to glue the three layers of veneer
(9.45 N/mm2 ), but in the case of the epoxy adhesive, the results were similar to the samples glued with
casein from series “Casein 3” and “Casein 1C” (about 105 N/mm2 ).
The trend for water absorption and thickness swelling after 2 and 24 h was similar. The lowest
values were measured for samples “Casein 1B”, “Casein 1D”, and “Casein 3”, with no considerable
differences. That means that the tested specimens soaked for 24 h absorbed about three times more
water compared to the values measured after 2 h. For the samples with the same formulation and
different application (”Casein 1A” and “Casein 1B”—left standing for one hour after mixing) a difference
of 33% of the thickness swelling was measured.
One very important physical property of the casein-bonded 3-layer plywood is the thickness
swelling. The samples “Casein 1D” and “Casein 2” had for both tests (after 2 and 24 h) a thickness
swelling less than 5%. Moreover, for the series “Casein 1A” a level of 6% thickness swelling is still
significantly low.

5. Conclusions
The casein glue mixtures are to be used effectively in the bonding of 3-layer ash plywood. The
samples manufactured with formulations with a higher lime amount (over 10%) achieved the highest
tensile shear strength after water storage. Their water-resistance is up to three times higher compared
with the samples glued with PVAc class D4. Both values for modulus of rupture and modulus of
elasticity were mostly higher for these testing specimens, compared with other samples bonded with
other amounts of casein, water, and lime. Another important factor regarding mechanical and physical
properties of the casein-bonded plywood is the amount of glue. An amount of 600 g/m2 glue showed
the best performances.
Significant differences between the various formulations for casein-based glues were found,
leading to the conclusion that there is an affinity between the ratio of the components, glue amount,
and physical and mechanical plywood performance.
In summary, the samples bonded with “Casein 2” and “Casein 3” had the highest water resistance
and mostly the highest mechanical properties of all casein glue formulations, also compared to PVAc (D4).
Only the samples bonded with epoxy had a higher water resistance due to the duroplast characteristics.
The big differences of variance coefficients, namely for shear strength between 3.33% and 55.55%,
MOE between 4.56% and 21.47%, MOR between 5.76% and 28.02%, and thickness swelling after
24 h between 12.81% and 81.97% are due to the inhomogeneous glue spread on the veneer surface,
particularities of the ash wood, for example extractive content, pH value, wettability, with influence on
the bonding strength, dimensional stability, and durability of adhesive joints [34].
We would also like to mention that the casein-bonded veneers were used for the sandwich
construction of skis (core layer) and tested this year in the Austrian Alps, with carbon-fiber reinforcement.
The testing of the skis is not the object of this study, but the gluability of casein glue on veneer sheets.

Author Contributions: Conceptualization, R.S. and E.M.T.; methodology, R.S.; validation, M.C.B. and A.P.;
formal analysis, A.P.; investigation, R.S.; resources, R.S.; writing—original draft preparation, E.M.T. and R.S.;
writing—review and editing, E.M.T.; visualization, E.M.T. and M.C.B.; supervision, M.C.B. and E.M.T. All authors
have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: Thanks to Ing. Thomas Wimmer (Salzburg University of Applied Sciences, Campus Kuchl).
Conflicts of Interest: The authors declare no conflicts of interest.
Polymers 2020, 12, 1745 9 of 10

References
1. Guo, M.; Wang, G. Milk protein polymer and its application in environmentally safe adhesives. Polymers
2016, 8, 324. [CrossRef] [PubMed]
2. Frihart, C.; Lorenz, L. Protein Adhesives. In Handbook of Adhesive Technology; CRC Press: New York, NJ, USA,
2018; pp. 145–175.
3. Salthammer, T.; Mentese, S.; Marutzky, R. Formaldehyde in the Indoor Environment. Chem. Rev. 2010,
110, 2536–2572. [CrossRef] [PubMed]
4. Anga, A.; Ashaaria, Z.; Leeb, S.; Tahirb, P.; Halisa, R. Lignin-based copolymer adhesives for composite wood
panels—A review. Int. J. Adhes. Adhes. 2019, 95, 102408. [CrossRef]
5. Blackwell, M.; Kang, H.; Thomas, A.; Infante, P. Formaldehyde: Evidence of carcinogenicity. Can. Med. Assoc.
J. 1983, 128, 248–249.
6. Vale, P.; Rycroft, G. Occupational irritant contact dermatitis from fibreboard containing urea-formaldehyde
resin. Contact Derm. 1988, 19, 62. [CrossRef] [PubMed]
7. Priha, E. Formaldehyde release from resin-containing wood board dusts. Appl. Occup. Environ. Hyg. Bd.
1996, 11, 465–470. [CrossRef]
8. Krief, P.; Coutrot, D.; Conso, F. Risque toxicologique professionnel lié à l’exposition aux poussières de bois
MDFOccupational-toxicological risk related to the exposure to MDF wood dust. Arch. Mal. Prof. Environ.
2008, 69, 655–666. [CrossRef]
9. Tudor, E.M.; Barbu, M.C.; Petutschnigg, A.; Réh, R. Added-value for wood bark as a coating layer for flooring
tiles. J. Clean. Prod. 2018, 170, 1354–1360. [CrossRef]
10. Solt, P.; Konnerth, J.; Gindl-Altmutter, W.; Kantner, W.; Moser, J.; Mitter, R.; van Herwijnen, H.R.W.
Technological performance of formaldehyde-free adhesive alternatives for particleboard industry. Int. J.
Adhes. Adhes. 2019, 94, 99–131. [CrossRef]
11. Tudor, E.M.; Barbu, M.C.; Petutschnigg, A.; Réh, R.; Krišt’ák, L. Analysis of Larch-Bark Capacity for
Formaldehyde Removal in Wood Adhesives. Int. J. Environ. Res. Public Health 2020, 764, 17. [CrossRef]
[PubMed]
12. Frihart, C.; Birkeland, M. Soy Properties and Soy Wood Adhesives, Soy Based Chemicals and Materials; Brentin, R.,
Ed.; ACS Publications: Washington, DC, USA, 2014; pp. 167–192. [CrossRef]
13. Eckelman, C. Brief Survey of Wood Adhesives; Purdue University Cooperative Extension Service: West Lafayette,
OH, USA, 1999.
14. Dickson, M.; Parker, D. Sustainable Timber Design; Taylor & Francis: New York, NJ, USA, 2014.
15. Dinte, E.; Sylvester, B. Adhesives: Applications and Recent Advances, in Applied Adhesive Bonding in
Science and Technology. Appl. Adhes. Bond. Sci. Technol. 2017, 119–134. [CrossRef]
16. Tudor, E.M.; Dettendorfer, A.; Kain, G.; Barbu, M.C.; Réh, R.; Krišt’ák, L. Sound-Absorption Coefficient of
Bark-Based Insulation Panels. Polymers 2020, 12, 1012. [CrossRef] [PubMed]
17. Broyard, C.; Gaucheron, F. Modifications of structures and functions of caseins: A scientific and technological
challenge. Dairy Sci. Technol. 2015, 95, 831–862. [CrossRef]
18. Ülker, O. Wood Adhesives and Bonding Theory, in Adhesives—Applications and Properties. InTech 2016, 19.
[CrossRef]
19. Audic, J.; Chaufer, B.; Daufin, G. Non-food applications of milk components and diary co-products: A review.
Le Lait 2003, 83, 417–438. [CrossRef]
20. Pizzi, A. Wood Adhesives, Chemistry and Technology; CRC Press: New York, NJ, USA, 1980.
21. Forest Products Laboratory. Casein Glues: Their Manufacture, Preparation and Application; U.S. Department of
Agriculture: Madison, WI, USA, 1980.
22. Echard, J.; Bertrand, L.; von Bohlen, A.; le Ho, A.; Paris, C.; Bellot-Gurlet, L.; Soulier, B.; Lattuati-Derieux, A.;
Thao, S.; Robinet, L.; et al. The Nature of the Extraordinary Finish of Stradivari’s Instruments. Angew. Chem.
Int. Ed. 2010, 48, 197–201. [CrossRef] [PubMed]
23. Truax, T. Gluing Wood in Aircraft Manufacture; U.S. Department for Agriculture: Washington, DC, USA, 1930.
Available online: [Link] (accessed on 4 August 2020).
24. Driver, D. Adhesive bonding for aerospace applications. In High Performance Mater Aerospace; Springer:
Dordrecht, Germany, 1995; pp. 318–339.
 Polymers 2020, 12, 1745 10 of 10

25. Müller, U.; Müller, H.; Teischinger, A. Durability of wood adhesives in 50-year-old aircraft and glider
Constructions. Wood Res. 2004, 49, 25–33.
26. Umemura, K.; Inoue, A.; Kawai, S. Development of new natural polymer-based wood adhesives I: Dry bond
strength and water resistance of konjac glucomannan, chitosan, and their composites. J. Wood Sci. 2003,
49, 221–226. [CrossRef]
27. Salzberg, H.K. Casein glues and adhesives. In Handbook of Adhesion, 2nd ed.; Van Nostrand Reinhold
Company: New York, NJ, USA, 1977; pp. 158–171.
28. Schwarzenbrunner, R. Entwicklung von nachhaltigen und wasserfesten Casein-Leim Rezepturen—Anwendung an
biologisch abbaubaren Skiern; Salzburg University of Applied Sciences: Salzburg, Austria, 2019.
29. McGann, T.; Fox, P. Physico-chemical properties of casein micelles reformed from urea-treated milk. J. Dairy
Res. 1974, 41, 45–53. [CrossRef]
30. Dunky, M.; Niemz, P. Holzwerkstoffe und Leime. Technologie und Einflussfaktoren; Springer: Berlin/Heidelberg,
Germany, 2013. Available online: [Link] (accessed on 4
August 2020).
31. EN 314-1:2005-03. Plywood—Bonding Quality—Part 1: Test Methods; CEN, European Committee for
Standardization: Brussels, Belgium, 2005.
32. EN 310:2005-12-01. Wood-Based Panels—Determination of Modulus of Elasticity in Bending and of Bending
Strength; CEN, European Committee for Standardization: Brussels, Belgium, 2005.
33. EN 317:2005-12-01. Particleboards and Fibreboards; Determination of Swelling in Thickness after Immersion in
Water, —Test Method; CEN, European Committee for Standardization: Brussels, Belgium, 2005.
34. Jiang, Y.; Schaffrath, J.; Knorz, M.; Winter, S. Bonding of Various Wood Species—Studies about Their
Applicability in Glued Laminated Timber. Mater. Jt. Timber Struct. 2014, 9, 365–374.

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license ([Link]

View publication stats