EXAMENSARBETE INOM TEKNIKOMRÅDET

TEKNISK KEMI
OCH HUVUDOMRÅDET
KEMITEKNIK,
AVANCERAD NIVÅ, 30 HP
STOCKHOLM, SVERIGE 2021

Bio-based water/dirt
repellant wood coating
INGRID JÖNSSON

KTH
SKOLAN FÖR KEMI, BIOTEKNOLOGI OCH HÄLSA
Abstract
The aim of this thesis project was to develop a fully bio-based water and dirt repellent wood coating with the
ambition to replace the current non-bio-based product on the market. Several wax and oil emulsions were
made and analyzed in terms of emulsion quality and stability. Several formulations were also tested on
different types of wood in terms of water absorption, weathering, surface pH and contact angle. Some
formulations seam to give similar water absorption as the reference, the not bio-based product and performs
similar on different types of wood with an exception on Wood type 4 where the bio-based formulations
performs better than the current reference product. Secondly the bio-based formulations form a less yellow and
rough coating compared to the current reference product. According to the weathering test the bio-based
formulations seams to perform better. However, the stability of the bio-based formulation is not as good as the
current reference product. Also, the developed bio-based conceptual formulations exhibited limited pH lowering
on Wood type 3 with alkaline pH.

Keywords
Emulsion, bio-based, coating, oils, wax, absorption, hydrophobicity, water repellency

Acknowledgement
I would like to give a special thanks to my supervisor Salman Hassanzadeh at OrganoClick for supporting me
during the project with valuable guidance and insights. I would also like to thanks the whole team at the FoU at
OrganoClick for making me feel like one of team.
Content
1. Introduction .................................................................................................................................................... 1

1.1 Aim............................................................................................................................................................ 2
2. Theory ............................................................................................................................................................ 3
2.1 Emulsion ................................................................................................................................................... 3
2.1.1 Stability .............................................................................................................................................. 3

2.1.2 Coating .............................................................................................................................................. 4

2.1.3 Water resistance and surfactants ...................................................................................................... 4
2.1.4 Contact angle .................................................................................................................................... 5
2.2 Oils and wax ............................................................................................................................................. 6
2.2.1 Oils .................................................................................................................................................... 6
2.2.2 Wax ................................................................................................................................................... 9

3. Chemicals and Materials ............................................................................................................................... 10

4. Experimental ............................................................................................................................................. 12
4.1 Emulsion ................................................................................................................................................. 12
4.2 Static hydrophobic test............................................................................................................................ 12
4.3 Contact angle .......................................................................................................................................... 13

4.4 Water absorption test .............................................................................................................................. 13

4.5 Weathering test ....................................................................................................................................... 13
4.6 Surface pH .............................................................................................................................................. 13
4.7 Stability test ............................................................................................................................................ 14
5. Result ............................................................................................................................................................ 15
5.1 Strategy .................................................................................................................................................. 15

5.2 Emulsion characterization ....................................................................................................................... 16

5.3 Static Hydrophobic test on untreated wood ............................................................................................ 19
5.4 Static hydrophobic test on Wood type 2-4 .............................................................................................. 22
5.5 Contact angle .......................................................................................................................................... 25
5.6 Water absorption..................................................................................................................................... 26
5.7 Weathering ............................................................................................................................................. 31

5.8 Surface pH .............................................................................................................................................. 32

5.9 Stability ................................................................................................................................................... 33
6. Conclusion .................................................................................................................................................... 35
7. Further aspects ............................................................................................................................................. 36
8. References .................................................................................................................................................... 37
1. Introduction
Due to climate change wood has become of greater interest as a resource of renewable material. For example
a sky scrape made in wood is planned to adorn Tokyo skyline in 2041 [1] and bottles made of wood are under
development to replace plastic bottles for soft drinks [2]. When wood is used as a material especially in
constructions and other outdoor applications it needs to be protected from degradation. Since degradation will
change the chemical structure and composition as well as its mechanical and physical properties of the wood it
can be detrimental for the function of the construction [3].

Wood degrades through several mechanisms and one of them is organisms that feed on the wood. These
organisms include different sorts of insects, molluscus, fungi and bacteria [4]. Weathering is another large
cause of degradation. In this type of degradation both physical and chemical degradation occur due to factors
like UV-light, moisture including snow, rain and dew, heat and cold variations, pollutants and abrasion
particulates in the wind [3]. For example UV-light will cause photo oxidation and photo chemical degradation of
lignin and water will be acting in hydrolysis of the cellulose and hemicellulose [3][5].

The complexity of the degradation is added by the complex structure of the wood. Wood is composed mainly
by cellulose, hemicellulose and lignin. Cellulose chains are bonded and packed together creating fibrils that are
associated with hemicellulose. The lignin are then encrusted around the fibrils making up the composite that
forms the different layers of the cell walls [6]. In different wood species there are different types of cells with
different functions and proportions. The most common cell type in spruce and pine is called tracheids and have
a width around 31-35 μm and a length of 3.1-3.4 nm depending on species and growth conditions. The
complexity gets even more intricate as the inner part of the tree (heartwood) is less permeable and more
durable against decay compared to the outer part of the tree (sapwood) since it contains more extractives [6].

An effective way to protect the wood from degradation is to coat it. Some protections are based on water born
emulsions with fatty structures that hydrophobize the wood and induce water and dirt repellence. When the
product is applied on a wood substrate and cures an uneven and hydrophobic surface is formed around the
wood fibers. This protects water and waterborne dirt from penetrate into the wood or stay at the surface of the
wood. Sequentially the form stability of the hygroscopic wood is better leading to less crack formation.
Secondly wood degrading organism like fungus will not thrive on the dry surface. However, most of the current
products are not fully bio-based therefore the goal of this project is to develop a fully bio-based emulsion to be
used as a wood coating that can be measured against the current non-bio-based reference products.

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1.1 Aim
The aim is to develop a bio-based, water and dirt repellent coating for wood.
The following criteria should be fulfilled by the developed product:

 The bio-based content should be greater than 95% to be classified as bio-based according to % Bio-
based Carbon Content ASTM D6866-20 Method B (AMS).
 The shelf-life should be longer than 2 years, since the product will be shipped and stored in shops
and homes.
 The product should be easily biodegradable.
 No large physical change like appearance and feeling should occur to the coated wood.
 The pH should be around 3 to 4 to have the same pH as natural wood to maintain the natural
environment of wood.
 The product should work on different types of wood products with different pH range and surface
chemistry.
 The product should be able to be diluted to enable a cheap and an effective production.

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2. Theory

2.1 Emulsion
Emulsions consist of three phases; two immiscible liquids and emulsifiers. Most of the emulsifiers are
surfactants; surface active agents. Surfactants have an amphipathic structure with a lyophobic group with little
attraction to the solvent and a lyophilic group with strong attraction to the solvent. When the two immiscible
liquids are mixed with emulsifiers during agitation small droplets are formed with the emulsifier oriented around
the droplets with lyophobic group adsorbed at the droplet surface and the lyophilic group pointing out towards
the solvent, see Figure 1. Without the emulsifier the two liquids will phase separate to lower the free energy by
minimizing the contact area. Hence, the emulsifiers stabilize the system by lowering the interfacial tension and
prevent the droplets to coalescence. The size of the droplet is highly dependent on the surface tension but also
on the agitation, its energy input, design of homogenizer and the flow of the liquids that is produced. Lower
tension and higher energy input results in smaller droplets [7].

Figure 1. Illustration of the three phases of an emulsion. Two immiscible liquids light and dark blue and the emulsifiers
oriented around the droplets.

2.1.1 Stability

The ability to keep the properties unchanged is referred to the emulsions stability. However, since emulsions
are thermodynamically unstable properties of the emulsion will change. Creaming, sedimentation, flocculation
and coalescence are some phenomena that change the properties. Creaming occurs when the droplets move
upwards in the emulsion due to their lower viscosity compared to the continuous phase and forms a top layer.
The opposite phenomenon is known as sedimentation. To reduce the creaming a weighting agent or a highly
dense emulsifier can be used to increase the density of the droplets and minimize the creaming. A thickener or
a gelation agent can be added to increase the viscosity of the continuous phase and in that way reduces
sedimentation. Mechanical agitation, gravity and Brownian motion keeps the droplets constantly moving
making aggregation possible. A flocculation is formed if the droplets keep their physical shape in the
aggregated form otherwise it is called coalescence. Aggregation will effect creaming and sedimentation as the
viscosity will increase and larger particles are subjected to larger gravitational force. The choice and
concentration of emulsifier will affect the degree of aggregation [7].

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2.1.2 Coating

Emulsions are used for many applications including coatings. The film formation of these coatings, latex
coatings can be divided into four stages, see Figure 2. In stage one the water starts to evaporate.
Consequently the solid concentration will increase until the particles are not allowed to be packed more
densely. In stage two the water at the interstices in between the particles starts to evaporate. The interfacial
and capillary forces will make the polymer particles deform and fill the voids that once was filled with water.
The deformation will only be possible if the Tg of the system is lower than the drying temperature. In stage
three the hydrophilic membranes breaks up forming aggregates in the film or on the surface of the forming film.
This allows the deformed particles to coalescence and fuse together. In stage four the polymer chains further
interdiffuse across the particle boundaries and entangle, creating a continuous film [8].

Figure 2. The four stages of film formation of latex coatings.

2.1.3 Water resistance and surfactants

The resistance towards water for a dispersed system film is dependent on several factors including distribution
of molecular weight and particle size, distribution of hydrophobic and hydrophilic spices, types and
concentration of additives and voids or other defects. The resistance towards water is detrimental for the
protective function of the film from a dispersed system (like latex, oil emulsions etc.). Since some of the
components in water based coatings are dispersible or soluble in water the improvement of water resistance is
a challenging goal [9].

For example in the case of latex-based formulations, when monodisperse latex is used the most efficient way
of packing the particles in the first phase of film formation is face-centred cubic structure, fcc. However a
polydisperse formulation will disturb the packing resulting in greater number of voids. The voids are regions
where the concentration of water, salt and surfactants can build up. During sintering the non-compatible
components with the forming film will be expelled into these voids and a minor part will also diffuse to the
surface. The concentration of these components in the voids will result in absorption of water through osmotic
pressure causing discoloration and blistering of the final coating [9].

The distribution of the surfactants in the film is dependent on the compatibility with the polymer as well as the
molecular weight of the surfactant. With a higher molecular weight the surfactants become more hydrophobic
resulting in higher solubility in the film. This will lead to the surfactant working as a plasticizer and increasing

4
aging but it also result in an increase of hydrophilicity of the film due to the hydrophilic character of the
surfactant, causing a less water resistant film. With a high hydrophilicity of the surfactant the more unlikely it is
to be soluble in the film instead it can be trapped in voids or pockets where they promote water adsorption
through osmotic pressure as described above [9].

Polymerisable surfactant also called surfmers have the possibility to covalently bind to the latex surface. This
will lead to better stability of the particles as the surfmers will not be able to desorb as conventional surfactants
may do. Desorption usually occur under high shear and can lead to coalescence. Another advantage is that
the water resistance of a coating will be improved. Since the surfactants are covalently attached to the particles
they will not be able to desorb and migrate to the surface of the film where they can attract water. Neither will
surfactants be trapped inside voids causing absorption of water [10]. For the surfmers to work they need to
have limited water solubility, moderate reactivity at the beginning of the polymerization so it does not get buried
inside the latex particle and high reactivity at the end so they covalently bind to the particles [11].

2.1.4 Contact angle

A liquids affinity towards a solid is referred to its wettability. A liquid drop with high affinity will spread on the
surface while a drop with low affinity will remain its shape. Wettability is an important property to get a proper
coating and a protective film. The wettability of a substrate is also a way to assess the water resistance [7].

The most important parameter to evaluate the wettability is the contact angle the drop makes against the
surface. With an angle of 0° there is perfect wetting and between 0° and 90° the surface is partially wetted but
between 90° and 180° the surface is considered as non-wetted and at 180° there is no wetting at all, see
Figure 3 [7].

Figure 3. Illustration of contact angle and wettability. From left to right: contact angle of 0°, 0°-90°, 90°-180° and 180°.

The contact angle is determined by the forces at the different interfaces, see Figure 4. This includes the force
acting between the surrounding and the solid phase making the drop spread and the forces acting between
surrounding and the surface of the drop making the drop shrink. The forces act to decrease the interfacial
areas and thereby decreasing the surface energy. For example the force acting to spread the drop lowers the
tension between the surface and the surrounding. The balance between the forces will determine the wetting
[7].

5
 Figure 4. The forces acting on a droplet placed on a surface determines the wettability.

2.2 Oils and wax

Vegetable oils have been used for protection of wood for a long time, both as a top coat or as impregnation.
With its hydrophobic character oils has the main function to reduce the moisture sensitivity [5]. By filling or
plugging the lumina of the wood cell and the pours of the cell walls the water uptake by the capillary effect will
be lower [12]. Waxes can be used as they are, in combination with other oils and resins as well as additives in
coatings to improve water resistance, gloss and softness [13]. Waxes are used in protection of wood in outdoor
application as it not only contributes to the water resistance but also the reduction of photo degradation.
Additionally, waxes can have other effect like biocidal and are generally more hydrophobic than oils [3] [14].
Moreover, it should be mentioned that wood treated with oil emulsions have shown similar water repellence as
wood treated with pure oil, illustrating the benefit of using oil emulsions in terms of material consumption [12].

2.2.1 Oils

Vegetable oils consist mainly of triglycerides i.e. esterified glycerol with fatty acids, see Figure 5. The fatty
acids can be of different length often 10-20 carbons and with different number of double bonds. Depending on
the fatty acid pattern, oils are grouped into three categories. The Non-drying oils are saturated and the semi-
drying oils have one to two double bonds while drying oils have two to three double bonds and are highly
unsaturated. Common drying oils are linseed oil and Tung oil while sunflower oil, soybean oil, safflower oil and
tall oil are examples of semidrying oils [15].

Figure 5. Example structure of a triglyceride.

6
In Table 1 fatty acid pattern are listed for some common vegetable oils [5][16][17] and in Figure 6 the fatty
acids are illustrated. The main fatty acid in Tung oil, about 80 % is α-eleostearic acid [18] while the main fatty
acid in castor oil is ricinoleic acid, also about 80 % [19]. However it should be mentioned that there are
differences in fatty acid pattern even if the oil is extracted from the same type of plant. These differences can
be attributed to origin and genetic variation of plants, seed and oil processes, refining and climate during
growing [15][20][21].

Table 1. Fatty acid pattern of different vegetable oils.

Fatty acids
Oils Palmitic Stearic Oleic Linoleic Linolenic
[wt%] [wt%] [wt%] [wt%] [wt%]

Linseed 5.5 3.5 19.1 15.3 56.6

Soybean 11.0 4.0 23.4 53.3 7.8

Tung - 4.0 8.0 4.0 -

Castor 1.5 0.5 5.0 4.0 0.5
Sunflower 6 4 42 47 1
Safflower oil 6.02 2.37 13.75 76.22 0.04
Refined tall 4 3 46 35 12

Figure 6. Structures of the most common fatty acids in vegetable oils listed in Table A.

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2.2.1.1 Drying of oils

The drying mechanism in which the oils form a three dimensional network is complex with many competing
reactions. The drying occurs through auto oxidation, a process that includes an incubation period, oxygen
uptake and cross-linking [15]. The mechanism for conjugated and non-conjugated fatty acids differ where the
mechanism for non-conjugated systems is better known and also most occurring in oxidative coatings [22]. The
drying mechanism of the non-conjugated system starts with a hydrogen abstraction from unsaturated fatty
acids containing allylic centers, see Figure 7. The formed radical undergoes rearrangement and can then react
with other radicals but most probably with oxygen due to its high concentration and availability. This results in
the formation of a hydroperoxide that decomposes under heat, sunlight irradiation or with the help of driers.
This decomposition can lead to both intermolecular chain scission and crosslinking [15]. Before the
crosslinking can occur there needs to be a build-up of hydroperoxide concentration to remove antioxidants that
work as inhibitors. Therefore, driers are added that will decompose hydrogenperoxides to increase the speed
of the drying [22]. Crosslinking occurs when the alkoxy group reacts with other radicals or with a double bond
[15]. The formed bond are peroxy linkages, ether bonds and carbon-carbon links where ether linkages are
most common in room temperature , carbon-carbon bonds at elevated temperatures and peroxy bond is in low
concentration and stable in the polymer network [22]. Fragmentations will always occur to different extent and
the decomposition products will cause a bit of smell [15].

Figure 7. Drying mechanism of non-conjugated fatty acids. Starting with a hydrogen abstraction followed by oxygen uptake,
hydroperoxide decomposition, crosslinking and chain scission.

8
The first reaction with a conjugated system is the direct addition of oxygen forming a diradical, see Figure 8.
These diradicals can react with double bonds or other radicals in the same manner as the non-conjugated
systems. The fact that diradicals are formed explains the faster drying of the conjugated oils. Cross-links from
conjugated oils are mostly carbon-carbon bonds which explain their higher durability [22].

Figure 8. Drying mechanism of conjugated fatty acids.

The drying of oil is slow but can be accelerated by addition of driers which consist of transition metal salts and
as mentioned earlier driers speed the drying by decompose the hydrogen peroxides. Driers can also promote
the formation of hydrogen peroxides or the uptake of oxygen. However, the driers will act during the whole
service life of the coating causing aging and breakdown [15].

When drying oils are thermally or chemically treated they are partly polymerized. This result in faster drying as
less crosslinking reaction is needed to form a film. Further, the viscosity will increase and the gloss and
hardness will be improved. Bodied oil or Stand oil are thermally treated drying oils in inert atmosphere and
without any additional substances. Blown oils are made by heating and at the same time blow air through the
oil. This result in even faster drying as it not only polymerizes the oil but also reduces the antioxidants.
Isomerized oils are made by heating the oil under alkali conditions to increase the conjugation for faster drying
[13]. Boiled oil are mixtures of drying oils, Stand oil and driers [23].

2.2.2 Wax
Waxes are complex mixtures of long-chain lipophilic substances [13]. Wax can also contain some pollutants
before it is refined [24]. Due to genetics and seasonal variations the composition of the wax from plants and
animals varies [14].

In Table 2 melting points of some natural waxes are listed [24].

Table 2. Common waxes and their melting points.

Melting point
Waxes
[oC]
Beewax 61-65
Wool lanolin 31-42
Carnauba 82-86
Candelilla 65-69
Ouricury 85
Bayberry-
48-50
myrtle
Spermaceti 45-49

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3. Chemicals and Materials
All chemicals used within the present invention are described in Table 3.

Table 3. Chemicals used for the project and their commercial name as well as their suppliers/distributors.
Chemical Bio-based content Biodegradability
[%]
Surfactant C 100 Inherently
Surfactant D 81 Readly
Surfactant E 100 Not readly
Catalyst F 0 Readly
Substance G 100 Readly (81.7%)
Co-surfactant H 100 Readly (80%)
Co-surfactant I 100 Readly
Co-surfactant J 100 Readly
Co-surfactant K 100 Inherently
Preservative L 100 Readly
Substance M 100 Readly
Wax N 100 Inherently
Wax O 100 Inherently
Wax P 100 Inherently
Oil Q 100 Inherently
Oil R 100 Inherently
Oil S 100 Inherently
Oil T 100 Inherently
Oil U 100 Inherently
Oil V 100 Inherently
Oil W 99.5 Inherently
Oil X 99.5 Inherently
Oil Y 100 Inherently
Oil Z 100 Inherently

Most of the chemicals are fully bio-based, except a part of the Surfactant D and Catalyst F. Most of the
materials are also readily biodegradable except Surfactant D. Surfactant C and Surfactant D are labeled as
toxic to aquatic life with long lasting effects in the pure and concentrated form. However, all formulations have
a content of Surfactant C lower than the toxic level.

The emulsifying system used in this project consists of several components. Primary emulsifiers are Surfactant
C-E where Surfactant D has been used to replace the Surfactant C in some formulations. Substance G which
is soluble in both fat and water is important at the beginning of the emulsification and the coalescence of
particles after wood treatment. Additionally Co-surfactant H-K helps to stabilize the emulsified system.
Substance M is a co-solvent and has been tested instead of Substance G and Oil S.

Oils and waxes are used in the formulations to bring water resistance to the final coating. As wax, mainly Wax
O has been used but also Wax P and N was tested. At the same time four categories of oils has been
evaluated. Oil S is a non-drying oil while Oil Q and R are semi-drying oils making up two of the oil categories 1
and 2 used in this project. In the case of drying oils, some dry faster, like Oil Y and Z making up category 4 and
in category 3 some oils dry slower and are cheaper, the oils in this category includes Oil T-X. The idea with the
four categories is that optimized performance will be reached as the penetration capacity of the non-drying oils
combines with the surface film formation of the drying oils. Beside oils, wax and the emulsifying system
Preservative L is also used.

10
Apart from the chemicals, wood pieces of sapwood from pine have been used in the water absorption tests.
Further, different types of pine wood products (Wood type 1-4) have been used in the static hydrophobic tests.
Description of the tests can be found in section Methods. Moreover, three batches of the current non-bio-based
reference product (RCP 1-3) have been used to investigate how the developed fully bio-based products
perform in relation to the present commercial products.

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4. Experimental
The description of each method used in this project can be found below.

4.1 Emulsion
All components except water and Catalyst F are melted and blended in a water bath during stirring. Catalyst F
is added to hot deionized water and mixed for a few seconds at 10 000 rpm with the homogenizer Polytron PT
1600 E. The fatty phase is then added to the water and the two phases are homogenized for 10 minutes at
15 000 rpm. 80 ml of the emulsion is then sonicated for 3 minutes at 10 microns (peak to peak) with MSE
M13569. All emulsions, both sonicated and non-sonicated are analyzed further with an optical microscope
(Nikon Microphot-FXA) and other techniques.

Some exceptions of this procedure were made. The rate of the homogenizer was 10 000 rpm for Formulation
1-5. For Formulation 1 and 3 a water bath of boiling water was used during homogenization to melt the lumps
with a buttery texture that was formed.

4.2 Static hydrophobic test

To test the formulations hydrophobic properties and ability to prevent water from penetrating the wood an
indicative test is performed a so called static hydrophobic test. The formulations were applied on Wood type 1
pieces with the dimension of 11.5×2.5×10 cm two times with one hour in between using a brush. The pieces
were dried for 24 hours at room temperature before six drops of water (~0.4 ml) were placed on the coated
wood with a pipette. Two drops were sucked up with paper after one and two hours and the wood pieces are
photographed and studied carefully. The experiment was performed in room conditions.

Exceptions from this method was done for Formulation 4, 8, 9, 10, 12, 14, 21-26, where only four smaller drops
where placed on the wood pieces and none where sucked up with paper. The current product, sample 26 and
41 has also been tested on Wood types 2-4 pieces with the same dimensions.

Absorption of water by the wood causes a color change of the wood; the wood darkens where water has been
absorbed and it is this darkening that is being observed in this experiment. Absorption is a complex process
where evaporation, capillary forces, hydrophilicity etc. have a role in the degree of absorption.

As mentioned earlier in this section, this test is indicative due to differences between each wood pieces and
structural differences in the wood pieces as well as processing including coating procedure and sucking up
water. Further, the darkening of the wood where drops have been placed and sucked up with paper, looks
differently from different angles and in different light.

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4.3 Contact angle
To test the hydrophobic properties of coated surface the contact angel on coated wood was performed with
PGX measuring head. Even though the two absorption tests described in 4.2 and 4.3 have better correlation to
the final performance this test gives an indication of the hydrophobicity and absorption as more wetting give a
greater chance to absorption. The contact angle is measured two times for each sample and after 1 second, 30
second and 1, 2.5, 5 and 10 minutes. The drops have a size of 4 μl. The contact angle is measured on coated
wood pieces from sapwood of pine with dimension of 5×1.5×3 cm. The formulations are applied on the wood
pieces two times with one hour in between using a brush. The wood pieces are then dried for 24 hours at room
temperature before the contact angle is measured.

4.4 Water absorption test

To confirm the results from static hydrophobic test and to give more distinguishable results, a water absorption
test was performed. Formulations were applied two times with one hour in between on wood pieces of pine
sapwood with the dimension of 5×1.5×3 cm. The wood pieces were dried for 48 hours at room temperature
and then weight before they were placed in a bucket with water. The pieces were then picked up and the
excess water was dried with paper before the samples were weight. This performance was done the first eight
hours and then after 24 hours and 48 hours. The percentage of absorbed water was calculated with equation 1
below where m1 and m2 are the weight of the wood pieces before and after it was placed in the water
respectively.

𝑚2 −𝑚1
𝑎𝑏𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 % = 100 ∙ (1)
𝑚1

It should be mentioned that this test is not definitive as the wood structure differs between and within each
wood pieces and coating procedure can also have an effect on the absorption.

4.5 Weathering test

To give an indication of how the formulations will work in real life conditions a weathering test was performed.
Formulations were applied two times with one hour in between on Wood type 1 pieces with the dimension of
11.5×2.5×10 cm. The wood was then dried at room temperature for 24 hours before it was placed outside on
the ground made of asphalt leaning towards a stone at ~40° angle. After 7 and 30 days the wood is checked
upon. This test was also performed with Formulation 49 on Wood type 3 pieces with the same dimensions.

4.6 Surface pH
To see how the final coating regulates the final surface pH of wood the surface pH of coated wood was
measured using the surface electrode SIAnalytics Blueline 27 pH. A two point calibration was performed
according to instruction with the use of two buffers. For each sample 3 measurements were taken by

13
placement of water drop on the coated wood surface and the electrode inside the drop in contact with the wood
surface.

4.7 Stability test

To test the shelf life of the formulation a stability test was performed using OrganoClicks own SOP for emulsion
stability where some formulations were put into ovens at 40 °C and 50 °C as well as in room temperature and
in a fridge at 4 °C. The formulations were checked for sedimentation, creaming, edge formation etc. after 3
days, 1, 2, 3 and 4 weeks. After 4 weeks the formulations were shaken and analyzed with an optical
microscope.

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5. Result

5.1 Strategy
In this project several formulations have been made. These formulations can be divided into groups according
to the purpose for why they have been made. Bellow follows a description of each group.

Understand the system- Formulation 1-21 and 51: The following formulations were made to investigate the
thresholds of the system and improve the stability of the first formulations. This was done by looking into the
process of emulsification; changing the speed and temperature during homogenization and sonicate the
emulsions after homogenization. Further the content, proportions and types of wax and oils were changed.
Changes in the surfactant system were also made by addition of Co-surfactant H, increased amount of
Catalyst F and Surfactant E and Co-surfactant I was changed to Co-surfactant J. It was also tested to
exchange a part of the Catalyst F to Catalyst B to see if similar stability could be achieved to a lower cost as
Catalyst F is expensive. All formulations were made of material already in place. Later in the project the
content of oils and waxes was halved once again to investigate the stability.

Different drying oils from category 3- Formulation 22-26: These were the first formulations with newly
ordered chemicals. All four categories of oils were used where the drying oils in category 3 (Oil T-X) were
varied to see how the stability and the hydrophobic property of the final coating was affected. Apart from these
oils Oil S, Oil Q and Oil Y was used.

Exclusion of one oil category- Formulation 27-30: In these formulations one of the oils were excluded from
the recipe of Formulation 26 (containing Oils S, Q, Y and W) to examine the effect on stability and the
hydrophobic effect of the final coating.

Different oils from category 4 and 1 - Formulation 31, 32 and 39: To investigate the effect on stability and
hydrophobicity of the final coating, Oil Y was exchanged to Oil Z in Formulation 31 and Oil S was exchanged to
Substance M in Formulation 32 compared to Formulation 26. Oil Z was also used in Formulation 39 but
contains a higher content of wax and can be compared to Formulation 36 with the same content of wax but
with Oil Y instead of Oil Z. To a sample of Formulation 31 extra Catalyst F was added after homogenization
and sonication to improve the hydrophobicity.

Increased wax concentration- Formulation 33-38: The resistance against absorption of a waxed wood
surface is highly dependent on the thickness of the wax layer. Therefore, the content of wax was increased
compared to Formulation 26 while the content of the oils was reduced keeping the concentration of oils and
wax constant. These formulations were also made to give an insight to how much wax the system could hold.

Mix of Wax O and Wax P- Formulation 40: A mixture of Wax P and Wax O was used with the aim to gain
better hydrophobic effect on the final coating due to the higher melting point of Wax O.

Changed proportions of oils- Formulation 41: The proportions of the different oils were change in
Formulation 41 according to results from testing Formulation 27-30 to improve the hydrophobic effect of the
final coating.

15
Lowered content of surfactants- Formulation 42-45: To improve the hydrophobic effect of the final coating
the content of the Surfactant C and Co-surfactant K was lowered. Due to the amphiphilic nature of the
surfactants, they can potentially attract water and rewet the final coated surface potentially resulting in more
water absorption and less hydrophobicity.

Substance M instead of Substance G- Formulation 46 and 47: In Formulation 46 and 47 Substance G were
exchanged to Substance M compared to Formulation 41 and 42 to see if the stability of the emulsion and
absorption of the final coating was improved. As Substance M is a larger structure compared to Substance G
and due to its hydrophobic character, it can be expected that the hydrophobic character of the final coating will
be affected. However, with a larger structure and corresponding lower hydrophilicity/surface activity the stability
can suffer.

Surfactant D instead of Surfactant C-Formulation 48-50: To improve the stability Surfactant D was used
instead of Surfactant C that was utilized in Formulation 41-43. The Surfactant D concentration was lowered
during these experiments for the same reason that Surfactant C concentration was lowered before, to reduce
the content of chemicals that can cause rewetting or decreased hydrophobicity. A part of sample 48 was
diluted three times to the half, one quarter and one eighth concentration to see the hydrophobic effect on the
final coating.

Final try- Formulation 52: A final try to improve the hydrophobic effect was made where Oil W was excluded,
the percentage of the remaining oils (Oil S, Q and Y) and Wax P were changed and Surfactant C was used as
one of the prime surfactants.

5.2 Emulsion characterization

Microscope images were taken of each emulsion to study the quality of the prepared emulsions in terms of
particle size, morphologies and droplet size distribution. The formulations were also examined by appearance.
The conclusions from these analyses are discussed below. In Figure 9 two examples of microscope images
can be seen, illustrating different droplet size, size distribution, emulsion stability and flocking. As it can be
seen in the right picture, an unstable emulsion with big particle sizes, large size distribution and flocculation is
distinguishable. This observation was accompanied with a buttery texture of un-emulsified fatty phase in the
liquid as well. At the same time, all of the parameters of emulsion quality are fulfilled in the sample at the left
side of Figure 9 where small particle sizes, narrow particle distributions and no flocculation are achieved.

16
 Figure 9. Microscope images of two different formulations. The distance from the corner of the frame to the vertical line on
the long side on the frame is 67 μm.

As mentioned above different angles were taken in Formulation 1-21 and 51 to improve the stability and the
following was concluded.

It was concluded that sonication, higher speed of the homogenizer and higher temperatures resulted in better
emulsion with improved stability with less/no formed solid particles and aggregation and smaller drop sizes.
This was also confirmed throughout the project.

From the investigation of the changes of oils and waxes it was concluded that Oil R alone is not stable in the
system while Oil Q is. It was observed that Oil R separates after a while from the system and created a layer of
oil on top of the emulsion. Further, it was clearly observed that with the applied emulsification system, the
presence of wax and a higher content of oils and waxes make the system less stable. This is expected
because when waxes cools down and crystallizes it forms particles with the ability to capture other particles
and fatty content creating larger structures. Moreover, when the ratio of oils and wax increases without
compensation of more stabilizing emulsifiers the system gets little bit unstable. From the microscope images it
was also concluded that combination of oils did not had an adverse effect on the stability. However, it was
concluded that a mixture of Wax N and Wax O gave worse stability with more aggregation and the use of only
Wax N gave marginal improvement with less aggregation but with larger droplets. Since Wax N did not improve
the emulsion it was not considered for the future formulations.

From the changes in the surfactant system no improvement was gained with higher content of Catalyst F. Nor
was any significant difference seen when a part of Catalyst F was exchanged to Catalyst B. More aggrgation of
droplets and more particles was seen with increased amount of Surfactant E. Better emulsion with improved
stability was gained by using Co-surfactant H and I and the combination gave even better emulsion quality.

With a better understanding of the system newly ordered materials were tested. In the first trials the different
drying oils in category 3 were tested. The quality of these formulations was similar to each other, hence
concerning the emulsion quality all five drying oils tested performs similarly.

No distinct difference was observed between the sonicated samples of the formulations where one oil category
was excluded. However, comparing the microscope images of the non-sonicated samples slightly more

17
flocculation was observed in the Formulation where Oil Q was excluded suggesting that this oil improves the
stability of the system.

By exchanging Oil Y to Oil Z in oil category 4 no improvement was realized. In fact some larger droplets were
seen in the microscope images. However, with addition of extra Catalyst F after homogenization rounder drops
with a smaller drop size was gained. On the other hand, replacing Oil S with Substance M in oil category 1 did
not result in any distinct changes in stability and in other terms of emulsion quality, particles aggregation and
drop size.

As another optimization trial in terms of stability and performance, the wax content was optimized and tested.
While initial increased amount of Wax O exhibited similar emulsion stability to the original concentration, after a
threshold concentration the emulsions started to show larger droplets and lots of yellow lumps.

The use of Wax P (a wax with a high melting point) resulted in lots of lumps as a consequence of the
solidification of the wax during homogenization. Part of the fatty phase was also stuck on the beaker wall after
homogenization. With a higher processing temperature this can possibly be avoided. The microscope image of
the sonicated sample showed a relatively stable system explained by the loss of fatty phase during
homogenization.

Similar stability was observed with different concentrations of the different oils as with the same concentration
of Wax O but equal concentrations of the different oils. Nor was any significant difference in stability observed
when exchanging Substance G to Substance M.

No distinct difference was seen in the microscope images when the concentration of Surfactant C was lowered
by ~17%. However, with a further ~37.5% decrease of Surfactant C more aggregation was noticed in the
microscope and more lumps were formed. With a lowered concentration of Surfactant C and a lower
concentration of Co-surfactant K (0.25% decrease) an even worse stability was observed with large droplets.
When only the concentration of Co-surfactant K was lowered by 0.25% the emulsion quality and stability was in
between the formulation where the concentration of Surfactant C had been decreased by ~17% and the
formulation where Surfactant C was decreased with ~37.5%.

More aggregation was observed as the concentration of Surfactant D and Surfactant C was gradually
decreased. However, the droplet sizes were smaller in samples that contained Surfactant D compared to the
samples that contained Surfactant C. Secondly, the deterioration in quality seen with decreased concentration
of Surfactant C in the sonicated samples was not seen in the sonicated samples with decreased concentration
of Surfactant D. Therefore, it was concluded that Surfactant D generally is a stronger emulsifier that
consequently improves the stability.

To test the ability to produce a formulation with high dry content and dilute it afterwards to improve the
industrial processability and productivity, a formulation with the double amount of dry content was prepared.
The microscope images of the sonicated formulation exhibited the same drop size compared to when half the
amount of dry content was used. However, more solid particles were formed during the homogenization. From
this test it was concluded that the amount of dry content that can be used is between those two dry contents.
No adverse effects were seen when the formulation was diluted later on.

18
More aggregation was seen in the microscope image of the not sonicated Formulation 52 compared to
Formulation 49 where the same amount of Surfactant D was used and Formulation 33 where the same amount
of Wax O was used but with different proportions of oils. Even though the not sonicated sample of Formulation
52 is not particularly good when it comes to stability the sonicated sample is comparable to the other
formulations, Formulation 49 and 33.

5.3 Static Hydrophobic test on untreated wood

Static hydrophobic tests were performed to give an indication of the formulations performance as a final
hydrophobic/water and dirt repellent coating. One example of how these test looked like is illustrated in Figure
10. The conclusions withdrawn from the pictures taken during these tests are discussed in the following
sections.

Figure 10. Example of static hydrophobic test. The darkened wood is where water has been absorbed.

Compared to the bio-based formulations the current non-bio-based reference product shows less absorption
according to the photographs taken during these experiments. However, this difference was not noticed during
the experiment where all bio-based formulations and the current product seamed similar. Later it was
confirmed that no large difference is observed between the bio-based formulations and the reference product,
see section 5.6.

During these tests a difference in absorption was seen between heart wood and sapwood. This is explained by
the higher content of extracts in the hart wood generating greater hydrophobicity of this wood part.

No difference was observed in absorption when the coated wood pieces were tested after one week, as a sign
of performance durability. This holds for both bio-based formulations and the current non-bio-based reference
product.

It was also tested to spray the formulations onto the wood instead of using a brush. This was made without any
difficulties indicating that the formulations produced in this project can be applied by different application
methods like spraying and brushing.

19
In Figure 11 a greater color change is observed when Wood type 1 is coated with the current non-bio-based
reference product than the developed bio-based formulations. Similar change is noted on Wood type 4, see
section 5.4.

Figure 11. Wood type 1 coated with the reference product and Formulation 26. In each picture the non-coated wood is on
the right. The right picture shows the color change when wood is coated with Formulation 26 and the left picture illustrates
the color change when wood is coated with the current non-bio-based reference product.

Some of the earliest formulations were relatively stable after one month and were tested with static
hydrophobic test. The result of this test indicates that Oil Q results in less absorption compared to Oil R and
that addition of Wax O result in less absorption. Further, no large difference was seen when the total
concentration of oils and wax was halved. Similarly, no difference was observed when the wax and oil
concentration was lowered later in the project. These observations emphasizes that the effective dose of the oil
and waxes in the developed formulation can be decreased. This conclusion is also confirmed by the results
from the performance of different dilution of bio-based formulation discussed later. Moreover, the addition of
Co-surfactant H and exchanging Co-surfactant J to Co-surfactant I resulted in similar absorption while the
usage of both Co-surfactant H and J resulted in an improvement.

Comparing the formulations with different drying oils from category 3 the test indicated that Oil W resulted in
least absorption and largest visually observed contact angle while Oil V resulted in similar absorption but lower
contact angle. Worst performance was gained with Oil X. Oil U and T resulted in less absorption than Oil X but
more absorption than Oil V. Lastly Oil U resulted in more absorption than Oil T. Hence Oil W was used in the
next formulations.

Comparing the pictures of wood coated with formulations were one oil category was removed no large
difference was seen between the formulations. However, wood treated with the formulation where Oil W was
excluded seemed to result in less absorption. This result indicated that Oil W improves the hydrophobic effect
of the final coating less compared to the other oils.

When Oil Y was exchanged to Oil Z in oil category 4 no distinct difference was noted. The opposite
observation was realized when Oil S was changed to Substance M and resulted in more absorption. This can
be explained by the chemical structure of the two ingredients, where the triglycerides in Oil S have a larger
structure compared to the unbranched structure of Substance M. Hence Oil S have less mobility and a smaller

20
plasticizing effect and therefore acts together with other hydrophobic ingredients with a greater steric hindrance
compared to Substance M preventing water penetration.

With addition of extra Catalyst F in the formulation more absorption was seen. As it can be concluded from this
result, due to the complex function of the Catalyst F in the emulsion and final coating, the optimum
concentration of Catalyst F need to be adjusted carefully.

No distinct change in absorption was noted when the wax concentration was increased gradually. However,
with an increase of wax it was noted that the water drops spread more but had a greater starting contact angle.
This fact was later analyzed more closely with a contact angle measurement, see section 5.5.

No major improvement can be noted when a mixture of Wax O and Wax P is used compared to when only
Wax O is used. However, it should be noted that a lot of the fatty phase was lost during the formulation
preparation with Wax P which could affect the performance of the final coating in this experiment. A process
optimization which provides a proper formulation is expected to potentially display enhanced effect on the
hydrophobicity and water absorption. If Wax P is considered to be used in the future, its improvement should
be weight against the required higher temperature during homogenization.

Improvement of absorption was seen when the concentration of Surfactant C was lowered by ~17%. However,
when the concentration was decreased by ~37.5% the absorption seemed to increase. This can be explained
by the loss of fatty phase due to inefficient emulsification which can be expected with a lower content of
emulsifier. Accordingly, the content of Surfactant C to give both good stability and little absorption needs to be
adjusted carefully. Further, when the Co-surfactant K content was lowered by 25% a bit more absorption was
seen. Again, this can be the result of lost fatty phase due to inefficient emulsification. Other explanations
include that the lower content of Co-surfactant K effect the compatibility between the emulsion and the wood
substrate resulting in less wetting of the wood fibers and hence less protective final coating. Another
explanation can also be that the droplet size is less homogeneous causing a less evenly spread film. No more
tests were performed on formulation with lower content of Surfactant C and Co-surfactant K due to its
instability which consequently limits its potential as a substitute of the current non-bio-based reference.

By changing Substance G to Substance M and keep the higher concentration of Surfactant C no difference
was noted. However, when Substance M was used instead of Substance G and the Surfactant C concentration
was lowered, more adsorption was seen. Similar to what has been discussed above, this can be due to the
loss of fatty phase as solid particles during emulsification.

Property wise, no significant difference was realized between emulsions with Surfactant D and Surfactant C
when comparing the absorption. However, as discussed earlier emulsification with Surfactant D at the same
concentration as Surfactant C seemed more efficient with lower particle sizes suggesting that a low
concentration can be used.

No noticeable difference was seen between the diluted compared to the non-diluted formulation suggesting
that a lower concentration result in the same performance of the final coating in regard to static hydrophobicity.
However, a water absorption test might show more distinguishable difference. Note that this result is not
comparable to the result from the formulations where only the oil and wax content has been halved. However,
the observed fact emphasize on the effectivity of the developed formulation with lower solid content
consequently enhancing the industrial productivity and final price.

21
Some improvement was noted when the proportion between the oils were changed compared to when all oils
were in the same concentration. Furthermore, similar absorption was noticed for Formulation 52 compared to
Formulation 49 with the same content of Surfactant D and Formulation 33 with the same wax content.

5.4 Static hydrophobic test on Wood type 2-4

As the future product should be applicable on different types of wood product Formulation 26 and 41 were
tested on Wood type 2-4. The result is discussed below.

An improvement was noted for the current non-bio-based reference product after one week with less
absorption and spreading on Wood type 4. The change over time is a thermodynamic state of the coating
where the coating arrange itself by phenomena like migration or self-assembly that is improved over time to the
most stable form. Compared to Wood type 4 no improvement was observed over time on Wood type 2 and 3
with the current non-bio-based reference product.

Formulation 26 and 41 performed similar with regards to absorption and spreading and there was no difference
noted after one week when these formulations were tested on Wood type 4. These two formulations also
showed less absorption and spreading compared to the reference on Wood type 4.

In correlation to the result from Wood type 1, the color of the wood changes when the coating is applied on
Wood type 4, see Figure 12 while no significant difference was noticed on Wood type 2 and 3.

Figure 12. Wood type 4 coated with the reference and Formulation 26. In each picture the non-coated wood is on the right.
The right picture shows the color change when wood is coated with Formulation 26 and the left picture illustrates the color
change when wood is coated with the current reference product.

On Wood type 3 coated with the reference the absorption after one week seemed to appear before the water
was spread compared to after 24 hours where the drops spread on the wood surface and then the water was
absorbed. Once again this difference can be the thermodynamic state of the coating over time. Formulation 26
and 41 were similar to each other and to the reference with respect to absorption and spreading. When the
drops had dried marks were left on the surface on wood coated with both the reference and Formulation 26
and 41 even if the marks were more pronounced with Formulation 26 and 41, see Figure 13 for comparison.
On the wood coated with Formulation 41 even white flakes were left on the wood surface. It was also noted

22
that something was dissolved into the drops as they whitened during the experiment and white spots were
noticed in the drops.

Figure 13. After static hydrophobic test on Wood type 3 coated with Formulation 41 (picture to the right) and the current non-
bio-based reference product (picture to the left).

It was speculated that the basic and hygroscopic surface of Wood type 3 along with the system with oils
resulted in some reaction. Therefore, the effect of extra acid addition and increasing the acidic power of the
bio-based formulation to cure this problem was tested. As can be seen in Figure 14, some improvement was
realized but this strategy could not solve the problem totally. However, presence of same marks for current
reference product rationalized other reasons behind this phenomenon like the effect of the applied second
coating (the reference) on the migration of the first coating (that is used to gain Wood type 3) to the surface
etc.

Figure 14. After static hydrophobic test on Wood type 3 coated with Formulation 49 to the left and 50 to the right where extra
Catalyst B and extra Catalyst B plus Catalyst F have been added to the formulations respectively. The left side of the wood
piece coated with Formulation 50 has been completely wetted by water under a tap.

23
Worth to mention from Figure 14 is that no marks can be seen when the wood is wetted completely and evenly
under a tap water (as most possible scenario when it comes to raining). Instead an even surface color change
happened. Secondly, when the pieces were washed under a tap the markings disappeared or became less
pronounced. Hence it was concluded that a small rain will leave marks but if the surface is completely wetted in
normal rain no marking will be left on the surface. Secondly, with repeated wetting of the wood no markings will
be seen.

As another test approving the migration of the first coating, a test of water droplets on uncoated Wood type 3
was performed. As it can be seen in Figure 15, the marks are present by localize wetting produced from water
droplets on Wood type 3 also. This observation confirms the fact that this color change is more characteristic of
the first coating rather than the second. The less marks using the current reference product than the not coated
or sample coated with the bio-based formulations is interesting observation worth to study more in the future.

Figure 15. Static hydrophobic test on uncoated Wood type 3.

When bio-based formulations were applied on Wood type 3 and 4 in their original concentration, a creamy
paste was formed unlike the reference. It was believed that this phenomenon could be correlated to high solid
content and faster absorption of water phase. Hence one bio-based formulation was diluted to half its
concentration and one quarter and applied on Wood type 3 and 4. As it can be seen in Figure 16, the paste
formation decreased with dilution. As it was discussed earlier a lower dry content seams to generate the same
hydrophobic effect and hence the problem with paste formation will be solved by its own.

24
 Figure 16. Application of diluted bio-based formulation on Wood type 4 (upper pictures) and Wood type 3 (lower pictures).
From left to right on each row is non-diluted, half concentration and one quarter of concentration.

5.5 Contact angle

As the static hydrophobic test indicated that an increase in wax content resulted in more spreading and a
greater starting visual contact angle, a contact angle measurement of these formulations were performed. The
result of the time dependent contact angle measurement of different samples during the first 10 minutes is
discussed below.

No pattern was seen between contact angle and Wax O concentration in Figure 17, neither if one study the
starting angles, the end angels or a mean of the angles or the change in contact angle. When the proportions
of the different oils were changed a small difference was seen at the beginning and a larger towards the end.
This could be an effect of less absorption with different proportions of oils. Compared to the references all
formulations produced in this project had a lower contact angle. The two references behaved differently where
RCP1 drastically decreased throughout the time period and RCP2 was stable at the beginning before it
decreased. Only the references and Formulation 34, 36 and 37 had starting contact angles above 90° which is
the boundary for hydrophobicity.

No large difference between the two measurements was noted for Formulation 33, 37, 38 and RCP1.
However, to get a more reliable result more measurements needs to be performed.

25
 130

120

110 33
34
100
35
Contactangle [°]

90 38
36
80
37
70 41
RCP2
60
RCP1
50

40

30
0 5 10 15 20
Time [min]

Figure 17. Time dependent contact angle over time for Formulation 33-38 and 41 as well as two batches of current
reference product, RCP1 and RCP2. The wax content increases with the formulation number where Formulation 33 has the
lowest content and Formulation 37 has the highest content of wax. Formulation 41 has the same wax content as Formulation
38 but the proportions of the oils has been changed.

5.6 Water absorption

To give more distinguishable result of the absorption, another type of absorption test was performed using
Method D. Below the findings from these tests are discussed.

No clear pattern was noted in water absorption with an increasing content of wax in Figure 18. Nor was any
clear pattern seen when the mean values of the absorptions for these formulations (33-38) were compared in
Table 4. When the proportions of the different oils were changed in Formulation 41 less absorption was
observed. Remember, looking at the mean values of the absorption Formulation 38 with the same wax content
as Formulation 41 but with equal proportions of the different oils, it has the largest absorption value and
therefor differs from the other samples with varying wax content. These two results is in line with the static
hydrophobic test, see section 5.3.

As seen in Figure 18 all formulations and the references followed the same trend and ended up at similar
absorption after 48 hours with an exception for Formulation 36 that drastically increased in absorption between
7 and 8 hours. It should be noted that this behavior is only seen for one of the measurements. This drastic
increase in absorption can be explained by the change in protection mechanism from water repellence due to
the microstructure of the surface during the first hours to the protection from the final film in a later stage.
Further a difference in absorption was seen for formulation 34, 37 and 38 compared to the other formulations
and the references between 3-8 hours. The RCP2 increased more in absorption between 8 and 24 hours

26
compared to RCP1. All Formulations and the references absorbed less water than the uncoated wood which
changed little in absorption over time.

50

33
40
34
Absorption [wt%]

35
30 38
36
37
20 41
RCP1
RCP2
10
Uncoated

0
1 8 15 22 29 36 43
Time [h]

Figure 18. Water absorption over time for Formulation 33-38 and 41 as well as RCP1 and RCP2 and uncoated wood. The
wax content increases with the formulation number where Formulation 33 has the lowest content and Formulation 37 has the
highest content of wax. Formulation 41 has the same wax content as Formulation 38 but the proportions of the oils has been
changed.

No distinct difference in absorption was seen when Surfactant C was exchanged to Surfactant D in line with
the result from the static hydrophobic test. Further, a marginal improvement with less absorption was seen by
lowered Surfactant D concentration. However, looking more closely on the absorption the formulation with
lower concentration of surfactant C showed less absorption than the formulation with higher content of
Surfactant C during the first 6 hours then the trend was opposite. Comparing the mean values of the
absorption in Table 4, the formulation with higher content of Surfactant C (Formulation 41) absorbed more than
the formulation with lower content of Surfactant C (Formulation 42) and the formulation with lower content of
Surfactant D (Formulation 49) absorbed less than the formulation with higher content of Surfactant D
(Formulation 48). All formulations absorbed less than the uncoated sample and all formulations except the
formulations with the higher content of Surfactant C absorbed less than the two references. Secondly these
Formulations showed similar behavior as the formulations in Figure 18.

27
It was also concluded that a lower content of oils and wax (in Formulation 51) resulted in similar absorption as
a higher content of oils and wax (in Formulation 41). However, it should be noted that the rest of the system
also have fatty properties. Hence even by 50% decrease of oils and wax no significant change was realized
since the system still had a fatty content higher than the effective hydrophobic dosage. This confirms the result
from the static hydrophobic test on Wood type 1.

From Figure 19 it can be concluded that all formulations where one oil category has been excluded showed
similar absorption over time, in line with the result from the static hydrophobic test. However, at the start the
formulations without Oil S and W had less absorption than the formulations without Oil Q and Y but at the end
of the time period the trend is opposite. Comparing the mean values of the absorption over the whole time
period in Table 4 it can be concluded that the formulation without Oil Y (Formulation 28) absorbed the most
water while the formulation without Oil S (Formulation 30) absorbed the least and the formulations without Oil
Q and W (Formulation 27 and 29 respectively) had an absorption in between. From the static hydrophobic test
it was indicated that Formulation 29 absorbed less water than the other formulations this also holds for the
early results in this test but not in respect of the mean value. Compared to Formulation 26 where all oil
categories were used, Formulation 29 and 30 absorbed less while Formulation 27 and 28 absorbed more.

Compared to the references (RCP1 and RCP2) Formulation 27-30 absorbed less water the first 8 hours.
However, after 48 hours this trend was revers but with a very low margin. The formulations also absorbed less
than the uncoated sample. Further while the references experienced extensive absorption in the first 8 hours,
the developed bio-based formulations had a drastic increase between 8 and 24 hours. This observation made
these bio-based formulations different from the other bio-based formulations discussed above as they showed
similar trend as the reference. This deviation in absorption can be explained by the different batches of wood
being used, batch A and B. For Formulation 29 and 30 batch B was used compared to the formulations
discussed above, the references and the uncoated sample where batch A was used. For Formulation 27 and
28 both batches were used for the two measurements and in Figure 19 the average of the two measurements
for each Formulation is shown. Figure 20 show the difference in absorption between the two batches of wood
when the same formulation (27 and 28 respectively) is used. This difference between batches makes
comparison between Formulation 27-30 and the references more difficult. It is believed that both the
references and the uncoated sample will behave differently with the second batch of wood also.

28
 50

27
Absorption [wt%]

40
28

30 29

30

20 Uncoated

RCP1
10
RCP2

0
1 11 21 31 41
Time [h]
Figure 19. Water absorption over time for Formulation 27-30 as well as RCP1 and RCP2 and uncoated wood. In
Formulation 27-30 Oil Q, Oil Y, Oil W and Oil S has been excluded.

60

50

40 RCP1
Absorption [wt%]

RCP2
30 27-A
27-B
20 28-A
28-B

10 Uncoated

0
1 11 21 31 41
Time [h]

Figure 20. Water absorption over time for Formulation 27 and 28 as well as RCP1 and RCP2. 27-A and 28-A represent
Formulation 27 and 28 respectively with the first batch of wood A while 27-B and 28-B represent Formulation 27 and 28
respectively with the second batch of wood B.

29
No large difference in water absorption was noted between the different drying oils from category 3. However,
according to the mean of the absorption over the whole time period in Table 4 the largest absorption is noted
for Formulation 25 with Oil W while Formulation 22 with Oil T have the smallest mean absorption and
Formulation 23, 24 and 26 with Oil U, V and X respectively have mean values in between. This is not in line
with the static hydrophobic test where formulation with Oil X performed the best then formulation with Oil V, T
and U and lastly the formulation with Oil W. All formulations showed similar trend as the formulations with one
oil category excluded and as discussed above this deviation from the references as well as the rest of the bio-
based formulations can be explained by the different batches of wood being used. Hence the comparison
between Formulation 22-26 and the current reference product, the uncoated sample and the earliest discussed
bio-based formulations is more difficult.

It was noted that during the first 8 hours Formulation 52 absorbed less than the references as well as the
uncoated sample and Formulation 49 with the same amount of Surfactant D and Formulation 33 with the same
amount of wax but different proportions of the oils. However, after 24 hours Formulation 52 absorbed more
than the other bio-based formulations and the references and after 48 hours it also absorbs more than the
uncoated sample. However, Formulation 52 used a different batch of wood compared to Formulation 33, 49
and the references, hence as mentioned before the comparison is difficult.

Table 4. Mean values of water absorption of tested formulation in Figure 18-24.

Mean values
Formulation Wood batch A Wood batch B
22 22.05
23 22.36
24 22.33
25 26.65
26 25.04
27 25.22
28 26.17
29 24.69
30 23.41
33 29.06
34 39.60
35 33.40
36 33.66
37 39.18
38 41.19
41 31.93
42 35.11
48 33.40
49 33.09
51 33.40
52 28.05
RCP1 34.89
RCP2 29.55
Uncoated 50.36

The mean values of the water absorption of the tested formulations in Table 4 illustrates the difference
between the two batches of wood where batch B result in lower absorption. Table 4 also reviles that
Formulation 52 absorbed more than the other formulations where the same wood batch had been used.
Further, the difference between the two references can be seen. Moreover, most of the formulations tested
with wood batch A had a mean absorption in between the two references. To have a better comparison
between the samples the weight increase of the wood piece when coating has been added can be calculated

30
by equation 2 where m0 is the weight of the uncoated sample and m1 is the weight of the sample when it has
been coated. The weight increase can tell which samples have more coating than the others and thereby
potentially better protection and less absorption.

𝑚1 −𝑚0
𝐶𝑜𝑎𝑡𝑖𝑛𝑔 𝑤𝑡% = 100 ∙ (2)
𝑚0

5.7 Weathering
To give an indication of how the formulations will perform in real life conditions a weathering test were
performed by placing coated wood outside. In Figure 21 pictures from this test is illustrated.

RCP1: 0 days RCP1: 1week RCP1: 1 month

49+Catalyst B: 0 days 49+ Catalyst B: 1 week 49+Catalyst B: 1 month

Figure 21. Pictures taken during weathering test. The pieces of wood are marked with formulation number: time outside. In
Formulation 49, extra Catalyst B has been added.

31
The color difference seen in Figure 21 over time is mainly due to the light effects during photographing but
some yellowing may have occurred of both coated and uncoated samples. It is difficult to judge the degree of
yellowing from these pictures though.

On the wood treated with RCP1 a dust layer has formed on the surface after one week while no dust can be
seen on wood coated with the bio-based formulation and the uncoated wood sample in Figure 25. This might
be due to the rougher surface or different surface charge density formed with the reference compared to the
smother surface with the bio-based formulations produced in this project. However, after one month wood
coated with the bio-based formulation also had a dust layer on the surface. This dust was easily brushed away.
Moreover, after 1 month a line was spotted at the bottom of the wood piece coated with RCP1. This was not
spotted on the wood coated with the bio-based formulation or the uncoated sample. This line is probably
caused by massive rain forming a waterline at the bottom as the rain flows against the coated wood piece.

Wood type 3 coated with Formulation 49 with extra Catalyst B became whiter/lighter after one week with both
sunshine and rain. No drop marks was seen confirming what has been stated under the section 5.4.

5.8 Surface pH
As woods natural pH is around 3-4, the pH for the final coating should also be around 3-4 so that the woods
natural functions are optimal and preserved with minimum change. Therefor the surface pH for coated wood
pieces was determined and the results listed in Table 5 below.

Table 5. Surface pH for Wood type 1 and 3 and coated with different formulations.

Wood type 3 Wood type 1

Coatings: Non RCP2 Formulation Formulation Formulation Non RCP2 Formulation

52 49 with x% 49 with 2x% 41
extra extra
Catalyst B Catalyst B

First 10.960 9.735 10.810 10.156 10.366 4.165 4.430 4.450

measure

Second 10.810 9.977 10.926 10.049 10.509 4.337 4.337 4.205

measure

Third 10.910 9.755 10.976 10.104 10.213 4.389 4.389 4.230

measure

Mean 10.893 9.822 10.904 10.103 10.366 4.117 4.385 4.295

As it is indicated in Table 5, no distinct difference in surface pH was noted between uncoated, Formulation 41
and RCP2 on Wood type 1 and all of them were around 4. On Wood type 3 no distinct difference was noted
between the uncoated and wood coated with Formulation 52 and both had a pH at almost 11. However, with
RCP2 the surface pH decreased with 1 pH unit. This means that the acid power of the new bio-based
formulations in relation to the alkaline power of the first coating that Wood type 3 is treated with is not

32
balanced. This challenge was addressed by addition of Catalyst B to the Formulation 49 and as it can be seen
in the table, it could successfully decrease the pH to around the RCP2 range. Worth to mention, considering
the amount of added Catalyst B, the pH decrease is considerable. The difference in pH between the RCP2 and
Formulation 52 may be a result of the coating process where the basic first treatment of Wood type 3 is mixed
with Formulation 52 when it is applied with a brush.

When the pH is measured on Wood type 3 and coated with Formulations 52 and 49 the pH decreased at the
beginning of the measurement and then the pH increased before the pH was stabilized. When the pH
increased it was observed that the wood surface under the drops whitened, similar to what was seen during
the static hydrophobic tests. This indicates that the first coating is dissolved or migrates in the second bio-
based coating into the drops or reacts with the formulations in some way unlike the reference. In the Table 5
the lowest detected pH are listed.

5.9 Stability
Formulation 33, 42, 49 and 49 with extra Catalyst B added, marked as 49 + Catalyst B was tested for stability.
Diluted samples of these formulations were also tested. These samples were diluted to 50%, 25% and 12.5%.
During the stability the samples were checked for edge formation, creaming and sedimentation.

It was noted that the formulations with a lower concentration formed edges faster than the corresponding
formulations with a higher concentration. This effect can be correlated to the dilution effect where viscosity
decreased a little bit and the balance of emulsifiers and stabilizers in the interphases of the hydrophobic phase
and water phase were changed. However, once the edges were formed there was no growth of the edges.

It was also noted that more creaming occurred with time and temperature. This was expected as higher
temperatures will speed up reactions and with a longer time more of these reactions can occur.

Further, the use of Surfactant D resulted in less sedimentation compared to the use of Surfactant C. This was
expected since systems with Surfactant D created smaller droplets. Secondly it was noted that lower
temperatures and higher concentration resulted in more sedimentation. Since higher concentration means
more collision between droplets it is expected that these samples will show more sedimentation. At lower
temperatures, the waxes are on their fully solid state which can contribute to aggregation compared to the
more deformable melted waxes. Further the higher kinetic energy at higher temperatures will prevent
aggregates to precipitate.

Comparing the degree of edge formation, creaming and sedimentation over time no distinct difference was
noted between Formulation 49 and Formulation 49 with added Catalyst B. Moreover, Surfactant C based
formulations shows more sedimentation over time even though the creaming and edge formation is similar to
formulations with Surfactant C.

Further, considering all three parameters (edge formation, creaming and sedimentation) over the performed
time period, Formulation 33 performed worse than the other samples. However, it is difficult to determine the
main reason of this observation since several parameters were changed at the same time, including different
concentrations of wax, Surfactant C and oils. However the proportion of wax and the different oils seems to

33
have an impact on the stability. This is in line with the discussion of the result in section 5.2. Further, it can be
expected that a higher concentration of Surfactant D and Surfactant C would stabilize the system more and as
seen previously in section 5.2, but the difference in the water absorption and hydrophobicity will not be large
between these two concentrations of surfactant as discussed in section 5.3 and 5.6. Further, from the result
discussed in section 5.2, 5.3 and 5.6 it was seen that a lower wax content could improve the stability without
affecting the absorption.

After shaking the samples after one month only some part of the sedimentation and edge formation was visible
and the rest of the emulsion was stable. According to the microscope images of the formulations taken after
one month no distinct difference can be seen between the different formulations or with different
concentrations of each formulation. Perhaps a greater difference could have been seen if the microscope
images were taken at earlier stages since almost all formulations had changed with respect to all parameters
after one month. However, more flocculation was formed compared to the images taken at the start.

34
6. Conclusion
From the microscope characterization it was concluded that the sonicated samples had the smallest droplet
size and least aggregation. Further it was concluded that Oil Z have an adverse effect on the emulsion quality
while Oil Q and Surfactant D improves the stability in terms of droplet size and aggregation. Moreover, the
thresholds of Surfactant D, Wax O and wax and oil content were determined.

The static hydrophobic tests on untreated wood generally showed that all of the formulations produced in this
project performed quite similarly in this test. The deviations in between all bio-based formulations and between
the current non-bio-based product and the bio-based formulations can be explained by the different content of
the coating as well as application variation, size of water drop, different wood structure etc.

From the static hydrophobic test on Wood type 2 it was concluded that the current product and the tested
formulations performed similarly. This is also true for Wood type 3 except that the formulations produced in this
project leaves more profound white marks. The opposite was observed with Wood type 4 where Formulation
26 and 41 performed better than the current reference product.

Only the results from Formulation 33-38, 41, 48, 49 and 51 can be compared to the current product in the
water absorption test as the same batch of wood was used. After 48 hours in this test, Formulation 33, 41, 48,
49 and 51 showed less absorption compared to the two batches of the current reference product even though
the difference was not large. Moreover, most of the formulations showed similar absorption as the current non-
bio-based reference product and compared to each other throughout the time confirming the small difference
observed with static hydrophobic test. However, from the results of Formulation 22-30 and 52 it can be
concluded that the wood have a large impact on the results hence more measurements have to be performed
with different batches of wood to give a more conclusive and comparable results.

Since the current reference product, unlike Formulation 41, formed an edge of another color at the bottom of
the wood piece and more dust were stuck on the coated surface during the weathering test, it can be
concluded that Formulation 41 performed similar, perhaps better than the current non-bio-based reference
product. The weathering test also indicated that no marks are formed on coated Wood type 3.

Form the stability test it was concluded that Surfactant D improves the stability. The stability test also indicated
that the stability needs to be improved as all formulations showed edge formation, creaming and sedimentation
even at room temperature. Comparing the microscope images at the start and after one month it was
concluded that more flocculation had occurred. When the samples were shaken after one month no creaming
was observed. It should be noted that reactions that impairs the stability behave differently on different
temperatures. Hence a non-accelerating stability test at room temperature gives a result closer to the real
conditions during storage.

35
7. Further aspects
According to the results some formulations performed in this project shows similar absorption of water and
appearance as the current bio-based reference product suggesting that these formulations can be candidates
for the new product. However, further tests and improvements need to be done.

The stability of the formulations needs to be improved either by changing the proportions between the
chemicals in the system or by addition of other co-surfactants and surfactants. Moreover, as discussed under
the section 5.9, higher concentration of Surfactant D and lower wax content can be used without interfering
with the absorption to any large extent. However, even if the concentration of Surfactant D is increased and the
wax content is lowered the stability is probably not good enough. Further, even though it is believed that the
current reference product has a longer shelf life than the current produced bio-based formulations, future
formulations needs to be compared to the current product as well. Furthermore, the process needs to be
optimized in the aspects of time, temperature, rate and flow during homogenization to possibly improve the
stability but also improve the effectiveness and processability.

Even though the weathering test showed good results and it was performed in April and May, a period with
large weather variation, an outdoor test for a longer time period needs to be performed, preferably two years.
The test pieces and environment could also be adapted to more similar real-life conditions. This will not only
give an idea of the physical changes but also whether fungus will thrive on the surface of the coated wood. The
outdoor tested pieces also need to be absorption tested after specified time periods to give an idea of the
hydrophobic performance and not only physical changes. Also, other types of coated wood should be tested
outside, including Wood type 2-4.

Repeated test on the formulations needs to be performed to give more reliable results with lower standard
deviation. Other experiments to test absorption and hydrophilicity can also be used to confirm result or give a
broader view of the performance of each formulation. During the project it was been discussed to measure the
roll-off angle, deformation during absorption and a rain test where coated wood pieces are exposed to artificial
rain and the gained weight is measured. Tests that are less dependent on the substrate could be used but
coatings no matter type and substrate is always heavily dependent on the substrate. Hence tests that are
performed where this aspect is not considered do not give a proper picture of the final performance.

More reliable tests and measuring methods of the physical changes during weathering can be performed. Here
climate chambers can be used to simulate rain, sunlight, eat etc. Good to have in mind is that almost all tests
in the coating industry are empirical.

While almost all the chosen raw materials were biodegradable, a final biodegradability test needs to be
performed to establish that the final formulation is biodegradable. Further test where fungi are applied on
coated wood samples could give an indication if fungi can thrive on the surface or not.

36
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www.kth.se