Cite this paper: Vietnam J. Chem.

, 2021, 59(1), 127-131 Article

DOI: 10.1002/vjch.201900198

Study of copper releasing rate from vinyl

copolymer/Cu2O/Seanine 211-based anti-fouling paint coating
Do Minh Thanh*1,2, Nguyen Anh Hiep1, Vu Dinh Sang3
1
Institute for Tropical Technology, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Cau
Giay, Hanoi 10000, Viet Nam
2
Graduate University of Science and Technology, Vietnam Academy of Science and Technology, 18 Hoang
Quoc Viet, Cau Giay, Hanoi 10000, Viet Nam
3
Hanoi University of Industry, Cau Dien, Tu Liem North, Hanoi 10000, Viet Nam
Submitted December 29, 2019; Accepted 6 February 2020

Abstract
The effects of Seanine 211 content rate on Cu releasing as well as coating properties were investigated. The process
of releasing Cu has been studied in dynamic conditions with Seanine content of 0, 3, 5, 10 % and static conditions using
Seanine content of 5 % (in weight). Under dynamic conditions, the Cu shall release at high speed in the first 2 days of
the test, then remain stable and proportional to the time according to the linear-line equation, maintained at ≈ 3.5
µg/cm2/day. Under static conditions, the process of Cu releasing is studied through the reduction of coating thickness,
the results show that the coating abrasion rate is also proportional to the time and according to linear-line equation.
With the content of 20 % Cu2O (in proportion) and 5 % Seanine (in proportion), the coat has the following properties:
relative hardness 0.5; impact resistance 65 Kg.cm; flexural strength 1 mm; adhesion cross cut at 1.
Keywords. Anti-fouling paint, Seanine 211, Copper(I) oxide.

1. INTRODUCTION is still the manufacturers’ first choice today.

Vietnam has 3,260 km of coastal line, excluding
islands, and over 49 seaports at various scales.
Marine economy as well as sea transport plays an
important role in the national economy of our
country.[3] Iron and steel structures which operating
offshore, such as oil rigs, ships etc. have suffered
from great damage not only due to metal corrosion
but also due to microbial fouling, causing large loss
to the operation, maintenance and reparation.
Therefore, the study of anti-fouling paints has been
interested by scientists, domestic and foreign
manufacturers.
Scientists have worked hard to find out
environmentally friendly materials to replace toxic
compounds such as organotin, including compounds
which are capable of killing extracted micro-
organisms from natural products such as those
derived from algae, resin etc. and control the release
of microbiological substances to prevent emissions
on a large scale. However, in fact, these organic
compounds are less antifouling-active than organotin
and copper compounds.[1,2,4,7,8] Because organotin
compounds are currently banned from using, Cu2O
However, the effects of copper(I) oxide on marine
life as well as human life have still been
controversial.[2,4,9] Therefore, how to reduce the
content of copper(I) oxide in anti-fouling paints
without decreasing the paint quality is a problem
raised to scientists and manufacturers. Also, the
usage of copper(I) oxide with anti-fouling organic
compounds is a highly concerned subject.
Seanine 211 is a 30 % solution of 4.5-dichloro-
2-n-octyl-4-isothiazolin-3-one in xylene, the Seanine
211 mixture remains unchanged for at least two
years at 22-25 °C and 6 months at 40 °C. Seanine
211 is an active ingredient widely used in anti-
fouling paint nowadays because it meets most of the
characteristics such as not containing heavy metals,
having good effects against fungi, bacteria, worm
algae, diatoms etc. Especially with its environmental
characteristics, Seanine 211 did won the very first
Green Chemistry Challenge Award in the Design of
Safer Chemical Products presented by the US
Environmental Protection Agency. Seanine 211 has
a very broad spectrum of activity when being used
with copper oxide.[1,2,4,5]
Within the scope of this study, we plan to clarify

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Vietnam Journal of Chemistry Do Minh Thanh et al.

the effect of Seanine 211 content on copper ISO 2409 standard; the flexural strength of the
releasing ability of the coating based on vinyl coating is determined by ГOCT 6806-53 standard.
copolymers and the properties of the products.
2.4. Copper releasing ability assessment
2. MATERIALS AND METHODS
PVC sheets sized 55 cm are covered by such paint
2.1. Materials with a coating thickness about ≈ 150 µm. Weighing
to record the initial weight of each plate at the
Cu2O Powder from Hangzhou Dayang Chem Co. starting point. Soaking these PVC sheets in artificial
Ltd, China. seawater (prepared according to ASTM D1141 at 40
o
- Vinyl copolymers, China C). Over a fixed period of time, this PVC sheet is
- Zinc acrylate copolymer, China removed, dried at room temperature and weighted to
- Modified resin, China measure the loss weight over such period.
- Anti-fouling ingredient Seanine 211 from Dow The formula for calculating the loss weight:
- Solvent: Xylene, acetone: Using pure grade
from China.
- Artificial seawater under Standard ASTM
where: Δm is the loss weight; m0 sample and sole
D1141.
sheet weight at starting point; mn sole sheet weight;
mt sample and sole sheet weight at the specified
2.2. Modulation fomula of manufacturing anti-
time.
contaminant, anti-fouling paints
The steel sheets sized 10×15 cm are covered by
such paint with a coating thickness about ≈ 150 µm.
Modulation fomula of manufacturing anti-
The samples are attached to the shaft and stirred in
contaminant, anti-fouling paints is presented in
brine at 100 rpm. Stirring solution is collected at
Table 1.
different times, analyzing the concentration by AAS
atomic absorption spectrum method. From which,
Table 1: Modulation formula of manufacturing
calculating the copper releasing rate according to
anti-fouling paints
this formula:[10]
Weight
Ingredients
Percentage (%)
Vinyl copolymers 30
Modified Rosin (50% in where: T: Copper releasing speed (µg/cm2/day); C:
20
xylene) Copper concentration in 1 liter of soaking solution
Zinc acrylate copolymers 20 (mg/liter); V: Volume of solution (liters); S: Testing
Cu2O powder 20 surface painted area (cm2); d: Number of immersion
Seanine 211 - days.
Additives 5
3. RESULTS AND DISCUSSION
Anti-fouling Seanine 211 is used with 0, 3, 5 and
10 % in total (which are correlative to M0, M1, M2, 3.1. The morphology of the coating copolymer
M3 samples). vinyl/Cu2O/Seanine
The paint mixing process is described as
follows: The mixing components are respectively The morphological structure of anti-fouling coating
fed into the ball mill at a speed of 100 rpm in 8 surface based on copolymer vinyl/Cu2O/Seanine is
hours. Then being filtered through a 270 mesh presented in figure 1.
strainer. From SEM images in figure 1, we can see that
the coating has heterogeneous structure, with the
2.3. Determination of the physico-mechanical dispersion of the additive phases, Cu2O powder in
properties the paint base, the size of additives as well as Cu2O
widely ranged from 100 nm to 2 µm. These particles
The relative hardness of the coating is determined by are evenly distributed in the paint base, which can
ISO 1522:2006 standard; the impact resistance of the explain the stability of the abrasion of the coating
coating is determined by ISO 6272-2:2011 standard; when being tested in artificial seawater under both
the adhesion cross of the coating is determined by static and dynamic conditions.

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Vietnam Journal of Chemistry Study of copper releasing rate from vinyl…

Figure 1: SEM images of the coating

3.2. Study on the copper release of the coating M3. The concentration of Cu released from the
coating at different contents of Seanine 211 is shown
The anti-fouling ability of paint strongly depends on in figure 3.
the Cu releasing rate, which is also the erosion speed
of the coating. Within the scope of this study, we
assess the abrasion rate of coating both in static and 500

dynamic conditions. 450

400
350
3.2.1. Static abrasion rate of 5% Seanine
Cu (mg/l)

300
250
The process of erosion is tracking over time and 200

obtained results shown in figure 2. 150

100
50
0.20
0
0 20 40 60 80 100
0.16 Time (day)
Lost weight (g)

0.12
Figure 3: Cu releasing concentration over time.
0.08 Seanine in portion: 0 %,  3 %, ● 5 %,  10 %

0.04 Figure 3 showed that samples contained Seanine

will affect the ability to release Cu in the first 2 days
0.00
0 10 20 30 40 50 of the experiment. In the samples with Seanine
Time (day) content of 0 %, 3 %, 5 % and 10 %, copper releasing
concentration after 2 days, respectively, is 53.1; 90;
Figure 2: Weight loss of the coating over
95.25 and 138 mg/l. This shows that when
experimental period
increasing Seanine content, the ability to release
copper in the coating will increase respectively.
Regarding experimental results after 43 days of
However, after 2 days, this releasing concentration
soaking, the weight loss of coating is very small (≈
tended to increase slowly for M1, M2, M3 samples
5.3 %). This shows that the abrasion rate occurs very
while still increased rapidly for M0 sample.
slowly in static conditions. Figure 2 also shows that
Especially, after about 25 days of experiment, the
the decrease in sample weight is proportional to the
concentrations of M0, M1, M2, M3 samples were
time according to the linear-line equation. This
193.1, 129.3, 160.1, 191.2 mg/l, respectively. Also
means that the abrasive speed remains constant
after 2 days, the copper concentrations in M0, M1,
throughout the experiment.
M2, M3 samples increased gradually and linearly
according to the linear-line equation, or this means
3.2.2. Dynamic abrasion speed
that the abrasion rate remained stable during the
experiment.
Anti-fouling Seanine 211 is used with 0 %, 3 %, 5 %
Some properties of anti-fouling paint with
and 10 % percent by weight of samples M0, M1, M2,
different Seanine contents are presented in table 2.

© 2021 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH Verlag GmbH www.vjc.wiley-vch.de 129

Vietnam Journal of Chemistry
Table 2: Some properties of anti-fouling paints in
different Seanine contents
Seanine content rate/
Properties of paint weight in total (%)
No
coating
0 3
Impact resistance
1 40
(kG.cm)
Flexural strength
2 1
(mm)
3 Adhesion (Point) 3 2
4 Relative hardness 0.48 0.50 0.50 0.53
Because Seanine has a ring structure in the
molecule, increasing Seanine 211 content in such
system will accordingly increase the relative
hardness of the coating. In addition, chlorine atoms
in the molecule also contributes to the adhesion of
the membrane. This is evident in models with and
without Seanine. However, increasing the Seanine
content in excess of 5 % makes the flexural strength
decrease. For anti-fouling paint systems, which are
submerged paint systems, their adhesion and flexural
properties are more concerned than relative
hardness.
The effect of Seanine contents on copper
releasing rate is presented in figure 4.
40
35
30
Cu (µg/cm2 /day)
25
20
15
10
5
0
0 20 40 60
Time (day)
Figure 4: Average Cu releasing speed over time
Seanine in portion: 0 %,  3 %, ● 5 %,  10 %
Figure 4 shows that in the first 2 days of testing,
when Seanine content increased from 0 to 10 %, the
Cu releasing rate increased accordingly, then all 4
rates of Cu releasing speed tended to decrease and
remained stable. After 2 days of experiment, the
average Cu releasing rate with the Seanine contents
of 0 %, 3 %, 5 %, and 10 % was 19.13; 27.56; 32.50
and 36.88 µg/cm2/day respectively. With 0 %
Seanine content, Cu releasing rate remained stable
after 15 days of experiment. Meanwhile, with the
Seanine content of 3 and 5 %, Cu releasing rate
remained stable after 20 days of experiment. With 5
© 2021 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH Verlag GmbH www.vjc.wiley-vch.de
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Do Minh Thanh et al.
% Seanine sample on the 19th day, the average Cu
releasing speed was 5.89 µg/cm2/day. From the 20th
day onwards Cu releasing rate of the coating was
more stable and maintained at ≈ 3.5 µg/cm2/day, this
rate maintained until the 98th day. With a stable
5 10 releasing rate and within this threshold, the coating
is resistant to marine microorganisms such as algae,
50 65 70
fouling and some other microorganisms.
1 1 2
4. CONCLUSION
1 1
It has been determined that Seanine 211 content has
an effect on Cu2O releasing process but is not
significant. Seanine 5 % content is suitable rate for
making anti-fouling paint. The average copper
releasing rate at stable stage ≈ 3.5 µg/cm2/day and
this process follow the linear-line equation in both
static and dynamic conditions. The coating with
good properties are considered for making anti-
fouling paint.
Acknowledgments. The authors are grateful to
Vietnam Academy Science and Technology for its
financial support by grant No VAST.03.04/20-21.
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Corresponding author: Do Minh Thanh

Institute for Tropical Technology
Vietnam Academy of Science and Technology
18 Hoang Quoc Viet, Cau Giay, Hanoi 10000, Viet Nam
Email: thanhnau.vn@gmail.com; Tel: +84- 988267333.

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