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Optimization of the water-based road-marking paint by experimental design,

mixture method

Article  in  Progress in Organic Coatings · April 2006

DOI: 10.1016/j.porgcoat.2006.01.006

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 Progress in Organic Coatings 55 (2006) 337–344

Optimization of the water-based road-marking paint by

experimental design, mixture method
Shohreh Fatemi a,∗ , Maryam Khakbaz Varkani a , Zahra Ranjbar b , Saeed Bastani b
a Chemical Engineering Departmant, Tehran University, Iran
b Iran Color Research Center, Iran

Received 4 October 2005; accepted 12 January 2006

Abstract
The main purpose of this research is formulating and optimizing a new road-marking paint which is an environmentally friendly product.
This paint is produced with an emulsion of an acrylic copolymer and contains the least of the volatile organic compounds. The formulation and
optimization procedure is carried out on the base of experimental design by the method of mixture in which the important paint properties are
modeled by using special cubic model. The present method has the capability of investigation the effect of raw materials at different levels with
fewer experiments than factorial and fractional factorial design.
In this research, the main parameters such as resin, pigment and filler were selected at different levels, and different samples were prepared
by combination of additives and other required reagents. The properties of wet and dry films of the samples were determined using ASTM
test methods. Different responses such as pigment volume concentration (PVC), latex critical pigment volume concentration (LCPVC), abrasion
resistance, hardness, gloss, no pick up time and surface drying time, were selected as the objective functions of this study. By running DX6 software,
using special cubic model and selection of desired range of end-use properties, the region of optimum paint formula was determined.
The accuracy of the model was examined by preparing a sample in optimized region and by determining its final properties, experimentally. The
results exhibit a good agreement between the model and experimental measurements. This product was compared with commercial solvent based
traffic paint and good quality was reported in end-use properties.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Water-based paint; Road-marking paint; Formulation; Experimental design; Optimization

1. Introduction components of water-based paints, giving them a well dust pro-

Over the recent years water-based road-marking paints have
extendedly been produced, under increasing environmental
restrictions. These coatings are widely recognized as the envi-
ronmentally friendly road-marking paints due to their water-
based resin composition and low level of volatile organic com-
pounds. Stricter environmental laws in 1950s have intensified
researches on water-based paints, leading to a gradual substi-
tution of solvent-based counterparts since 1970s [1–3]. Less
volatility, more safety especially against fire risk and bet-
ter hygienic conditions during production and application are
the main advantages of using water-based paints. The water-
dispersible resins (e.g. acrylic emulsion resin) are the basic
∗ sented to determine the optimum paint formula, using analysis
Corresponding author. Tel.: +98 21 6111 2229; fax: +98 21 6111 2229.
E-mail addresses: Shfatemi@ut.ac.ir (S. Fatemi), ranjbar@icrc.ac.ir
(Z. Ranjbar).
tection [4–6].
Water-borne road-marking paints comprise around 90% of all
traffic paints in USA. This proportion is 70 and 15% for Australia
and Europe, respectively. Although these paints dry relatively
slowly, the problem can be moderated using techniques like thin
layer spraying [7].
The main goal of this study was to find an optimum for-
mula for production of a water-based traffic paint with a rela-
tively short drying time, high durability and reasonable price.
To fulfill this task, numerous costly time-consuming trials are
needed. Therefore, selecting a correct method to perform multi-
parametric tests at several levels is essential.
In this study statistical experimental design helped us to
investigate the effect of several variables, like resin, pigment,
filler and other additives at several levels. Here a model is pre-
of variance on the results of paint property tests. This research
represents a new method to formulate and optimize coatings. In

0300-9440/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2006.01.006
338 S. Fatemi et al. / Progress in Organic Coatings 55 (2006) 337–344
this method it is possible to get worthy results by doing the least
experiments [8,9].
2. Experimental design
To attain the optimum formula, numerous experiments are
needed. Each experiment involves a series of tests. Simultane-
ous alternation in system variables and their consequents have
to be taken under close examination. The experimental design is
a procedure among the methods with statistical analytical bases.
The aim of this method is to determine system sensitivity to each
parameter. This method is quite beneficial because the behav-
ior of system can be easily verified depending on the factors
incorporated [8].
Each experiment has two sides, experimental design and sta-
tistical analysis of the data. To analyze the data, the experiment
has to be organized in a way that right and credible data can be
collected and eligibly computed. The general algorithm of the
experimental design is proceeding by following steps:
(1) recognition and expression of the problem;
(2) choosing system variables and range of variation for each
one;
(3) choosing objective function, this comprises all useful infor-
mation about the system;
(4) choosing one of the experimental design methods;
(5) performing the experiments and getting the response;
(6) analyzing the data to investigate the effect of the parameters
on the objective function;
(7) conclusion about the system.
The only way to attain an optimum paint formula is to per-
form several experiments. In the laboratory, after running the
initial experiments and solving some problems occurred in for-
mulation, a primary formula was obtained and selected as the
basis for experimental design. Then the main components of the
water-borne paint (i.e. resin, pigment, filler) were selected as
the input variables of the system [9]. The range of variation for
each component has been considered about 15% more or less
than its basic value in the original formulation. Since a favorable
quality control is depending on several traffic paint properties,
only one objective function is not sufficient to be considered for
the formulation. Therefore, a few important end-use properties
of traffic paint comprising Taber abrasion resistance, hardness,
gloss, no pick up time, surface drying time, as well as PVC and
LCPVC of the samples are considered as objective functions
of the statistical analysis. Finally at optimization step, a weight
coefficient allocated for each test result, contributes to show the
degree of importance of each property in the product.
Previous works have applied fractional factorial method,
which is not efficient for multi-level experiments, and is mostly
applied for two levels of variables. On the other hand, when
the variables of experiments are only the components of the
product, sum of the weight fractions resulted by this method is
not exactly 100% because two equal experiments may repeat
in design table and this causes equal responses in the analy-
sis [8]. So in this study, instead of using fractional factorial we
Fig. 1. Experimental design space, 1: maximum amount, 0: minimum amount,
(a, b, c) = (resin, pigment, filler).
took advantage of a new method named mixture design which
has not the problem of factorial method. In 1979, Robert Snee
[8] clarified the qualification of the mixture method when sum
of the values of variables attains 100%. The sum of three frac-
tions has to be one in three-fractional designs. In this condition,
experimental valid points are located on a triangular page across
(0, 0, 1), (0, 1, 0) and (1, 0, 0). Each head and its opposite side
indicate the highest and the lowest values of a fraction in the for-
mulation, respectively. After testing the produced samples, the
responses appear on the triangular page like a map with contour
curves. Each curve represents the same response with different
formulations.
With regard to the presented method in this research, 10 dif-
ferent samples have been developed according to Fig. 1. For
example, a composition of three compounds (resin, pigment and
filler) is presented in this figure at the center point (1) which each
component covers 33% out of the total and their maximum val-
ues are located at the heads of the triangle [8,9].
3. Experiments
To prepare each sample, a water-soluble copolymer acrylic
emulsion resin, pigments and their additives were used. Their
properties are indicated in Table 1.
Table 2 presents weight percent of the main components for
preparation of the samples according to the experimental design
of mixture method, pointing at Fig. 1. As it is noticed, the main
components (resin, titanium dioxide and carbonate) of the 10
samples are selected in six different levels.
For each sample, different end-use properties are measured.
Some of these properties are related to wet and some other to dry
paint films, which were determined by standard test methods as:
1. Taber abrasion (ASTM D4060-01)
2. Hardness (ASTM D3363-00)
3. Adhesion (ISO2409:1992)
4. Gloss (ASTM D523-89)
5. Density (ASTM D1457-98)
 S. Fatemi et al. / Progress in Organic Coatings 55 (2006) 337–344 339

Table 1
Ingredient properties
Chemical identification Physical and chemical properties

Appearance Solubility Odor Boiling range (◦ C) Density Viscosity (mPa s)

in water (g/cm3 ) at 23 ◦ C

Resin Acrylic emulsion copolymer Liquid Soluble Almost odorless 60–100 1.05 15–100
Dispersion agent Alkyl ammonium salts Liquid Insoluble Of organic solvents 100–200 0.91 >80
Anti-foaming Waxes-mineral oils non-siliconate Liquid Insoluble Almost odorless >300 0.89 30–200
Plasticizer Glycohol Liquid Soluble Mild odor 168–172 0.90 21
Coalescence agent Ester alcohol Liquid Insoluble Moderate 255–260.5 0.95 –
Pigment TiO2 Solid Insoluble Odorless – 4.1 –
Filler CaCO3 Solid Insoluble Odorless – 2.7 –

6. Surface drying time (ISIRI:339)
7. No pick up time (ASTM D711-89)
Two other properties, PVC and LCPVC, which affect mostly on
the final paint properties are calculated by the following equa-
tions [10]:
V (titan + carbonate)
PVC =
[0.4 × V (resin)] + V (titan + carbonate + plastistizer + disper. + antifoam. + coalecence)
1
LCPVC =
1 + (OA × ρp /(93.5 × ε))
OA is the oil absorption of pigment mixture (titanium diox-
ide + carbonate) which is measured by ASTM D281 for each
sample separately. ρp is the pigment density which is calculated
from the additivity rule, in each sample. ε is the binder efficiency
which is selected 0.7 in this work [11].
The critical pigment volume concentration for a latex paint
is invariably less than that for its solvent-type counterpart. In
effect, this means that at their respective CPVC points a larger
volume of latex polymer (Vlatex ) than of solution binder (Vsol ) is
required to bind a given solid volume of pigment. On observing
this relationship, Berardi [12] was prompted to call the ratio of
these volumes a binder efficiency.
Vsol
ε=
Vlatex
Binder efficiency of 1.00 corresponds to a 100% resin binding
ability. Latex polymers have efficiency values less than this.
The binder efficiency can be calculated from knowledge of the
measured LCPVC for a given pigmentation, together with the
pigment density and oil absorption value [11].
The measured and calculated properties are presented in
Table 3.
(1)
(2)
4. Results and discussion
When there is just sufficient binder present to fill the voids
between pigment particles in the dry paint, the paint is said to be
at the CPVC [10]. CPVC and PVC are influential factors, which
control the paint quality.
Fig. 2 presents PVC and CPVC of each sample, obtained
from Eqs. (1) and (2), comparatively. In this figure, sample nos.
6–8 show high CPVC with high and very close PVC. In contrast,
samples 4, 5 and 9 show very low PVC with significant difference
of CPVC and PVC.
High PVC shows high pigment volume concentration in the
paint but these kinds of paint needs sufficient binders to fill the
voids between pigment particles in dry paint, so high CPVC is
required too.
(3) One of the most important end-use properties of traffic paint
is abrasion resistance which is shown in Table 3. Samples 4,
5 and 9 represent lower abrasion resistance with respect to the
others. Another important property of traffic paint is adhesion.

Table 2
Formulation of paint, based on main ingredients (wt%)
Resin TiO2 CaCO3

1 29.5 20.4 50.1

2 28.7 27.8 43.5
3 27.8 35.5 36.7
4 41.8 16.7 41.5
5 35.2 18.6 46.2
6 25.7 15.4 58.9
7 24.7 22.2 53.1
8 22.1 11.5 66.4
9 34.8 26.4 38.8
10 30.4 13.5 56.1
Fig. 2. The PVC (%) and LCPVC (%) of 10 samples.
340 S. Fatemi et al. / Progress in Organic Coatings 55 (2006) 337–344

Table 3
Tests results
Property 1 2 3 4 5 6 7 8 9 10

Taber abrasion (mg) 94 94.7 90.5 107.2 100.3 82.9 74.8 63.8 95.0 91
Density (g/cm3 ) 1.654 1.736 1.770 1.500 1.615 1.770 1.740 1.800 1.611 1.644
Hardness (N) 9 8 7 8 9 6 9 8 6 7
No pick up time (min) 15 17 17 33 27 20 16 13 17 18
Surface drying time (min) 14 17 18 20 15 15 18 16 19 13
Gloss (%) 4 4 6 5 5 3 4 3 5 4
Gloss after 7 days (%) 3 4 5 4 4 3 4 3 4 3
Adhesion 5B 5B 5B 4B 4B 5B 5B 5B 4B 5B
PVC (%) 55.44 55.59 54.90 44.65 50.55 60.00 59.09 63.21 49.59 55.16
LCPVC (%) 59.6 58.3 56.1 59.9 59.0 61.3 58.6 62.3 57.4 61.0
LCPVC (%) − PVC (%) 4.17 2.76 1.17 15.30 8.45 1.33 −0.48 −0.86 7.81 5.80
Price (US$/kg) 1.629 1.734 1.957 1.778 1.682 1.407 1.589 1.251 1.774 1.940

Adhesion property of the samples 4, 5 and 9 is measured as 4B
which is lower than the other samples (Table 3). It is concluded
that high difference of CPVC from PVC causes reduction of
traffic paint quality. So the best quality of the paint appears when
it works at CPVC.
In Fig. 3 the contour chart of CPVC is presented by running
the statistical model. The model shows approximately a linear
relationship of CPVC from titanium dioxide to filler content,
because oil absorption measurements of pigments show higher
OA for titanium dioxide than for filler. In Fig. 4 the contour
chart of PVC is presented by the model in which higher PVC
is determined with respect to higher content of both filler and
titanium dioxide.
As mentioned above the difference of CPVC from PVC is
an important factor to change the paint property. Fig. 5 repre-
sents the statistical model of CPVC (%) − PVC (%). This figure
shows higher PVC and negligible difference of CPVC from PVC
around the right corner of the triangle where the samples around
this part show best end-use properties.
Fig. 6 presents the Taber abrasion curves; it is clear that
increasing PVC and decreasing CPVC − PVC cause improve-
ment of the paint quality and lower abrasion.
Fig. 7 illustrates that no pick up time depends on the amount of
pigment mixture. An important factor in water-based traffic paint
is drying no pick up time which needs higher level of pigment
mixture then higher PVC is required. Fig. 8 shows that increasing
resin fraction and decreasing filler, increases the surface drying
time of the paint. It is concluded that paint formulas with higher
PVC are more desirable to cause higher rate of drying on the
road.

Fig. 3. Latex critical pigment volume concentration (%). Fig. 4. Pigment volume concentration (%).
 S. Fatemi et al. / Progress in Organic Coatings 55 (2006) 337–344 341

Fig. 5. Difference of LCPVC (%) from PVC (%). Fig. 7. No pick up time (min).

Fig. 6. Taber abrasion (mg), weight of paint removed from surface after 2000
round. Fig. 8. Surface drying time (min).
342 S. Fatemi et al. / Progress in Organic Coatings 55 (2006) 337–344

Fig. 9. Gloss (%), angle of 60◦ . Fig. 10. Hardness (N).

According to Fig. 9, increasing the resin and titanium diox- To ensure of model accuracy and its results precision, as an
ide composition increases the paint gloss. The positive effect of example, one optimized formula pointed in Fig. 13 was selected,
titanium dioxide on the gloss depends on the very fine particles made in the laboratory and verified by quality control tests.
of pigment which is used in this study, but increasing the content In Table 5 the results of the experiment and the model have
of filler reduces this property.
Fig. 10 shows the contour chart of the hardness. It seems
moving down the chart which has lower absolute difference of
CPVC and PVC improves the hardness of the paint. So the model
confirms better quality when working at CPVC.
Fig. 11 exhibits the estimated price curve based on feed com-
position for producing 1 kg paint. The figure shows lower price
estimation when working at high composition of filler.
In the other part of the experimental design using DX6 pack-
age, the optimization process was applied to attain the optimum
formula region. Permitted range of properties for presented
model was defined regarding to the minimum CPVC, PVC dif-
ference and required end-use properties. The range of input
variations is indicated in Table 4. After running the program,
results are derived in Fig. 12 which shows a colored limited
region within the limited contours.

Table 4
Selected range of optimized paint properties
Property Range

Taber abrasion (mg) ≤85

Hardness (N) ≥8
No pick up time (min) ≤18
Gloss (%) ≥3
|LCPVC − PVC| (%) <2
PVC (%) >58
Fig. 11. Price (US$/kg).
 S. Fatemi et al. / Progress in Organic Coatings 55 (2006) 337–344 343

Table 5
Comparison of the results obtained from experiment and statistical model
Property LPVC (%) − PVC (%) Taber (mg) Gloss (%) Hardness (N) No pick up time (min) Drying time (min) Price (US$/kg)

Exp. 1.4 77 3 9 15 13 1.5

Model 1.32 78.58 3.14 8.5 15.75 13.89 1.54
ARD (%) 5.7 2 4.7 5.5 5 6.4 2.7

Fig. 14. Comparing properties of optimized paint with commercial solvent-

based paint.

been compared with each other and absolute relative deviation

is determined as follows:
| exp . − mod.|
ARD =
exp .
The results of comparison between the model and experi-
ments show that present statistical model can predict properties
of the new samples with acceptable accuracy.
Fig. 12. Results of running optimization program in desired ranges. At final stage, the end-use properties of a commercial
solvent-based paint were compared with this optimized paint.
As it is clarified in Fig. 14, the optimized paint showed
acceptable and comparable properties against the solvent-based
paint in sense of abrasion resistance, hardness, gloss, hiding
power, adhesion, density, no pick up time and price. The new-
produced paint is economically competitive with the solvent
based paints currently existing in the market as shown in this
figure.

5. Conclusion

In this study we proposed an optimum formula for production

Fig. 13. Selection of one point from optimized area with model predicted char-
acteristics.
of water-borne traffic paint based on acrylic emulsion resin. The
new paint has the least VOC and is environmentally friendly.
The main properties of this paint are studied: Taber abrasion
resistance, adhesion, hardness, gloss and no pick up time. Dif-
ference of CPVC from PVC is a very important factor to reach
to the high quality. Working at high PVC with least difference
of CPVC is proposed.
On the other hand, formulation and optimization of this paint
was carried out for the first time with a new experimental design
method. In this method the least number of the experiments can
estimate different responses in several levels simultaneously.
This method can offer the optimized region formulation with
appropriate accuracy. The new formulated paint exhibits com-
 344 S. Fatemi et al. / Progress in Organic Coatings 55 (2006) 337–344
petitive quality with respect to the commercial solvent-based
paint.
Acknowledgement
We would like to thank propagation and reconstruction the
Industrial Development and Renovation Organization of Iran,
which has supplied this work from SBDC designs.
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