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Vasile Alecsandri University of Bacau, Faculty of Engineering, Department of Chemical and Food Engineering,
157 Calea Marasesti, 600115 Bacau, Romania
2
Gheorghe Asachi Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection,
Department of Environmental Engineering and Management, 73 Prof.dr.docent D. Mangeron Street, Iasi 700050, Romania
3
Ecole Nationale Suprieure de Chimie de Rennes, CNRS, UMR 6226,
Avenue du Gnral Leclerc, CS 50837, 35700, Rennes Cedex 4
4
European University of Brittany
Abstract
The interest in waterborne paints amelioration increased lately due to the toxicological effect of certain ingredients on human
health, the restrictive environmental legislation and the depletion and escalation in price of raw materials. Research efforts in
formulating waterborne paints are directed to insure low volatile organic compounds (VOCs) emission while maintaining and
even improving their properties.
This paper presents a waterborne paint formulation process. The required main ingredient was an alkydic resin with 51.3 % w/w
non-volatile-matter content, 51.6 mg KOH/g acidity, 8.5 pH, 80 s flow time. Aiming the highest values for paint viscosity,
elasticity and hardness and the lowest VOCs emission, the optimal composition concerning the resin neutralization, type and
amounts of neutralization agents, co-solvents and water were determined by Response Surface Methodology (RSM). As
consequence, the resin was neutralized with a mixture of ammonia and triethylamine in 1:1.8 ratio and solubilized with butanol
and butyl glycol co-solvents (2.8:1 ratio). Pigments and filling material were used in a 2.6:1 ratio reported at resin content. The
final product can be described as a homogenous, viscos fluid, with 152 s flow time and 22.5% VOCs content. In the optimized
drying conditions, it formed a film with a fineness of 40 m, a semi-gloss aspect, a good adherence, an elasticity (after 7 days) of
5.5 mm and a hardness of 45, 93 and 104 s (after 24 h, 3 and 7 days respectively).
Key words: alkyd resin, enamel, mathematical optimization, primer, waterborne paint
Received: November, 2014; Revised final: February, 2015; Accepted: February, 2015
1. Introduction
In recent decades, conventional paints are
more and more replaced by environmentally friendly
formulas (Broek, 1993; Traumann et al., 2014)
whose use is recommended due to ecological
considerations, specifically the reduction of VOCs
emissions) (Tucaliuc, 2014) and economic aspects
(low volumes of organic solvents which tend to have
a limited availability and are expensive). This type of
paints includes powder, high-solids, polyurethanes,
Author to whom all correspondence should be addressed: e-mail: lgavrila@ub.ro; Phone: +40 234 524 411 ext. 145; Fax: +40 234 580 170
278
Required
amounts, %
5-60
15-35
0-40
0.05-1.5
0.02-5
0-4
0-4
0-20
0-20
15-40
Development and optimization of water based paint formula in order to reduce VOCs emissions
Amine amount M a A R
(1)
56100
nY
A0
Ai n X i n
i1
Aii n Xi2 n
i1
A X X
ij n i n
i1 ji1
(3)
Table 2. Code and level of independent variables chosen for the 1st RSM optimization
Symbol
Variables
Percentage of alkyd resin neutralization, %
Co-solvent, % w/w
Deionized water (including water from NH3 solution 25% w/w), % w/w
Coded
Uncoded
x1
x2
x3
X1
X2
X3
Levels
-1
0
1
Actual values
60
70
80
15
20
25
20
25
30
Xi
10
5
5
Table 3. Code and level of independent variable chosen for the 2nd RSM optimization
Symbol
Variables
Coded
Uncoded
x1
X1
x2
X2
Deionized water (including water from NH3 solution 25% w/w), % w/w
x3
X3
Levels
0
1
Actual values
1/1.5
1/2
1/3
(0.33) (0.50) (0.66)
1/3.3
1/2.6
1/2
(0.3)
(0.4)
(0.5)
25
27
29
-1
Xi
0.16
0.1
2
279
Table 4. Tests applied for developed paints, primers, intermediate paints and enamels
Test
Determination of flow time by use of
flow cups
Determination of fineness of grind
Determination of water content
Determination of non-volatile-matter
content
Determination of VOCs content
Determination of hardness
Drying test
Environmental testing
Reference method
ISO 2431 (2012)
ISO 1524 (2013)
ISO 760 (1994)
ISO 3251 (2008)
ISO 11890-1
(2007a)
ISO 1522 (2007b)
Cross-cut test
280
Apparatus used
Viscosity cups (ISO 2431; = 4 mm and 5 mm) (Multilab,
Romania)
Grindometer ZGR 2024 (Rom Tech, Romania)
Air oven POL-EKO STD (Nitech, Romania)
Pendulum hardness tester type 707KP (Inspiratech 2000 Ltd.,
England)
Ballotini glass pearls (CDS Consultants, England)
Digital Coating Thickness Gauge (Elcometer Instruments
GmbH, Germany)
Cross Hatch Cutter (Paint Test Equipment, England)
Development and optimization of water based paint formula in order to reduce VOCs emissions
Characteristics
Amino resin
Luwipal LR 8334
Melarom 31
Urezit 80
Alkyd resin and amino resin ratio
9/1
10/1
9/1
viscous homogenous liquid
Alkyd resin
Appearance
Drying time at 20 C
- at dust, min
- type C, h
Persoz hardness1, s
- after 24 h
- after 3 days
- after 7 days
Resistance to water immersion2, 24 h
60
24
60
24
60
24
60
24
43
68
75
slightly matted
34
58
65
30
54
60
27
45
50
matted
slightly matted
determined on films applied with hand-drawn scraper, on glass plates, of 120 m wet thicknesses; 2films sprayed on samples covered with
primer based on the same binder as the applied paint
Table 6. 1st RSM test for paint formulation and the observed and predicted values for viscosity, hardness and VOCs
Run
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Neutr. agent
(NH3)1
% w.
g
n.r.3
60
0.94
60
0.94
60
0.94
60
0.94
60
0.94
60
0.94
60
0.94
60
0.94
60
0.94
70
1.10
70
1.10
70
1.10
70
1.10
70
1.10
70
1.10
70
1.10
70
1.10
70
1.10
80
1.25
80
1.25
80
1.25
80
1.25
80
1.25
80
1.25
80
1.25
80
1.25
80
1.25
Co-solvent
(BuOH)
% w.
g
mix4
15
23.29
15
25.23
15
27.53
20
33.65
20
36.71
20
40.38
25
45.88
25
50.47
25
56.08
15
23.33
15
25.27
15
27.57
20
33.70
20
36.76
20
40.44
25
45.95
25
50.55
25
56.16
15
23.37
15
25.31
15
27.61
20
33.75
20
36.82
20
40.50
25
46.02
25
50.63
25
56.25
Water2
% w.
mix
20
25
30
20
25
30
20
25
30
20
25
30
20
25
30
20
25
30
20
25
30
20
25
30
20
25
30
g
31.06
42.06
55.06
33.65
45.88
60.56
36.71
50.47
67.29
31.11
42.12
55.14
33.70
45.95
60.66
36.76
50.55
67.40
31.15
42.19
55.23
33.75
46.02
60.75
36.82
50.63
67.50
Viscosity,
s
Obs.5
Pred.6
% (w/w)
1476.1
148
1445.2
141
1383.2
141
1395.5
140
1334.9
133
1343.3
132
1213.2
119
1091.7
112
1114.8
111
1455.3
147
1448.1
140
1375.5
140
1365.5
139
1336.8
133
1354.6
132
1218.4
119
1105.7
112
1109.2
111
1464.1
146
1447.0
140
1373.2
140
1386.8
139
1314.7
133
1335.6
132
1225.4
119
1082.9
112
1131.1
111
Persoz hardness,
s
Obs.
Pred.
% (w/w)
1075.5
107
1053.7
105
1017.1
101
1091.6
109
1082.1
108
1062.4
105
1074.3
107
1063.3
106
1044.8
104
1121.0
112
1103.8
110
1063.1
106
1135.0
114
1120.9
112
1094.4
110
1122.5
111
1112.7
111
1092.6
109
1124.1
112
1103.2
110
1060.8
106
1142.4
114
1133.0
113
1116.6
110
1126.8
112
1112.1
111
1093.6
109
VOCs,
%
Obs.
Pred.
2%
17.21
17.13
17.10
17.05
17.07
17.13
22.63
22.61
22.58
22.61
22.50
22.76
28.10
28.17
28.00
28.25
28.99
28.48
17.26
17.31
17.22
17.14
17.17
17.12
22.76
22.68
22.66
22.59
22.59
22.65
28.20
28.13
28.13
28.12
28.00
28.25
17.40
17.62
17.38
17.36
17.29
17.24
22.99
22.88
22.72
22.69
22.70
22.66
28.22
28.22
28.12
28.11
28.11
28.15
25% aqueous NH3 solution; 2total amount of water (incorporating water from the NH3 solution); 3% w. n.r. - percentage of neutralized resin;
mix. - total amount of tested paint; 5Obs. - observed value; 6Pred. - predicted value
1y
(4)
0.0633 x12
0.0393 x 22
0.0763 x32
(5)
(6)
281
Equation 4
2.903
0.967
0.950
0.916
368.042
20.93
Equation 5
0.511
0.983
0.974
0.960
10.593
41.00
Equation 6
0.184
0.999
0.998
0.996
1.928
102.02
Equation 7
0.11
0.951
0.925
0.854
0.573
18.52
Equation 8
1.6
0.964
0.945
0.901
124.969
26.29
Equation 9
0.106
0.741
0.604
0.348
0.485
4.31
282
Equation 4
< 0.01
74.7
< 0.01
< 0.01
77.8
< 0.01
2.74
69.7
91.9
69.7
Equation 5
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
0.300
100.0
100.0
0.0112
Significance, p %
Equation 6
Equation 7
< 0.01
< 0.01
35.1
< 0.01
< 0.01
0.262
66.2
0.166
41.8
0.0389
61.1
2.00
32.6
38.9
4.96
100.0
9.0
60.2
16.3
60.2
Equation 8
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
4.28
42.1
0.779
3.30
0.540
Equation 9
< 0.01
0.193
68.1
0.0105
62.1
3.72
40.8
21.7
31.8
74.7
Development and optimization of water based paint formula in order to reduce VOCs emissions
Desirability, %
Viscosity, s
Hardness at 7 days, s
VOCs, %
3rd
0.214147
0.210315
0.627537
Factor
Percentage of neutralized alkyd resin
Co-solvent
Water
1st
128.22
110.58
23.79
98.64
1st
67
21
27
Value
2nd
127.99
110.75
23.83
95.39
Real value
2nd
3rd
68
72
21
21
27
28
3rd
128.00
111.42
23.77
95.82
Fig. 1. 3D response surface plots for the 1st process of paint formulation optimization
283
(7)
y 88.9 6.15 x1 3.35 x 2 2.95 x3 1.45 x1 5 x2
(8)
6
(9)
For these equations, the registered R2 and adj.
R (Table 7) were between 0.741 and 0.951 and
between 0.604 and 0.925 respectively. The predicted
R2 and adjusted R2 in this study indicate that only
7.5, 5.5 and 39.6% respectively of total variations
could not be explained by the models. Their values
and Adeq. Precision reveal an acceptable degree of
accuracy for the behavior of the obtained
2
Table 10. RSM test for intermediary paint formulation and the observed and predicted values
for elasticity, hardness and VOCs
Run
Neutralization
agent
25%NH3/Et3N
ratio
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
1
1/5
1/5
1/5
1/5
1/5
1/5
1/5
1/5
1/5
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/3
1/3
1/3
1/3
1/3
1/3
1/3
1/3
1/3
Co-solvent
BG/BuOH
ratio
5.74
5.74
5.74
5.74
5.74
5.74
5.74
5.74
5.74
5.91
5.91
5.91
5.91
5.91
5.91
5.91
5.91
5.91
6.10
6.10
6.10
6.10
6.10
6.10
6.10
6.10
6.10
1/3.3
1/3.3
1/3.3
1/2.6
1/2.6
1/2.6
1/2.0
1/2.0
1/2.0
1/3.3
1/3.3
1/3.3
1/2.6
1/2.6
1/2.6
1/2.0
1/2.0
1/2.0
1/3.3
1/3.3
1/3.3
1/2.6
1/2.6
1/2.6
1/2.0
1/2.0
1/2.0
41.12
42.70
44.41
41.12
42.70
44.41
41.12
42.70
44.41
41.19
42.77
44.48
41.19
42.77
44.48
41.19
42.77
44.48
41.26
42.85
44.56
41.26
42.85
44.56
41.26
42.85
44.56
Elasticity,
mm
Water1
% w.
mix2
25
27
29
25
27
29
25
27
29
25
27
29
25
27
29
25
27
29
25
27
29
25
27
29
25
27
29
g
48.95
54.90
61.33
48.95
54.90
61.33
48.95
54.90
61.33
49.03
54.99
61.43
49.03
54.99
61.43
49.03
54.99
61.43
49.12
55.09
61.54
49.12
55.09
61.54
49.12
55.09
61.54
Obs.3
% (w/w)
4.52.0
4.50.6
4.71.1
4.61.1
4.60.3
4.72.4
4.51.2
4.70.7
4.70.6
4.90.9
4.90.1
5.10.4
5.10.2
5.30.6
5.40.2
5.31.4
5.30.7
5.50.6
5.20.6
5.30.6
5.60.2
5.50.1
5.50.6
5.60.9
5.30.3
5.50.3
5.51.4
Pred.4
4.4
4.5
4.6
4.6
4.7
4.8
4.6
4.6
4.7
5.0
5.1
5.2
5.2
5.3
5.4
5.2
5.3
5.4
5.2
5.3
5.5
5.4
5.5
5.6
5.4
5.5
5.6
Persoz hardness,
s
Obs.
% (w/w)
1113.8
1073.7
982.9
1011.9
982.2
951.5
993.7
971.1
955.1
992.5
950.8
902.1
911.6
891.1
842.7
873.3
863.3
842.6
913.3
893.8
870.6
912.7
896.2
863.3
871.5
862.1
861.1
Pred.
111
106
100
103
100
95
98
96
93
98
94
89
91
89
85
88
87
85
94
91
87
89
87
85
87
87
86
VOCs,
%
Obs.
2%
24.10
23.88
23.80
24.00
23.81
23.75
23.89
23.90
23.80
24.10
24.00
23.88
23.92
23.70
23.88
24.30
23.87
23.91
24.20
24.10
23.83
24.25
23.91
23.89
24.20
24.30
23.91
Pred.
24.06
23.92
23.85
23.93
23.79
23.73
23.98
23.86
23.81
24.12
23.95
23.85
24.03
23.86
23.77
24.13
23.97
23.89
24.23
24.02
23.89
24.17
23.98
23.85
24.31
24.12
24.01
total amount of water (water from NH3 solution included); 2mix. - total amount of tested paint; 3Obs. - observed value; 4Pred. - predicted value
284
Development and optimization of water based paint formula in order to reduce VOCs emissions
Fig. 2. 3D response surface plots for the 2nd process of paint formulation optimization
285
Table 11. Optimized process variables and related response functions values
Maximum coordinates
Variable
X1
X2
X3
1st
1.202349
-0.785468
-0.256345
Coded value
2nd
-0.514089
0.316674
0.316809
Factor
3rd
-0.407585
Neutralization agent ratio
0.505326
Co-solvent ratio
-0.295560
Water
Maximum characteristics
Response function
1Y
2Y
3Y
Elasticity, mm
Hardness at 7 days, s
VOC, %
Desirability, %
1st
5.3
91
24.07
100.00
1st
0.69
0.3
26
Real value
2nd
3rd
0.42 0.43
0.4
0.5
28
26
Value
2nd
3rd
5.1
91
23.76
100.00
5.1
91
23.85
100.00
286
Development and optimization of water based paint formula in order to reduce VOCs emissions
Ingredients
Pigment dispersion phase
Water thinnable alkyd resin
Neutralization agent, NH3 (25% in water)/Et3N = 1/1.8
Butanol
Butyl glycol
Red iron oxide
Molybdenum orange
Manganese dryer (Mn 5% in solvent system)
Zinc dryer (Zn 10% in solvent system)
Extender, CaCO3
Talc
Deionized water
Completion phase
Water thinnable alkyd resin
Neutralization agent, NH3 (25% in water)/Et3N = 1/1.8
Deionized water
64.50% solids, 27% water, 164.52 g/L VOC, density 1960 20 kg/m3
19.87
0.22
5.95
2.13
10.00
7.50
0.13
0.13
5.50
3.04
7.55
18.34
0.20
19.41
White topcoat
Red topcoat
Liquid product
viscous homogenous liquid
190
197
30-35
Film product
semi-glossy
60
24
6
60
24
6
good
35
69
45
72
slightly matted
no modification
287
288