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A new study on binder performance and formulation modification of anti-

corrosive primer based on ethyl silicate resin

Article  in  Progress in Organic Coatings · February 2009

DOI: 10.1016/j.porgcoat.2009.02.006

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 Progress in Organic Coatings 65 (2009) 410–413

Contents lists available at ScienceDirect

Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Short communication

A new study on binder performance and formulation modification of

anti-corrosive primer based on ethyl silicate resin
Faegheh Hoshyargar a , S. Ali Sherafati b , Mohammed M. Hashemi a,∗
a
Department of Chemistry, Sharif University of Technology, P.O. Box 11365-9516, Tehran, Iran
b
Research and Development Laboratory, Arash Rang Company, P.O. Box 33616-55719, Hashtgerd Industrial Zone, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Zinc-rich ethyl silicate coatings are quite successful in protecting steel against corrosion under severe
Received 11 October 2008 exposing conditions. In spite of providing excellent cathodic protection to steel structure after film curing,
Received in revised form 7 February 2009 two-component zinc-rich ethyl silicate coatings have some limitations, one of which is inadequate shelf
Accepted 27 February 2009
life as a result of in-can binder gelation.
In this work, the preparation steps of ethyl silicate such as pre-hydrolysis, dehydration and organometal-
Keywords:
lic reactions were surveyed and herein an approach towards understanding the cause and effect
Ethyl silicate binders
relationship of the use of ingredients is presented. The effects of water and catalytic acid dosages on gel
Zinc-rich ethyl silicate primer
Pre-hydrolysis
time under accelerated conditions and the effect of alcoholic solvent order on the rate of the hydrolysis and
Partial hydrolysis dehydration reactions were studied via Karl-Fischer test determining the water content of hydrolysate.
Gel time A thriving optimization in shelf life without any loss in physical–mechanical characteristics of the final
Shelf life film (e.g. hardness, adhesion, solvent and salt spray resistance) was obtained.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction corresponding produced alcohol [13] are discussed in the litera-

Many different methods have been developed for protecting
iron and steel against rusting among which, utilizing sacrificial
zinc is the most effective and practical method [1]. Elemental zinc
can be introduced within an organic or inorganic coating in dust
form. Comparing to organic zinc-rich coatings, inorganic ones have
numerous advantages and disadvantages [2]. Among the advan-
tages, inorganic zinc-rich coatings are high-temperature resistant
[3].
Among alkyl silicate binders, ethyl silicate is the most popular
and easiest-to-use choice. General structure of ethyl silicate resin
contains a polyethoxy siloxane with 1–9 Si atoms per molecule and
average formula of Si(OC2 H5 )2.33 O0.835 as shown in Scheme 1.
Since ethyl silicate has no binding ability [4], it is necessary
to hydrolyze it in order to provide such characteristic. Water is
the counterpart reactant in hydrolysis and the final product is
a hydrolysate which is the actual reactive agent in the follow-
ing reactions [5]. Acids and alkalis are both adequate catalysts to
hydrolyze ethyl silicate. Acidic condition would result in a prod-
uct which is used as paint media [6–8]. Hydrolysis of ethyl silicate
[3,9,10] and governing factors such as quantity of water, quan-
tity of acid [11], size and type of alkyl group [12] and, therefore,
ture.
By providing sufficient quantity of water, the condensation reac-
tion reaches to gel phase. Thus, normally 80–90% of required water
for complete hydrolysis is added to the blend [14] and it is kept
in sealed cans away from water or humidity, until the application
time when pre-hydrolyzed solution is mixed to zinc powder. Also, if
dehydration reaction exceeds a certain proportion (even with con-
trolled dosage of water), the solution goes to gel phase. Hence the
initial composition of pack A should be formulated carefully in a
way that the reaction slows down and, subsequently, a satisfactory
shelf life for binder is obtained.
Total hydrolysis of pure ethyl silicate can be given as shown in
Eq. (1):
Si(OEt)4 + 2H2 O → SiO2 + 4EtOH (1)
whereas ethyl silicate hydrolyzed to ‘x’ degree is illustrated by Eq.
(2) [3]:
Si(OEt)4 + 2xH2 O → SiO2x (OEt)4(1−x) + 4xEtOH (2)

Binder is prepared according to Table 1.

Further information about mechanism of condensation of alkyl
∗ Corresponding author. Tel.: +98 21 66165313; fax: +98 21 66005718. silicates and film curing of zinc silicate coatings can be found in the
E-mail address: mhashemi@sharif.edu (M.M. Hashemi). literature [3,15].

0300-9440/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2009.02.006
 F. Hoshyargar et al. / Progress in Organic Coatings 65 (2009) 410–413 411

Scheme 1. Structure of commercial ethyl polysilicate (TES-40), n = 1–9.

Table 1
Specifications of ethyl silicate binder.

S. no. Ingredient Quantity

1 Ethyl polysilicate 6000/S1 a or 208 − 1.48 H1 b

2 Water 0.36 (H2 c − H1 )
3 Solvent 6000/S2 d − ESe − Wf Fig. 2. Influence of water quantity on viscosity of binder in accelerated conditions
a (55 ◦ C).
% SiO2 in ethyl polysilicate.
b
% hydrolysis in ethyl polysilicate.
c Table 2
% hydrolysis desired.
d
Ethyl silicate binder composition (quantity of HCl modified).
% SiO2 desired.
e
Weight of ethyl polysilicate. S. no. Ingredient Amount (%)
f
Weight of water.
Blank Sample 1 Sample 2

1 Distilled water 4.06 4.092 4.1

2. Experimental 2 Isopropyl alcohol 44.2 44.2 44.2
3 Aromatic solvent 14.1 14.1 14.1
2.1. Materials 4 Auxiliary resin 3.4 3.4 3.4
5 TES-40 34.2 34.2 34.2
6 HCl 37% 0.04 0.008 –
Ethyl silicate-40 (TES-40) purchased from Wacker, auxiliary
100 100 100
resin from Clarient, alcoholic solvents from Bidestan Co., aromatic
solvent from Iran petrochemical Commercial Co., HCl 37% from Gha-
tran Shimi Co. and laboratorial grade distilled water were used. gel time from 28 days to 43 days whereas decreasing its amount
would not sensibly change the gel time.
2.2. Instruments
3.2. The effect of water quantity on gel time
AFNOR Cup # 2.5 (Sheen) and Carl-Fischer Apparatus 684 KF
Coulometer (Metrohm) were used. As calculations show, the quantity of water in blank advances
the hydrolysis reaction to 89.9%. This is believed to be too much
2.3. Binder synthesis and, thus, samples 3 and 4 were prepared, with amounts of water
calculated for 85% and 80% partial hydrolysis, respectively (Table 3).
Auxiliary resin was dissolved in alcohol and stirred for 30 min. Fig. 2 shows changes in viscosity in accelerated conditions.
TES-40 and aromatic solvent were then added and agitated. The As observed in Fig. 2, gel time of sample 4 (80% hydrolysis)
mixture of distilled water and hydrochloric acid calculated for par- has distinctly increased. Two-pack zinc-rich ethyl silicate coat-
tially hydrolysis of ethyl silicate is added dropwise and then agitated ing obtained with this binder (Table 4), did not show neither
until the exothermic reaction subsides. physical–mechanical nor chemical loss as shown in Table 5.

3. Results and discussion 3.3. The effect of alcoholic solvent order on the rate of hydrolysis

3.1. The effect of acid quantity on gel time
Three samples were prepared with different amounts of acid and
their viscosity was measured using AFNOR cup # 2.5 in different
times (Table 2). As Fig. 1 shows, omitting acid would increase the
The mass balance for water, Htotal , equals to the initially added
water, Hinitial , minus the water consumed in hydrolysis reac-
tion, Hhydrolysis , plus water produced in condensation reaction,

Fig. 1. Influence of acid quantity on viscosity of binder in accelerated conditions Fig. 3. Influence of water concentration, Htotal , on hydrolysis rate monitored by Karl-
(55 ◦ C). Fischer test in early minutes.
412 F. Hoshyargar et al. / Progress in Organic Coatings 65 (2009) 410–413

Table 3 Table 6
Ethyl silicate binder composition (quantity of H2 O modified). Ethyl silicate binder composition (quantity of alcoholic solvent modified).

S. no. Ingredient Amount (%) S. no. Ingredient Amount (%)

Blank Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8

1 Distilled water 4.06 3.65 3.23 1 Methyl alcohol 44.2

2 Isopropyl alcohol 44.2 44.2 44.2 2 Ethyl alcohol 44.2
3 Aromatic solvent 14.1 14.51 14.93 3 Isopropyl alcohol 44.2
4 Auxiliary resin 3.4 3.4 3.4 4 Isobutyl alcohol 44.2
5 TES-40 34.2 34.2 34.2 5 Aromatic solvent 14.1 14.1 14.1 14.1
6 HCl 37% 0.04 0.04 0.04 6 Auxiliary resin 3.4 3.4 3.4 3.4
7 TES-40 34.2 34.2 34.2 34.2
100 100 100
8 1% solution of HCl 4.1 4.1 4.1 4.1

100 100 100 100

Table 4
Specifications of sample 4 (mixing ratio pack A/pack B = 1/2.55).

S. no. Ingredient Amount (%)

Pack A Pack B Total

1 Distilled water 3.23 – 0.91

2 Isopropyl alcohol 44.2 – 12.45
3 Aromatic solvent 14.93 – 4.2
4 Auxiliary resin 3.4 – 0.96
5 TES-40 34.2 – 9.63
6 HCl 37% 0.04 – 0.011
7 Zinc dust – 91 65.37
8 Mica – 9 6.47

100 100 100

Hcondensation : Fig. 4. Influence of water concentration, Htotal , on hydrolysis rate monitored by Karl-
Fischer test after 4 days.
Htotal = Hinitial − Hhydrolysis + Hcondensation (3)
4. Conclusion
Moreover, the concentration of produced ethyl alcohol in hydrolysis
reaction, Atotal , is equivalent to consumed water, Hhydrolysis :
The rate of hydrolysis reaction of ethyl silicate in acidic condi-
tions depends both on the concentration of H3 O+ and concentration
46
Atotal = H
18.01 hydrolysis
(4) of alkoxides. The mechanism is consequently SE2 and steric strain
is therefore an important factor. That is why changing the alcoholic
It is theoretically possible to measure the reaction rate, the solvent (primary to secondary and tertiary) alters water consump-
monomer conversion degree (condensation progression) and the tion and the reaction rate. Water/alkoxide and acid/ethyl silicate
average structure of final polyethoxy siloxane by measuring Htotal resin weight ratios are of great importance.
and Atotal . The reaction rate in primary alcohol without side chains (methyl
Different alcohols such as methyl, ethyl, isopropyl and isobutyl and ethyl alcohol) would be higher than that of primary alcohol
alcohol were used to prepare samples 5–8 (Table 6) and the Htotal with side chains having steric effect (isobutyl alcohol) and much
value was measured by Karl-Fischer test at different times in early higher than secondary alcohol (isopropyl alcohol).
minutes (Fig. 3) and after 4 days (Fig. 4). The shelf life of silicate binder was enhanced decreasing the
Comparing data in Figs. 3 and 4 shows the completion of hydrol- water/alkoxide ratio. The optimum water amount is adequate for
ysis reaction in early minutes as the reaction starts by addition of 80% progression of hydrolysis reaction.
1% solution of HCl. Under these conditions, the ethyl silicate binder is ready to be
used after 4 h rather than 24 h which is recommended by most of
the manufacturers.
Table 5
Results of physical–mechanical and chemical tests for sample 4.
Acknowledgements
Test name Measuring Standard Result Options
unit
We are grateful to P. Rooshenas (Arash Rang’s R&D Department)
Hardness (Persoz) s ASTM D4366 210 16 h cured in and H. Raghami for their helpful discussions. We would also like
[16] Benmary bath to thank Prof. M. Ghandi and Mr. Hamzehlou from the University
Hardness (Persoz) s ASTM D4366 140 1 week cured
[16] in ambient
of Tehran for access to laboratorial equipments and Karl-Fischer
temperature apparatus. This work was performed as a part of dissertation thesis
Adhesion (cross cut) Visual ASTM D3359 4B – of F.H.
standard [17]
Solvent resistance 50 double ASTM D4752 4a DFT = 50–75 ␮
(MEK Rub) rub [18] References
Salt spray resistance hb ASTM B117 2060 –

[19] [1] G.M. Charles, SSPC Painting Manual (2002) 125–137.

[2] N. Karakasch, Corrosion Management, Zinc Coating Review—2000 and beyond,
a
Very slight polishing. May 2001.
b [3] G. Parashar, D. Strivasta, P. Kumar, Prog. Org. Coat. 42 (2001) 1–14.
Time necessary for appearance of red corrosion in scratch.
 F. Hoshyargar et al. / Progress in Organic Coatings 65 (2009) 410–413 413

[4] H.F. Payne, Organic Coating Technology, vol. 1, Wiley, New York, 1964, p. 594. [13] A.F. Trotman-Dickinson, E.G. Rochow, Comprehensive Inorganic Chemistry
[5] H.G. Emblem, Res. Ind. 23 (12) (1978) 207. Chapter XV: Chemistry of Silica, Pergamon Press, New York, 1973.
[6] H.D. Cogan, C.A. Sellerstrom, Ind. Eng. Chem. 67 (1947) 1364. [14] S. Mukherjee, Paintindia 49 (7) (1999) 31.
[7] R.K. Iler, The Colloidal Chemistry of Silica and Silicates, Cornel University Press, [15] O.C.C.A. Australia, Surface Coatings, vol. 2, Chapman & Hall, New York, 1984, p.
Ithaca, NY, 1955. 484.
[8] G.H. Emblem, Fridry Trade J. 132 (1975) 1364. [16] ASTM D4366, Hardness of Organic Coatings by Pendulum Damping Tests, ASTM,
[9] C.P. Alain, Introduction to Sol–Gel Processing, Kluwer Academic Publishers, 1995.
Boston, 1998. [17] ASTM D3359, Measuring Adhesion by Tape Test, ASTM, 1995.
[10] British Patent No. 1,292,938 (1972), to Anderson Development Co.; Chem. Abstr. [18] ASTM D4752, Measuring MEK Resistance of Ethyl Silicate (Inorganic) Zinc-rich
77 (1972) 36575v. Primers by Solvent Rub, ASTM, 1987.
[11] R.S. James, Mod. Paint Coat. 6 (1983) 48. [19] ASTM B117, Operating Salt Spray (Fog) Apparatus, ASTM, 1997.
[12] T. Ginsberg, I.G. Kaufman, Mod. Paint Coat. 10 (1981) 138.

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