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Parashar2001 PDF
Parashar2001 PDF
Review
Ethyl silicate binders for high performance coatings
Geeta Parashar a , Deepak Srivastava b , Pramod Kumar a,∗
a Department of Oil and Paint Technology, H.B. Technical Institute, Kanpur 208 002, India
b Department of Plastic Technology, H.B. Technical Institute, Kanpur 208 002, India
Abstract
Surface coatings based on ethyl silicate binders are categorised as inorganic coatings, whereas the conventional surface coatings which
are mainly based on organic binders are referred to as organic coatings. Zinc-rich inorganic coatings based on ethyl silicate are quite
successful for the protection of steel against corrosion under severe exposing conditions such as underground, marine atmosphere, indus-
trial atmosphere, nuclear power plants, etc. These coatings provide unmatched corrosion protection to steel substrates exposed to high
temperatures. Because of the formation of conductive matrix out of the binder after film curing, zinc-rich coatings based on ethyl silicate
binder offer outstanding cathodic protection to steel structures. These coatings are mostly solvent-borne, but recently water-borne versions
of the same have also been developed. However, the commercial success of water-borne systems is not yet well established.
In the present article, the processes of hydrolysis of ethyl silicate in the presence of acidic and alkaline catalysts have been elaborated to
produce ethyl silicate hydrolysates of desired degree of hydrolysis. Effect of various factors such as amount of catalysts, amount of water,
type and amount of solvent, reaction temperature and reaction time has been discussed. Calculations to find out the amount of water and
solvent required to yield the product of desired degree of hydrolysis have also been illustrated. Typical recipes useful for the preparation
of ethyl silicate hydrolysates suitable for use as coating binders have also been presented. The chemistry and mechanism involved in
the preparation of binder and the curing of film has also been discussed. This article also summarises the effect of various factors, viz.
particle size and shape of zinc pigment, presence of extenders in the formulations, and the application technique on film performance.
© 2001 Elsevier Science B.V. All rights reserved.
Keywords: Inorganic coatings; Silicate binders; Ethyl silicate coatings; Zinc silicate coatings; Heat resistant coatings; Anticorrosive coatings
0300-9440/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 0 - 9 4 4 0 ( 0 1 ) 0 0 1 2 8 - X
2 G. Parashar et al. / Progress in Organic Coatings 42 (2001) 1–14
adjacent zinc particles, and between the zinc particles in the 2.1. Alkali metal silicate binders
film and the steel substrate is required [3].
In the case of zinc-rich ‘organic’ coating films, zinc par- For the manufacture of coatings based on alkali metal
ticles can be encapsulated by the organic binder, and hence silicates, the silicates based on alkali metals such as
the zinc particles have restricted electrical contact. Conse- sodium, potassium and lithium, along with the quarternary
quently, the zinc particles can provide only a small amount ammonium silicates have been reported to be suitable
of galvanic protection limited to the amount of free zinc in [8]. Alkali metal silicates are relatively simple chemi-
the coating formulation [4]. cals, which can be water soluble depending on the ratio
On the other hand, in the zinc-rich ‘inorganic’ coatings of silica to alkali metal oxide. The ratios of silica to
(commonly referred to as zinc silicate coatings), the binders alkali metal oxide of different silicates [8], which can
(inorganic) used are alkali silicates and alkyl silicates, which be used as binder systems in paints, have been given in
can chemically react with the zinc particles in the coating Table 1.
film to form a zinc silicate matrix around the zinc particles The ratio of silica to alkali metal oxide, in addition to the
[5]. This zinc silicate matrix is electrically conductive and type of alkali metal, has a remarkable effect on curing char-
chemically inert [2]. In addition, the silicate based binders acteristics and properties of the dried films [9]. The effect of
can chemically react with the steel substrate also to result in ratio of silica to alkali metal oxide on coating characteristics
an excellent adhesion and abrasion resistance of the dried/ has been shown in Table 2.
cured film [6]. The coatings based on alkali metal silicates having sili-
Inorganic zinc silicate coatings are included in the cat- ca to alkali metal oxide varying from 2.1:1 to 8.5:1 are
egory of high performance coatings [7], as these are the water-borne due to solubility of the used alkali metal oxide
most weather resistant coatings available today [5]. They in water. These coatings are generally sub-classified into
can provide an unmatched protection against corrosion for baked, post-cured and self-cured coatings.
steel structures exposed to temperatures up to 400◦ C [2].
2.1.1. Baked coatings
These are the coatings which require heating to convert the
2. Silicate binders for inorganic paint coatings coating films into water insoluble form. These coatings are
characterised by their extreme hardness and suitability for
Inorganic paint coatings based on silicate binders can be application over an acid-descaled surface. Baked coatings
classified [6] as shown in Fig. 1. still have limited use today.
Table 1
Ratios of silica to alkali metal oxide in alkali silicates [8]
S. No. Silicate Chemical composition Ratio of silica to
alkali metal oxide
1 Sodium silicate SiO2 :Na2 O 2.4–4.5:1
2 Potassium silicate SiO2 :K2 O 2.1–5.3:1
3 Lithium silicate SiO2 :Li2 O 2.1–8.5:1
G. Parashar et al. / Progress in Organic Coatings 42 (2001) 1–14 3
Table 2
Effects of ratio of silica to alkali metal oxide on coating characteristics
S. No. Ratio of silica to alkali metal oxide Effect on coating characteristics
1 Higher Higher the viscosity of the solution
Higher the drying speed of the film
Higher the curing speed of the film
Higher the susceptibility to low temperature
Higher the chemical resistance of the coating films
2 Lower Higher the specific weight of the solution
Higher the solubility in water
Higher the pH value of the solution
Higher the susceptibility to water
Higher the adhesion and binding power
2.1.2. Post-cured coatings conditions, even a small amount of water will cause the
These are the coatings which are cured by the application silicate to gel. To avoid this problem, remedial steps must
of chemicals such as an acid wash just after application of therefore be taken to exclude all water at the manufactur-
the film to convert the film into a water insoluble condition. ing stage, and from the application equipment. If water is
These coatings are formulated mainly on sodium silicate excluded, the liquid component can remain stable for an
having higher ratio of silica to sodium oxide. This develop- indefinite period of time. These coatings are available in the
ment has led to the use of inorganic zinc coatings on large market as single-pack and two-pack systems. In single-pack
field structures. system, amines, which provide hydroxyl ion in the form
which is non-reactive with organic polysilicate until they
2.1.3. Self-cured coatings are exposed to moisture, are used [8].
With further advances in silicate technology, further
higher ratio alkali metal silicates have become available. Of 2.2.2. Acid catalysed coatings
the cheaper types, potassium silicate is preferred. Reliable In these type of coatings, rapid curing may be achieved
self-curing coatings are available today, based on high under most conditions. However, the period over which the
ratio potassium silicates with potassium oxide to silica ra- partially hydrolysed silicate remains stable is limited, and
tio ranging from 1:2 to 1:5.3. If further higher ratios are the product thus has a finite shelf life. Coatings based on
required, and instability is to be avoided, it is necessary to acid catalysed binder are mainly two-component systems,
use lithium silicate with lithium oxide to silica ratio as 1:2 and the liquid component of these coatings gel in a period
to 1:8.5. Lithium silicate based coatings are preferred for of 6–12 months. The problem associated with one-pack
use in food areas. Excellent curing rates can be achieved system of this type is that zinc chemically reacts with the
with some lithium silicates, but their higher cost tends to acid catalyst present in the binder system, due to which pH
restrict their use at the present time. of the system increases, which causes gelling in the con-
tainer. Hydrochloric acid [10–27], sulphuric acid [28,29],
2.2. Alkyl silicate binders phosphoric acid [30], formic acid [31], etc., are the acids
which are used as catalysts.
Alkyl silicates such as ethyl silicate, methyl silicate etc.
can be used as binders for the formulation of solvent-borne
coatings. However, one of the commercial forms of ethyl 3. Hydrolysis of ethyl silicate
silicate (popularly known as ethyl silicate-40) as solution in
organic solvent(s) is most commonly employed. Alkyl sili- Ethyl silicate, by itself, has no binding ability [32]. To
cates, as such, do not have any binding ability but when their introduce binding ability, it is necessary to hydrolyse ethyl
alcoholic solutions are hydrolysed with calculated amount of silicate by treating it with water, so that a gel can form from
water in the presence of acid or alkali catalyst, they acquire the resulting ethyl silicate hydrolysate. The actual binding
sufficient binding ability. On the basis of the type of catalyst agent is this gel [33].
used for the hydrolysis, these coatings can be sub-classified Usually, the hydrolysis of ethyl silicate is carried out
as follows. under alkaline or acidic conditions. Acids or alkalis are
used to catalyse the hydrolysis reaction. Hydrolysis under
2.2.1. Alkali catalysed coatings alkaline conditions normally results in fairly rapid gelation.
For the hydrolysis of ethyl silicate, bases like ammonia, Alkali catalysed hydrolysis procedures are generally pre-
ammonium hydroxide, sodium hydroxide and some amines ferred when ethyl silicate is to be used for the production
are generally used as catalysts [2]. One of the greatest of refractories. Acid hydrolysis procedures are commonly
drawbacks of this system is related to the fact that in basic employed for the production of paint media. Several
4 G. Parashar et al. / Progress in Organic Coatings 42 (2001) 1–14
Table 3
Typical compositions for single stage procedures for the hydrolysis of ethyl silicate
S. No. Quantity of ethyl silicate-40 Quantity of water Quantity of acid Quantity of solvent
1 6l 2l 50 ml concentrated HCl 4 l ethanol
2 1368 parts (by weight) 138 parts (by weight) 0.16 parts (by weight) 12 N HCl 1517 parts ethanol (by weight)
3 1.6 l 100 ml 6 ml 0.1 N HCl 840 ml 640 p industrial methylated sprit
4 45 parts (by weight) 53 parts (by weight) 0.1 part (by weight) 37% aqueous HCl 49.6 parts ethanol (by weight)
procedures for the acid hydrolysis of ethyl silicate are silicate, solvent, acid and water for their preparation. If ethyl
available [34–36]. silicate is treated simultaneously with a glycol monoether
Hydrolysis procedures in which a specified quantity for alcoholysis and water for hydrolysis, a hydrolysate with
of ethyl silicate is added at the start of the reaction are a long shelf life is obtained [48]. This hydrolysate can be
termed as ‘single stage’ procedures, while those in which successfully used as a paint medium. Generally 80–90%
ethyl silicate is added usually after a specified temperature hydrolysis of the ethyl silicate is carried out for the binder
rise or time interval are termed as ‘two-stage’ procedures. preparation [2].
Some two-stage procedures require two types of organic
silicates. Typical compositions for the single stage [37–40] 3.1. Factors governing the formulation of ethyl silicate
and two-stage procedures [37,41,42] taken from the patent binders
literature have been given in Tables 3 and 4, respectively.
Out of many possible ethyl silicate hydrolysis procedures, There are some important factors, which can affect the
one can be considered on its merits. hydrolysis of ethyl silicate and the formulation of ethyl sili-
Mcleod [43] prepared silicate binder system by hydro- cate binders. These factors are discussed hereunder one by
lysing ethyl silicate-40 in butyl cellosolve in the presence one.
of acid catalyst with 5% (part basis) water at 140◦ C. Some
other workers [44–46] also prepared binder systems by using 3.1.1. Effect of quantity of water
pure ethyl silicate or ethyl silicate-40 of different properties. Quantity of water and the quantity of acid catalyst used
Some special procedures include the use of silica aquasol for partial hydrolysis are the most important factors for for-
and the use of titanic acid ester in a two-stage process. If mulating acid catalysed ethyl silicate binder systems. Water
large amount of phosphoric acid is used in the hydrolysis to be used in hydrolysis must be calculated after subtracting
of ethyl silicate, hydrolysates which gel rapidly can be ob- the quantity of water (if any) going into the paint formula-
tained. Conditions for the hydrolysis of ethyl silicate without tion from the extender pigments and the solvents used in the
use of an acid or a base catalyst to obtain binding solutions formulation. Excessive water in the formulation can lead to
have also been established [47]. gelling of the binder system in the cans or very poor applica-
Acid hydrolysates of ethyl silicate eventually set to a gel tion properties and gelling of mixed paints in the application
on standing. The relatively short shelf life of some acid equipment. Less than optimum quantities of water can result
hydrolysed ethyl silicate solutions can cause difficulties in in an uncured film lacking hardness and film integrity [49].
their use. As a result of the development of methods for
preparing ethyl silicate hydrolysates having a long stor- 3.1.2. Effect of quantity of acid
age life, hydrolysed ethyl silicate solutions have become Less than optimum quantity of acid can result in silica
available commercially. These solutions, often referred to precipitation, thus making less silica available for binding
as prehydrolysed ethyl silicate solutions, are of particular than required. Excessive quantity of acid will result in accel-
interest as paint media. erated condensation of silanol with silanol (≡SiOH) groups
Ethyl silicate hydrolysates having a long storage life can or with alkoxy groups (≡SiOR) resulting in reduced shelf
be obtained by careful choice of the proportions of ethyl life of the binder system [49].
Table 4
Typical compositions for two-stage procedures for the hydrolysis of ethyl silicate
S. No. Quantity of ethyl Quantity of water Quantity of acid Quantity of solvent Quantity of alkyl silicate
silicate-40 (first lot) (second lot)
1 14 parts 2.15 parts (by volume) 18 parts concentrated HCl 50 parts 160 p industrial 11 parts ethyl silicate-40
(specific gravity 1.18) methylated spirit
2 6000 parts 2000 parts (by volume) 50 parts concentrated HCl 8000 parts isopropanol 2000 parts methyl silicate
(specific gravity 1.18) (50% SiO2 )
3 340 parts Nil 40 parts 0.1 N HCl 140 parts isopropanol/ 130 parts isopropyl silicate
water azeotrope (38% SiO2 )
G. Parashar et al. / Progress in Organic Coatings 42 (2001) 1–14 5
(1)
(3)
The empirical equation for ethyl silicate hydrolysed to x In order to prepare a binder that is 85% hydrolysed, the
degree of hydrolysis, SiO2x (OC2 H5 )4(1−x) , can be used to weight of water to be added can be calculated by Eq. (11).
derive the equivalent weight of the commercial ethyl polysil-
Weight of water = 0.36(85 − 41.66) = 15.6 kg
icate and its exact degree of hydrolysis. This allows calcu-
lation of the amount of water necessary to give a binder of The amount of solvent that must be added to give a final
any desired percentage hydrolysis. Equivalent weight can silica content of 18% is calculated from Eq. (12).
be obtained by substituting atomic weights in the empirical = ( 6000
18 ) − 146.34 − 15.6 = 171.4 kg
formula.
The solvents that can be used are ethanol, isopropanol,
Equivalent weight ethoxyethanol, ethoxy ethyl acetate or mixture of these. The
= SiO2x (OC2 H5 )4(1−x) = 28 + 16(2x) + 45(4 − 4x) solvent and ethyl silicate are combined and agitated. Water
containing some acid catalyst is added and the mixture is
= 28 + 32x + 180 − 180x = 208 − 148x
then agitated until the exotherm subsides. The binder is ready
or for use after 24 h of preparation.
In general, curing of ethyl silicate involves hydrolytic
Equivalent weight = 208 − 1.48 H (H = %hydrolysis) polycondensation occurring in two steps. The first is
(9) reversible as shown in Eq. (13).
nSi(OC2 H5 )4 + 4nH2 O → nSi(OH)4 + 4nC2 H5 OH (13)
The concentration of SiO2 in the ethyl polysilicate is equal
to In the absence of alcohol, the silicic acid formed under-
Molecular weight of SiO2 × 100 goes polycondensation as given in Eq. (14):
Equivalent weight of ethyl polysilicate nSi(OH)4 → SiO2 + 2nH2 O (14)
or Because Eq. (14) contributes 2 mol of water for each mole
60 × 100 of ethyl silicate, only 2 mol of water are needed for 100%
% SiO2 = (10) hydrolysis of the reactants. Thus according to Eqs. (13) and
208 − 1.48 H
(14), the total water necessary for 100% hydrolysis will rep-
Calculation for the amount of water to be added to one resent 17.36% by weight of the ethyl silicate used. If ethyl
equivalent weight of ethyl polysilicate to prepare a binder silicate-40 is used as the raw material, then for 100% hydrol-
of any desired degree of hydrolysis is given as ysis, 14.5% water by weight of ethyl silicate-40 is required.
Weight of water = 0.36(% hydrolysis desired 3.4. Paint compositions based on ethyl silicate binder
−% hydrolysis in ethyl polysilicate) (11)
For the formulation of paints based on hydrolysed ethyl
The amount of solvent to be added to achieve the desired silicate binder, care should be taken for the selection of
silica content of the binder is determined from the following pigments, because with this binder system, only those pig-
equation: ments are suitable which are chemically inert, non-basic and
not very reactive. Thus lead chromate, strontium chromate,
Weight of solvent to be added mica, talc and zinc dust are some of the pigments which can
6000 be suitable to formulate ethyl silicate based coatings. Partic-
= − weight of ethyl polysilicate
% SiO2 desired ularly good protection against high temperature and rust can
−weight of water added (12) be obtained if zinc dust is used as the pigment. Some typical
formulations of these paint systems are given hereunder:
For example, to prepare 85% hydrolysed binder contain-
ing 18% SiO2 from commercial ethyl silicate containing Formulation 1 [51]
41% SiO2 , calculate the % hydrolysis in the ethyl polysili-
cate from Eq. (10), as below: S. No. Ingredient Amount (%)
6000 1 Ethyl silicate (partially hydrolysed) 20.0
41 =
208 − 1.48(H) 2 Anti-settling agent (Bentone 38) 1.4
H = 41.66 3 Talc 4.0
4 Toluene 5.3
This allows the calculation of the equivalent weight of the 5 Isopropanol 5.3
ethyl polysilicate using Eq. (9). 6 Cellosolve 4.0
7 Zinc dust 60.0
Equivalent weight of ethyl polysilicate
100.0
= 208 − 1.48(41.66) = 146.34
G. Parashar et al. / Progress in Organic Coatings 42 (2001) 1–14 7
protons catalyses the hydrolysis reaction. The mechanism sodium hydroxide, ammonium hydroxide, etc. can effect
then corresponds to an electrophilic substitution in which this type of reaction.
an (H3 O)+ hydronium ion attacks the oxygen of one of the The silanol group (≡SiOH) resulting from the hydrolysis
alkyl groups. of silicon alkoxide can be converted to oxo ligand. For this
In the intermediary complex of this mechanism, the reaction, base is a necessary catalyser, and the reaction can
coordination number of Si increases. The rate of reaction be as given hereunder:
depends as much on the concentration of H3 O+ as on the
one of the alkoxides. The mechanism is consequently an
SE2 , and steric strain is also an important factor. The rate of
hydrolysis decreases as the length of alkyl group increases.
The reaction mechanism is as given below: (17)
(18)
(19)
(16)
than hydrolysis. Silanols are protonated more easily when During the curing process, first of all, most of the solvent
they are present at the end of the polymer chain. is lost by the evaporation which leads to the concentration
In basic conditions, they build siloxane bridge by another of the zinc ethyl silicate mixture. At this point, coating is
SN2 mechanism. This mechanism involves two interme- uncured and sensitive to moisture or water.
diary complexes with penta coordinated silicons. In basic
conditions, condensation rate is not only proportional to
the concentration of OH− anions but also superior to that
of hydrolysis. Furthermore, since the reticulation inside the
silicon polymers is more developed than when conditions
for acidic catalysis are used, hence the denser solids are
obtained.
(22)
The moisture and carbon dioxide in the air react with each
(21) other to form carbonic acid, as shown below:
5. Coatings are not flexible. Performance comparisons between zinc dust primers and
6. They are higher in cost as compared to the conventional zinc flake primers have shown that chromated zinc flake
coatings. systems outperform zinc dust primers (of same vehicle type)
7. The major problem with this system is that the cure rate in both salt fog and bullet hole studies.
of alkyl silicates is dependent upon relative humidity. In
dry climate, cure rate may be reduced greatly, especially 7.2. Extender pigments
at temperature below 10◦ C and where the films of high
thickness are involved [59]. The metallic zinc content in the dry film is a very im-
8. However, alkyl silicate primers have somewhat better tol- portant parameter to be emphasised in the technical specifi-
erance for slightly poorer surface preparation than the cations of zinc-rich paints. According to the most technical
alkali silicate based paints, but a properly cleaned (sand specifications, minimum content of metallic zinc in the dry
blasted) surface is a must for these coatings. film required is 75% (by weight) for zinc-rich paints based
on ethyl silicate. For the same metallic zinc content in dry
Under cathodic protection, organic binder based zinc-rich
film the solids balance can be made using only the binder
primers have tendency to degrade, and also to cause blis-
and zinc dust or partial substitution of binder with auxiliary
tering of the subsequent coats. In this respect, inorganic
pigments. It is observed by Land quest that metallic zinc
zinc-rich primers have superlative record. Another reason
content in the dry film is not only a factor determining the
for the popularity of zinc silicate primers is their capacity
performance of this kind of paints while Fragata et al. [60],
to offer longer anticorrosive protection at lower dry film
Del and Giudice [61] and Pereira et al. [62] verified that the
thickness and at lower zinc loading levels [2].
chemical nature of the binder and the zinc particle size are
These systems form coherent adhesive coating of silica
also very important.
which results due to hydrolysis and gelation of the ethyl
In order to obtain contrast between sand blasted steel
silicate binder. Because of inertness and refractoriness of
substrate and the paint, some manufacturers use colour-
silica, these systems are heat stable and durable.
ing pigments such as chromium oxide and iron oxide, and
because of technical reasons some other manufacturers use
extender pigments such as barytes, mica, talc etc.
7. Factors influencing film performance Experimental studies have been carried out by Fragata
et al. [63], on ethyl silicate based paints having a metallic
There are various factors, which affect performance of the zinc content of 75 and 60% (Table 5). Panels coated with
applied ethyl silicate zinc-rich coatings. These factors are these paints were subjected to salt spray, field exposure and
discussed hereunder one by one. electrochemical tests. The results showed that addition of
fillers agalmatolite (A) and barytes (B) to the paints with
7.1. Particle shape and size of zinc pigment 60% metallic zinc in the dry film improves their behaviour.
Salt spray results for 75% zinc content up to 2060 h of
Zinc is most commonly used as zinc dust in ethyl sili- exposure did not show any influence of fillers.
cate based zinc-rich coatings. Zinc particles are generally In the paints which contain fillers, for the same metallic
spherical in shape. Studies have been carried out by Hare zinc content in the dry film, the PVC/CPVC ratio is higher,
[59] using zinc flakes in organic zinc-rich primers and ethyl which leads more porous and permeable films due to which
silicate zinc-rich primers. It was theorised that a flat plate the electrical contact between zinc particles and steel sub-
zinc particle can be utilised advantageously in several ways. strate improves. These factors contribute to the improve-
Theoretically, zinc dust particles having a particle diame- ment of paint performance from the galvanic point of view.
ter of about 10 times the thickness of a zinc flake platelet It is important to mention that effectiveness of the zinc-rich
would require much more minimum primer film thickness paint does not depend solely on electrochemical factors.
for a given degree of protection than would the flake do. Some other factors such as mechanical properties viz. cohe-
In a 25 micron film thickness, as many as 20 zinc flake sion, flexibility, etc. are also important. So the addition of
platelets might be superimposed as compared to approx- auxiliary pigments should be controlled carefully in order
imately three rows of spheres of zinc dust. The lamellar to not impair the physical and chemical characteristics of
nature of the flake would ensure a significantly enhanced the films.
electrical contact area. In fact, reactivity of zinc flake in salt In inorganic zinc silicate coatings, water, ground mus-
fog environments was found to be too great to provide the covite mica is also used widely. On the basis of experimental
sort of long-term performance profile required. Apparently, studies, Hare [64] reported that upgraded corrosion resis-
zinc flake produced far more current than was necessary to tance and reduced cost of the system can be obtained by
protect the steel cathode, and was soon exhausted. Hence re- using flake zinc in combination with mica and zinc potas-
duction of zinc reactivity by the addition of small quantities sium chromate. It is also observed in the mica modified
of inhibitors such as potassium chromate along with mica formulations that they produce reduced amount of zinc cor-
extender significantly improved performance effectiveness. rosion product, which indicates the general reduction in zinc
12 G. Parashar et al. / Progress in Organic Coatings 42 (2001) 1–14
Table 5
Salt spray results of ethyl silicate coatings pigmented with zinc dust and fillers
Paint designation Metallic zinc con- Main components Time (h) necessary for appearance of
tent in the dry film of dry film red corrosion in scratch (ASTM B-117)
Zn60 60.0 Ethyl silicate 460
Zinc dust
ZnA60 60.0 Ethyl silicate 740
Zinc dust
Agalmatolite
ZnB60 60.0 Ethyl silicate 660
Zinc dust
Barytes
Zn75 75.0 Ethyl silicate 2060
Zinc dust
ZnA75 75.0 Ethyl silicate 2060
Zinc dust
Agalmatolite
ZnB75 75.0 Ethyl silicate 2060
Zinc dust
Barytes
corrosion. This effect is thought to be related to the control zinc content while a greater fraction of the zinc initially
of current transfer that such non-conductive extenders might present remained unoxidised after a given period of time.
allow. Electrical conductivity is reduced in this case not only
by the resistance of the vehicle cover but also by the mica 7.3. Application techniques
laminate.
Besides these, various other conductive extenders have Application techniques and relative humidity also have
been used such as cadmium, aluminium, magnesium, iron influence on the curing of inorganic zinc ethyl silicate based
and carbon along with zinc dust. Of these, only cadmium primers [57]. The experimental results also revealed that
with zinc and inhibitors gave results comparable to normal curing is affected by incorrect mix ratio of base to filler,
zinc-rich primers. Others have proved to be inferior. Prob- inadequate mixing and/or settling out of the zinc portion,
lems of toxic fumes during welding, however, precludes and this will be dictated by spray equipment and technique,
the use of cadmium in these coatings. Out of various exten- and also by spray parameters such as air pressure, nozzle
ders used in ethyl silicate based zinc-rich paints, the best sizes, distance from the surface, etc. It was also reported
results have been obtained from di-iron phosphide (Fe2 P), that spray coating methods yielded results which were not
which is a refractory conductive compound. In ethyl sili- readily reproducible and gave both poor and good curing
cate zinc-rich coatings evaluation of this extender has been results, while flow coating methods yielded reproducible re-
carried out by Filire et al. [65]. Results of the test carried sults conforming to manufacturers’ data sheets under the
out by them show that it is possible to replace up to 25% of conditions tested.
zinc with minimal decrease in the ability of the coating to
provide cathodic protection to the steel substrate. Composi-
tions of some ethyl silicate vehicles formulated with higher
8. Areas of applications for zinc-rich inorganic silicate
concentration of Fe2 P lead to abnormally high zinc corro-
paints
sion products. Ethyl silicate zinc-rich coatings with Fe2 P
additions tend to act as porous electrodes probably because
Because of the excellent corrosion protection offered by
a majority of the metal and conductive extender particles
these coatings to steel, these coatings find applications in
maintain electrical contact between each other and with the
various critical fields [66]. Some of their application areas
steel surface. This explains the greater ability of silicate
are given hereunder:
coatings to provide cathodic protection to the steel substrate.
Further, the inclusion of Fe2 P extender does not disturb 1. Harbour structures. The corrosion conditions encoun-
the marked capability of ethyl silicate zinc-rich paints to tered by off-shore petroleum production platforms are the
develop barrier coats. The weldability of primers is also most severe. Many hundreds of drilling and production
improved by the use of Fe2 P. Zinc appears to be consumed structures have been coated with inorganic zinc silicate
more efficiently in the presence of Fe2 P with the result that coatings, located in the highly humid tropical areas of
improved corrosion protection is obtained with lower initial Indonesia, Singapore and the Persian Gulf to the United
G. Parashar et al. / Progress in Organic Coatings 42 (2001) 1–14 13
States Gulf coast and extending into the Arctic areas of and lithium silicates and alkyl silicates such as ethyl sili-
Alaska and the North Sea. The inorganic coatings based cate are commonly employed as inorganic binders. Ethyl
on hydrolysed ethyl silicate, applied alone or overcoated silicate based binders have proved to be superior to alkali
for additional protection and for safety colouration, are metal silicates in overall performance, despite the fact that
providing outstanding protection to these essential pieces former ones produce solvent-borne compositions, whereas
of equipment. alkali metal silicate based coatings are water-borne. Ethyl
2. Bridges. Bridges, like off-shore structures, are extremely silicate based coating films are self-curable at room tem-
vulnerable to corrosion, perhaps so since many bridge perature in the presence of adequate atmospheric moisture.
structures are formed from structural steel shapes, with The final (cured) films of ethyl silicate based coatings are
all the corners, edges, crevices and surface defects in- composed mainly of silica, or silica and zinc, if zinc is used
herent in such shapes. One of the very early bridges as a pigment. Therefore, cured films of ethyl silicate based
coated is a Drawbridge across a Tidal river in Florida. (inorganic) coatings are considered better, in view of envi-
This bridge was coated in 1956 with the open grill work ronmental aspects, than organic coatings which invariably
being the most difficult part of the structure to fully produce films composed of organic polymers. The films of
protect it. It is still well protected by the original single these coatings, being silica based, are resistant to temper-
coat of inorganic zinc silicate coating. Other bridges ature up to 400◦ C, where most organic coating films fail.
such as Baleman bridge in Tasmania which was coated Further, films of zinc-rich ethyl silicate based coatings pro-
prior to installation, the golden gate bridge on the orig- tect the substrate (steel) by providing much more effective
inal Morgan Whylla pipeline, are some examples of full cathodic protection than that provided by zinc-rich organic
protection provided by inorganic zinc silicate paints over coating films. In addition, ethyl silicate based binders react
many years of continuous exposure. with the iron (substrate) chemically, and hence provide un-
3. Nuclear power facilities. One interesting application of matched adhesion to restrict corrosion creepage, if any kind
inorganic zinc silicate paints is the protection of nuclear of corrosion at all starts on the substrate. The films, being
power plants. The steel surface within the reactor building rock-like hard and quite rough, provide excellent inter-coat
requires coating with a 40-year expected life. In fact, it is adhesion to the subsequent coat.
hoped that such surfaces will never have to be painted af- On account of these attractive features, ethyl silicate based
ter the plant goes into operation. Alkyl silicate inorganic coatings can be successfully used for high performance
zinc-rich primers are used in nuclear applications for applications in critical areas such as harbour structures, nu-
many reasons. These primers are applied at 3.0 mil min- clear power plants, etc. As on today, no organic coating is
imum thickness, mainly at the steel plate manufacturer’s available which can match these inorganic coatings in terms
factory before shipping to the job site. These coatings of long-term corrosion protection performance clubbed
are unaffected by ␥-rays or neutron bombardment. with their high temperature resistance. It can, therefore, be
4. Tank coatings. One of the major uses of inorganic zinc expected that ethyl silicate based coatings will find wider and
coatings has been in the lining of ship tankers, primarily wider application in further more challenging areas in future.
for transporting refined fuel. One of the oldest docu-
mented applications of inorganic zinc coatings is the
No. 1 centre tank in Utah standard. This was applied in References
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