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From Volume 3 Paper 18 JSCE,

http://www.jcse.org/volume3/paper18/v3p18.php?commentmode=1

Corrosion resistant zinc silicate coatings: A Review


David Scantlebury and Michael Walsh
Corrosion and Protection Centre, UMIST, PO Box 88, Manchester, M60 1QD, UK
scantlebury@manchester.ac.uk

Abstract

Zinc metal containing coatings, especially those based on silicate binders are very popular anti-
corrosive primers. This review explores the history of their discovery, compares them with more
conventional organic systems, and discusses the proposed mechanisms of cure. The protection
mechanisms are summarized and specific features such as minimum zinc content are emphasized.
Recent electrochemical studies are examined and the various models are discussed.

Keywords: metallic zinc powder, silicate binder, epoxy binder, review, cure mechanisms,
protection mechanisms

Introduction

Early developments

The extraction of zinc was first carried out commercially in Bristol in 1743. As part of the
process, powdered zinc oxide was obtained by roasting sulphide ores which was then reduced by
distillation with carbon. Thus early on in the history of zinc, both zinc oxide and zinc metal were
available in a finely divided form and the use of these materials in paints is a natural extension.
Before the rise in rutile titania as an opacifying pigment, zinc oxide was very popular. It is still
used in can lacquers for the containing of proteinaceous products. Sulphur containing proteins
cause black staining with the iron of the can. Fortunately zinc zulphide is colourless. Zinc
phosphate dihydrate is currently popular as an anti corrosion primer pigment. Zinc metal powder
has always been readily available as zinc is produced by condensation from the vapour and it has
a long history as a pigment is paints. According to Nelson writing in volume 2 of the classic five
volume series edited by Mattiello zinc dust pigments have been used since 1840 with very early
French and German work quoted in his article. According to Munger, the use of metallic zinc in
paint coatings for the protection of steel from corrosion dates back to the 1930s. These coatings,
with a high quantity of zinc included, are used as a primer or final coat and can be spray applied,
dipped or brushed.

The scientific developments of these coatings, predominantly organic, which contain zinc in high
quantities started in Cambridge in the 1940's with Evans & Mayne. This early work incorporated
95% by weight of zinc into a variety of binders. These included chlorinated rubber lacquer,
polystyrene lacquer, linseed oil, medium stand-oil, and an aqueous emulsion of linseed oil.
Panels were exposed into seawater with a scratch line in the coating to expose steel. Evans &
Mayne explain the excellent protection being due to the cathodically protective nature of the zinc.
This in part is due to the necessary particle to particle to substrate contact of the zinc. Evans &
Mayne based the incorporation of zinc pigment on the original work of sacrificial protection of
iron or steel in seawater by Davy in 1834. However, they also stated that paints pigmented with
zinc dust had been employed against atmospheric attack since the 1840. It was also found earlier
that this type of paint gave temporary protection to uncoated sections of a steel substrate in
outdoor exposure .

The first documented use of silicate binders is regularly referred to be the application of a water-
borne sodium silicate zinc dust coating to the Morgan Wyalla above ground pipeline in Australia.
The coating was cured with the heat and was reported to be in excellent condition after more
than 50 years.

Zinc silicate coatings

It is said by Munger that the entire development of zinc silicate coatings began with the
Australian, Victor Nightingalls dream of forming a zinc coating that would be the equivalent of
galvanizing but be applied by painting techniques. His starting point was to produce a material
similar to the mineral willemite (zinc silicate, Zn2SiO4) as a thin film on a metal surface. It was
said that the produced material was a durable and corrosion resistant coating.

Characteristics of zinc-rich coatings

Coatings that are pigmented with zinc particles can have an organic or inorganic binder. Organic
binders such as epoxies, phenoxies, chlorinated rubbers, silicones and vinyls have been used.
Inorganic binders are either sodium silicates or ethyl silicates. The inorganic binders can be self-
curing and water or solvent reducible.

Inorganic zinc silicate coatings are often used as primers and are top coated with paints that do
not contain zinc.

Organic and inorganic zinc coatings

The differences between organic and inorganic zinc coatings have been summarized by Hafford
et al . It is said that organic zinc coatings are more compatible with topcoats, more flexible, less
dependant on atmospheric moisture to cure but are difficult to apply under high or low ambient
temperatures. With inorganic zinc coatings it is said that the surface preparation is more rigorous,
there is better corrosion protection, better toughness and better abrasion resistance than is seen
with organic zinc coatings. Inorganic zinc coatings also dry faster under optimum conditions and
once the coating is formed there is better temperature resistance.

O.Connor and Bowen give the advantages of both organic and inorganic zinc coatings. These
can be seen in table 3.
Table 1 Advantages of organic and inorganic zinc coatings
Inorganic
Organic
Outstanding corrosion protection Outstanding corrosion protection

Fast drying Tolerant of wider temperature variations


during application
Can be applied over lower class surface
Excellent resistance to petroleum solvents
Tolerant of greater variation in dry film
thickness Perform well without a topcoat in pH 5-10

Less prone to mud cracking Excellent heat resistance up to 400oC

Perform well without a topcoat in pH 5-10

Good film flexibility

Formation of zinc rich coatings

Hare compares the film forming characteristics of both organic and inorganic zinc rich coatings.
It is stated that the morphology and structure of organic and inorganic zinc rich films are
different especially with regard to the early stages of film formation. The film formation
chemistries include dehydration, neutralisation, solvent loss or hydrolysis of the primary vehicle
and silication with the zinc pigment. Authors such as Munger have detailed reactions that include
ionic zinc within the reaction mechanism. This is in some way backed up with unpublished data
of a zinc silicate coating with 0% zinc content. This coating was unable to cure.

Hare goes on to present a stylistic representation of postulated structure of inorganic zinc-rich


film. It shows how silicate vehicle is bonded to zinc atoms on particles of zinc dust pigment.
Figure 1 Postulated structure of inorganic zinc rich film by Hare

The stated advantages of this system are given as there being no encapsulation by the binder, the
film being porous to allow ingress of electrolyte. There is also good film strength, adhesion,
electrical conductivity and cathodic protection.

Cure of coating

Coatings of this type that are two-pack solvent borne usually require no further treatment to
attain cure. The cure reaction proceeds after the mixing of the two packs. This mixing initiates
the chemical reaction that enables the coating to dry and cure forming a film of desired
properties. There is a short, finite pot life of the coatings once mixing has occurred. Two-pack
coatings can be formulated with current and proposed environmental, health and safety standards
including volatile organic compound (VOC) regulations . These changing regulations have lead
to a move towards low VOC containing coatings with solvents such as water. Typically these
contain the pigment and solvent in one part and the binder and solvent in the other part along
with a small amount of water and acid, either HCl or H2SO4. The reaction mechanism is
suggested as that in figure 2.
Figure 2 Cure reaction of inorganic zinc silicate coatings based on tetraethylorthosilicate

Byrnes & Vincent state that there are two stages of formation with ethyl silicate binders, these
being: solvent evaporation, where a firm dry film is formed that is able to tolerate mechanical
handling; and atmospheric moisture reacting with the ethyl silicate binder in hydrolysis,
releasing ethanol.

Eccleston however, goes further into the complex reaction mechanism stating the reaction
processes as being hydrolysis, condensation and solvent evaporation. Although both authors vary
in the amount of detail in which the reaction mechanism is discussed, they both agree that the
end result is the zinc particles are bound to each other and the substrate by inorganic silicates.
The reaction mechanism of Eccleston is shown in figure 3.
Figure 3 Cure reaction mechanism proposed by Eccleston

Before the reaction takes place the material is prehydrolised to a known degree by adding a small,
exact amount of water. The solution is also slightly acidic, as stated earlier. The alkoxy group
goes to silanol groups with alcohol in the hydrolysis reaction. Along with this alcohol there is the
alcohol in the bulk mixing solution, which begins to evaporate on application. As the zinc is
added the acid is neutralised making the silanol groups more reactive, they then either react with
each other to form the silica matrix and water; or react with ethoxy groups to produce ethanol.
The water produced in the condensation reaction goes on to promote further hydrolysis.

It must be remembered that the above reactions can continue after the coating appears to be dry.
It is therefore important to understand the rate of cure before any of the coatings can be either
exposed or over-coated. This is illustrated in figure 4, which features a time-line representation
by Ginsberg.
Figure 4 Representation of the changing composition of the coating with time

As the above figure illustrates, and the various authors confirm, the greatest changes in the
formation of the coating take place in the initial stages after the coating has been applied.
Therefore the conditions in which the application takes place can have a significant effect on the
film formation. This is an area studied by Eccleston who developed a gas chromatography
method for the analysis of cure.

Eccleston states that zinc silicate coatings can be touch dry in minutes and are resistant to rain
within half an hour. This compares well with water-borne alkali silicates that become resistant to
rain in approximately 24 hours. Differing conditions can lead to premature coating failure.
Application conditions that lead to failure are known either qualitatively or anecdotally, such as
application under low humidities. It is not uncommon in the coating industry to spray the freshly
coated substrate with water when the humidity is low as under conditions of less than 40%RH
the coating will not cure. Although as part of the investigation by Eccleston showed, the spraying
with water is at its most effective while the coating is still wet.

The assessment of cure has been subject to different analytical techniques. These include infra-
red spectroscopy (IR) and nuclear magnetic reasonance spectroscopy (NMR). Both Byrnes &
Vincent and Eccleston have each developed a gas chromatographic method of analysis for the
cure analysis. Byrnes & Vincent utilised the ethanol eluent peak to characterise the amount of
cure. As figure 3 shows, the ethanol is liberated from the first stage of the condensation reaction
and as time continues this should reduce as the cure becomes more complete. Byrnes & Vincent
took four different brands of zinc rich silicate coatings and used them in analysis, the results of
which can be seen in figures 5 & 6.
Figure 5 Degree of cure vs. time by Gas Chromatography

Figure 6 Double rub sensitivity test results

The result of the testing show that there are different rates of cure for the samples used and that
total hydrolysis is not needed for solvent resistivity. However, it is unclear as to whether there
were any individual manufacturer specifications for the application of these coatings and if they
were followed. There is a clear correlation between the GC technique and the MEK double rub
sensitivity test.

Eccleston used a GC technique to investigate the various conditions that can prevail during the
initial application stages. Using an alkoxy:silicon ratio (from eluent peaks) analysis was
completed at different times and relative humidities. The results can be seen in figures 7 & 8.
Figure 7 Degree of cure vs. time at constant temperature

Figure 8 Degree of cure vs. time at constant absolute humidity (0.0115g moisture/g dry air

From these results Eccleston concludes:

That the atmospheric conditions in the initial period after coating application is critical to
the film formation and it is strongly influenced by temperature and humidity.
Zinc dust accelerates the hydrolysis and cure is rapid.
The water produced in the condensation reaction goes on to hydrolyse 40% of the alkoxy
groups, and at low %RH the water quickly evaporates and is not available for further
hydrolysis. Also as an increase in temperature will cause both water and solvent to
evaporate more quickly and the film will have less time to complete its reactions.
Hot & dry conditions should be avoided during application and drying (water could be
sprayed onto the coating before it becomes dry). Hot conditions alone are not too
detrimental unless accompanied by a low %RH.

This section has discussed the chemical reactions involved in the formation of the dry coating
film in the cure process and the idea that zinc is involved within the reactions. At this point, there
has been no mention of the role of the steel substrate within the film forming process. Chemical
bonds are desirable for adhesion between the coating and substrate. It is stated by Munger that
bond types of Si-O-Fe-, from the silica matrix to an iron atom located at the steel substrate
surface, are present at the coating/substrate interface (figure 9). Although supporting data is not
presented.

Figure 9 Representation of chemical bond between matrix and substrate

The protection mechanism of zinc rich coatings

Introduction

It is stated a number of times within this document that the majority of the available literature
concerns zinc rich coatings. Very little is available on low-level zinc containing ethyl silicate
coatings aside from authors concluding that this type of coating does not afford any protection to
steel. The mechanisms and investigations into them that appear in this section are almost all
concerning zinc rich coatings. The use of this information forms the basis of understanding to the
performance data that will be obtained for the subject coating.

Comments on the protection mechanism

Although there is a general agreement of there being two stages in the protection mechanism,
there appears to be most discussion on the type of secondary effect. The type of literature that
appears comes in the form of either reviews or experimental papers. Occasionally review papers
do include original experimental work but with others the experience of the author with the
coating type may be simply of literature rather than practical. This section includes comments by
a number of authors, some of whom are very well represented. Specific aspects of their work are
discussed at a later stage; initially it is the comments on the mechanism that are discussed here.

The above paragraph mentions a general agreement of the mechanism with discussion
concerning the second stage of protection. This is opposed by Romagnoli & Vetere who state
that there is not a universally accepted theory for the protection mechanism. However, some
agreement is with Evans & Mayne who suggest a cathodic protection stage, where the zinc acts
as a sacrificial anode, followed by a subsequent stage where the substrate is protected longer than
is expected by galvanic action alone. This is by either blocking of the pores within the coating by
zinc corrosion products; or the inhibitive action of zinc basic compounds on the steel substrate.
Experimental work carried out by Romagnoli & Vetere suggests zinc contents above 85% by
weight are needed for the particle-to-particle-to-substrate electrical contact. A mention is also
made of a 50% by weight zinc containing coating whereby the authors dismiss this as being too
low zinc content. As zinc content decreases the protective action diminishes. Impedance work
carried out suggests a pore filling action by the zinc basic salts with properties dependant on
particle size and content of zinc.

It is stated by Hare that the zinc rich type of coating is sacrificial and that the galvanic activity is
a consequence of a deliberately engineered electrochemical cell (figure 11). The principles of
this cell are the same as those that form the basis of hot dip galvanising and anodes such as zinc
and magnesium. When there is no electrolyte (dry conditions or incidental, light atmospheric
wetting) Hare states that zinc corrosion is low and the steel substrate is protected by the marginal
barrier effects of the primer. The cell is only active when electrolyte is present and when this is
the case any exposed steel is protected by a local cell action and is covered by zinc corrosion
product. Over time, according to Hare, the anode is polarised by zinc corrosion products such as
zinc carbonates, zinc sulphate and zinc hydroxide. These products are said to fill the pores in the
film structure forming a hard inorganic film. The mechanism is then transformed from cathodic
protection to a barrier effect. Cathodic protection is said to be minimal after approximately 3
months and this lengthens to 3 years with atmospheric exposure. Hare concludes that there
remain questions concerning the barrier stage of protection.

Figure 10 a) An Illustration of a simplified electrochemical cell within the coating and b)


Anode & cathode reactions

According to Lindquist the continued protection is related to the inhibition of the steel by the
basic zinc corrosion products within the film and a locally raised pH. The zinc salts are formed
due to the corrosion of the zinc itself or due to the galvanic action. The influence of pH is also
mentioned by Ross & Lingard who state that the pore blocking mechanism is of greater
importance than the galvanic stage. It is also stated that the cathodic protection stage results in a
high local pH, which protects the steel and encourages the formation of insoluble, protective zinc
compounds.
O.Connor & Bowen state that following the galvanic stage the build up of corrosion product of
zinc or white rust such as zinc carbonate and zinc oxide fills the pores within the coating. This
stops air and moisture reaching the substrate below.

Scantlebury et al agree that there is a galvanic stage of protection but state that the second stage
of protection is contentious. Two suggested mechanisms are the corrosion products act as
chemical inhibitors or by blocking the pores. By a combination of monitoring current with time
and impedance it was concluded that the second stage of protection is a combination between the
two, i.e. zinc corrosion products acting as chemical inhibitors and blocking pores. This is a point
upon which Armas agrees where it is stated that the main part of the mechanism is the cathodic
protection of the steel by the zinc. As the exposure time increases the deposition of inhibiting
zinc compounds at the base of the coating pores is followed by the sealing of the porous structure
by zinc corrosion products.

Feliu on work that utilizes impedance for both the galvanic and barrier stage states that the
galvanic stage becomes inactive after a short time. The second stage, it is said, is not sufficiently
classified and is dependent on zinc content. The ethyl silicate coatings of the type studied by
Feliu are said to favor cathodic protection.

Other authors agree that there is a galvanic stage to the protection. The second stage follows
what has already been stated in this section where there is either a pore sealing or inhibiting
barrier formed.

Summary

It has been observed that there are many differences of opinion within this subject area, but there
are main underlying agreements. These are summarized below:

There are two stages in the mechanism of protection of high zinc content coatings. The
first is the cathodic protection of the steel substrate by the zinc pigment that acts as a
sacrificial anode. This is set up in the traditional corrosion cell of anode, cathode,
electrolyte and electrical connection.
The second stage of protection uses the zinc corrosion products that are formed from the
cathodic protection stage. Almost all of the literature suggests that there is a pore
blocking action within the coating by the corrosion products. There is some suggestion of
the corrosion products being inhibitors.
The higher pH within the coating has some effect on the protection mechanism. This
raising of the pH is due to the production of the basic zinc corrosion product.
The success of the protection is dependent on the amount of zinc that is within the
coating.

Minimum zinc content for performance

There are two types of information source that is found in the literature: those who quote a
minimum zinc content for the starting point of cathodic protection and those who offer data of a
minimum zinc content. The minimum zinc content is of great importance to this study because
those quoted in the literature are invariably much higher than that of the coatings that will be
studied in this thesis. Agreement between authors concerns the definition as to why there is a
minimum zinc content of the coatings. This it amount of zinc necessary for particle-to-particle-
to-substrate connectivity, which is discussed by Ross & Lingard in terms of conductivity of the
dry film. It is stated that the conductivity is related to the zinc content, film thickness and the
internal resistance of the dried film when it comes into contact with the electrolyte. Absolute
values are shown in table 2.

Table 2 - Literature values of minimum zinc content of ZRPs


to give cathodic protection
>85% by weight

>83% by weight

75% to 95% by weight

~90% by weight

Table 2 also illustrates the predominance of zinc rich coatings in the literature.

The performance of zinc-rich silicate coatings

The monitoring of potential with time is one of the basic techniques of corrosion science. It
allows for a comparison between coating systems and different research. Abreu et al have
offered an explanation of the change of potential with time in relation to zinc rich coatings. This
is represented as figure 11 below.

Figure 11 Evolution with immersion time of the corrosion potential of a zinc rich
paint/steel plate system
The periods (I, II & III) are defined as follows:

Period I: The corrosion potential shifts to more negative values, towards the potential of zinc
plate. There is a rapid initial stage, due to the activation of the zinc particles in the coating,
followed by stabilisation at or near to the potential of zinc.

Period II: The potential now begins to move towards the protection potential of steel where the
end of the cathodic protection stage is reached. The process now transfers to the second stage of
protection.

Period III: The potential has passed the protection potential of steel and is now moving towards
the potential of iron. The coating surface would now be beginning to show signs of iron rust.

Although the timescale may change there is a correlation between the proposal detailed above
and other data found within the literature. What is clear is that the activation period that takes
place initially is often missed in the data collection process or the scales of the data axes are not
adjusted for its observation. Work completed by Armas shows the behaviour of a zinc ethyl
silicate coating, at two different film thicknesses, on immersion in artificial seawater when
potential is monitored with time (figure 12)

Figure 12 E vs. t for an 83.8% by weight zinc containing ethyl silicate coating. Plot 4 shows
150mm dry film thickness coating and plot 5 shows 75mm coating. Other plots are for zinc
containing epoxy coatings

It is clear from figure 12 that the film thickness has a distinct effect on the performance of the
coating when immersed. It also shows that the ethyl silicate binder is more effective in this
environment than the epoxy type coating.

Scantlebury et al monitored the corrosion potential of a zinc rich ethyl silicate primer under
immersion conditions in 3% sodium chloride solution. The effect of a large bare area on the
potential was also monitored (figure 13)
Figure 13 Potential vs. time for a 63% zinc ethyl silicate coating a) full intact film
and b) 15% bare steel, immersed in 3% sodium chloride solution

Scantlebury described the coatings as a Zinc particle coating more or less surrounded by a
cement of ethyl silicate, and was applied to an abrasively blasted panel with a film thickness of
50 10mm. The authors comment that there is an insignificant amount of corrosion present after
33 months outdoor exposure (Sines, Portugal). It can be seen that the curve for the zinc ethyl
silicate coating in figure 13a exhibits a similar shape to that explained by Abreu. However the
change in potential is 55mV in figure 14a and as it is below 1000mV/SCE after 50 days this is by
no means a complete curve and the protection given by the zinc pigment would last for a much
longer time period.

Figure 13b shows the affect of 15% bare steel on the coating. The move towards the potential of
steel is greatly increased compared to that of a completely covered panel. This illustrates how in
high zinc content coatings the particle to particle to substrate contact is maintained to provide
protection to an exposed area. If the exposed steel were several magnitudes smaller in size it
would be expected that the zinc corrosion product would cover the small gap in the coating.
When the area is large, such as in the above research, then the protective capacity of the zinc is
reduced to protecting the exposed area and being rapidly used up. This would have a detrimental
influence on the formation of any barrier by the corrosion products of zinc.

Lindquist, Meszaros and Svenson studied eight commercial zinc rich primers in an
electrochemical investigation, of which four were of the ethyl silicate type. The potential of the
systems was taken during immersion in aerated 0.1M sodium chloride solution, approximately
0.6% by weight sodium chloride. The four coatings were made up with zinc contents of 83%,
87%, 91% & 93% by weight. The change of potential with respect to time can be seen in figure
14.
Figure 14 Potential vs. time for exposure in 0.1M sodium chloride solution for four
commercial ethyl silicate zinc rich coatings on steel

It can be seen that the 87% and 91% by weight zinc coatings were no longer protecting the steel
at the end of the test as they exceeded the protection potential of 780mV/SCE. The 83% and 93%
by weight zinc coatings were still protecting the steel by cathodic protection at the end of the test.
The authors make brief comment as to the possible differences in performance, namely different
vehicle formulations and incorporation of extenders. As these formulations are not given it is
difficult to obtain any useful comparative understanding of the mechanisms taking place between
the coating systems. However, each curve does show the expected shape and the authors
comment on the complete loss of cathodic protection in the worst performing coatings. The
authors state that after being exposed for a week the solid zinc metal was white in colour due to
the formation of corrosion product and the ethyl silicate zinc rich coatings were also more or less
covered in white deposits. They go on to say that this white deposit was due to the corrosion of
the zinc particles at the surface of the paint film and X-ray diffraction showed the white deposits
to be a mixture of several zinc compounds including Zn4CO3(OH)6.H2O and Zn5(CO3)2(OH)6.
As stated earlier in comments on the mechanism, Lindquist says that the corrosion protection of
these coatings lasts longer than the period of galvanic activity. However, no details of sample
condition at the end of the test were given.

Feliu et al considered the performance of ethyl silicate zinc rich coatings that cover a wider range
of zinc content. The composition of these coatings is given in table 3.
Table 3 Composition of ethyl silicate zinc rich coatings as used by
Feliu & co-workers as given by manufacturer
Vehicle type Components
Ethyl silicate Zinc dust: 84%, 78%, 50% by weight

Ethyl silicate

Bentonites (antisettling agent)

Silica (extender). Only in the formula


with lower zinc contents

Solvents

The coatings were applied to a dry film thickness of 50-60mm and were exposed by immersion
in 3% by weight sodium chloride solution. The performance by measurement of potential with
respect to time was shown to be quite different for the levels of zinc used in the exposure (figure
15)

Figure 15 Potential vs. time for three different zinc ethyl silicate coatings immersed in
3%wt sodium chloride solution

The potential curves (figure 15) show that the coating containing 50% by weight zinc does not
attain a potential at which it can provide cathodic protection to the steel substrate. It is stated,
however, that it provided protection for 1 day. Unless problems occurred with the data collection
or the reproduction of the data this statement of the protection provided is not verified by data. If
the development of the potential with time curve explanation of Abreu [33] is followed, then the
initial drop in potential could have been missed in the data collection. Although it is fair to say
that with lower zinc contents it would be expected that this trend of potential moving towards
that of zinc will be extremely short-lived.
A difference of 6% by weight zinc between the higher-level zinc coatings shows a large
difference in the cathodic protection performance. The 84% by weight coating maintains a
potential lower than 900mV for 110 days whereas the 78% by weight coating maintains this
potential for 20-40 days. This would appear to show the importance of higher zinc content when
concerned with the performance of these zinc rich coatings in exposure media such as 3% by
weight sodium chloride solution.

Summary

There are a number of different parameters available when monitoring potential with time. These
can include variables such as exposure media, zinc content, film thickness and substrate
condition (smooth or rough). When considering performance it is important that it is related to
the conditions of exposure. Table 4 shows the conditions, where available, of the research
completed by the authors discussed in the above section.

The performance can be compared, with regard to the exposure conditions, by using the time to
reach the protection potential of steel. This is where the cathodic protection of the steel by the
zinc is no longer effective. This is summarised in table 4.

Table 4 Experimental parameters of the presented literature work on ethyl


silicate zinc rich coatings with the time for each coating to reach the protection
potential of steel
Zinc content Time to Film thickness Exposure
Author
(%wt) EProt (a)(Days) (mm) media
~40 75
Artificial
Armas 29 83.8
Seawater
+100 150
Scantlebury37 63 +100 50-10 3%wt NaCl(c)
83 +60

87 10-15
Lindquist 26 ~100(b) 0.1M(d) NaCl
91 10-15

93 +60
50 1

Feliu 31, 34 78 20-40 50-60 3%wt NaCl

84 110
a) EProt abbreviation of the protection potential of steel
b) Approximation from measurement of presented cross-section image
c) 3% by weight Sodium Chloride solution
d) 0.1M sodium chloride solution equivalent to ~0.6% by weight solution
General observations:

As zinc content is increased, the time taken to reach Eprot is increased. This can be seen
through the work of Feliu . No inferences can be made from the work of Lindquist due to
the differing composition of the individual coatings within the study. The difference in
time to reach EProt observed between the work of Scantlebury and Feliu can also said to
be a consequence of the different composition. It can be seen that the film thickness used
is similar and the exposure media is quoted as being the same but the time to reach
EProt of the 63% by weight coating is as long as, if not greater, than that of the 84% by
weight coating.
As the film thickness is increased, the time taken to reach EProt is increased. This can be
seen through the work of Armas who used two different film thicknesses with the same
coating within the study.
The variety of exposure media used shows that there is no standard method of test
exposure generally used. Much of the work would be completed using a set of solutions
so that information can be related to that of the literature. It may be inferred however, that
Armas has aimed to model the real conditions of exposure that this type of coating would
need to perform in. It is this point that is considered later when the exposure regime of
this research is detailed.

The role of zinc content in the formation of corrosion products

As stated earlier, the zinc content has a direct affect on the performance of the zinc silicate
coating systems. It has also been established that the initial protection mechanism of this type of
coating is through cathodic protection and that the level of zinc content is of great importance.
This level of zinc content influences the overall particle-to-particle-to-substrate contact. Work
done by Morcillo et al offers a schematic representation of the type of conduction pathways
within the coating (figure 16). This is dependant on the amount of zinc within the coating that
allows the pathways to form.
Figure 16 Schematic representation of electronic (A & B) and ionic (C, D & E) conduction
pathways within a zinc rich silicate coating

Pathways A & B depend upon the zinc content of the coating, which in reality is much thicker
than the above representation. This ensures an electrical connection between the zinc anodes and
steel cathode. Pathways C, D & E are ionic conduction paths formed by macro- or micro-cracks
and voids between the particles or in the binder. The electrolyte then fills these areas and
contributes to ionic conduction.

Morcillo et al go on to present SEM micrographs of unexposed coatings with zinc levels of 84%
and 50% by weight zinc. These are shown in figure 17.

Figure 17 SEM images of a) 84% & b) 50% by weight zinc ethyl silicate coating

Observing figure 17 it is apparent that there is a higher number density of zinc particles in (a)
thus increasing the particle contact. The zinc particles in (b) are very much individual in nature
with little contact with surrounding zinc particles. It is this level of zinc content (as in (b)) that
the subject of a recent publication in this journal. Morcillo et al go on to describe the formation
of corrosion products in these coatings. It is stated that the zinc particles will only be the site of
the anodic reaction of the corrosion process when in contact with the steel substrate, where the
cathodic reaction takes place. The corrosion product is said to form some way from the zinc
particles, in the capillaries full of electrolyte that facilitate the ionic conduction between the
anodic and cathodic zones. These capillaries are said to form in the favourable conditions in
ethyl silicate binders with high amounts of zinc present. The wetting of the particles by the
binder is of particular importance. Termed pseudo-wetting, the non-polar nature of the ethyl
silicate binder makes it difficult to wet the zinc particles, as opposed to binders of the epoxy type
that wet particles relatively easily (termed effective wetting).

Ginsberg illustrates the binder distribution in zinc rich ethyl silicate coatings. An idealised
approach suggests a particle completely surrounded by a uniform thickness of binder (figure 18a).
When considering the contact between particles Ginsbergsuggests a meniscus of binder is
formed between particles due to the surface tension (figure 18b)

Figure 18 Patterns of binder distribution in a zinc-rich coating

Morcillo 34 idealises the position of corrosion product formation when the zinc is in contact with
the substrate, as explained above, illustrated in figure 19. When the zinc is isolated the corrosion
process is located on the same surface i.e. the zinc particle wetted by the electrolyte. Morcillo
states that the corrosion products form in the locality of the particle, which increases the
electrode polarisation and reduces the zinc corrosion rate (figure 20)

Figure 19 Idealised representation by Morcillo of zinc particles and the corrosion product
when the zinc particles are in contact with steel. The particles are in contact as (a)
individual particles and (b) a cluster of particles.
Figure 20 Idealised representation by Morcillo of zinc particles and the corrosion product
when the zinc particles are isolated from the steel and each other. The particles are (a)
single and (b) a number of particles close together.

One of the differences between the inorganic ethyl silicate binder and organic binders containing
high zinc content can be seen when comparing the above idealised representations with an SEM
image produced by Theiler (figure 21). This shows a relatively thick layer of corrosion product
on the surface of a 95% by weight zinc organic coating. The internal film characteristics of the
organic coating does not allow for a similar mechanism to take place as in the ethyl silicate
organic coatings.

Figure 21 Corrosion product on the surface of an organic zinc rich coating , indicated by
the white arrow.

Extended protection of zinc containing coatings

It has been said by a number of authors that the protection afforded by zinc pigmented coatings
is longer than the period of cathodic protection suggests. There are a number of suggested
reasons as to this extended protection.

It has been suggested that there are two stages of protection: cathodic protection followed by
barrier formation. The investigation into barrier properties is usually carried out using
electrochemical impedance spectroscopy (EIS). EIS is generally used with organic coatings but
its use with inorganic zinc coatings will be shown.

The use of EIS with coatings, especially organic coatings, is well established and is frequently
presented . The use of EIS with zinc containing coatings is said to produce results unlike any
other type of coating

Lindquist in a study of commercial zinc containing coatings found that, in general, following 60
days immersion the coatings exhibited little galvanic action. This was founded by a high
impedance/resistance inferring low galvanic activity. The extended protection by the coatings
was attributed to the inhibitive properties of the zinc salts produced during the cathodic
protection stage. The extended performance was also said to be influenced by a high pH (9) in
the film.

Feliu states that the corrosion protection mechanism in zinc-rich coatings is in the first instance
cathodic protection, followed by a barrier effect of the coating pores being sealed by corrosion
products.

The use of EIS by Feliu shows the changing shape of the Nyquist plot illustrating the resistance
of the film. An example of this is given in figure 22.
Figure 22 Evolution with time of impedance diagrams (Nyquist) for zinc-rich silicate
coatings in 3.5% by weight sodium chloride solution, from Feliu

It is stated by Feliu that the coatings are currently in the cathodic protection stage where the high
frequency arc and low frequency tail (figure 22) correspond to the zinc coating behaving as a
porous electrode.

Once the coatings have passed the cathodic protection stage, Feliu states that the interpretation
of the high frequency arc and low frequency tail changes (figure 23). It is then said to show the
insulating characteristics of the binder and the zinc corrosion products on the zinc and steel.
Figure 23 - Evolution with time of impedance diagrams (Nyquist) for a zinc-rich silicate
coating containing 84% by weight zinc in 3.5% by weight sodium chloride solution, from
Feliu

It is stated by Feliu that an increase in time of the chord length of the higher frequency arc may
be attributed to a rise in the resistance of the coating due to:

Incorporation into the coating of insoluble and protective zinc corrosion products.
An increase in the average thickness of the insulating layer on zinc particles electrically
connected to the base steel.
A decrease in the number of zinc particles connected to the base steel.

The results of his work lead Feliu to conclude that there is a reinforcing of the barrier effect with
zinc contents greater than 90% by weight, when the zinc content drops to below 70% by weight
there are fewer possibilities for a barrier to develop and last, and at 50% by weight zinc there is
no barrier formation.
Scantlebury states that there is a combination of further protection within zinc-rich silicate
coatings. It is said that the extended period of protection is due to the inhibitive effect of zinc
salts at the surface combined with pore blocking by the corrosion product.

There is an agreement between Abreu Real and Szauer that a pore blocking mechanism by the
voluminous zinc corrosion product produced in the cathodic protection stage attains the barrier
effect.

The effect of zinc content

The zinc content and its particle size is important in determining the extent of cathodic protection
in a zinc-rich silicate coating. This is due to the relationship of specific surface area and the
desire for electrical continuity . The effect that the zinc content has on the cathodic protection
within the coatings has said to be governed by the binder and pigment material used .

Theiler states that there is an optimum zinc content for each type of binder material used. Too
much zinc results in a large anodic area compared to the cathodic area and a small current
density is drawn from the active zinc. This low current density allows the zinc to passivate by not
changing the pH within the film and the protective action is lost. A small anode area would result
in a high current density and the zinc would be used rapidly.

The PVC/CPVC ratio

The pigment volume concentration/critical pigment volume concentration (PVC/CPVC) is of


great importance to the successful performance of inorganic zinc-rich coatings. As has been
stated, contact between pigment and substrate is necessary to establish cathodic protection. If the
ratio is too low then there is total encapsulation of the pigment particles by the binder and inter-
particle contact is minimal. The number of internal pores within the film is also insufficient to
promote galvanic activity. Too much zinc would afford cathodic protection to the steel but with
the risk of having too little binder to keep the pigment on the steel substrate. The zinc pigment
would also be exposed and have an increased corrosion rate that would lead to a shorter life of
the coating.

However, it can be said that inorganic zinc rich primers are less susceptible to the requirement
for specific loading. The binder used is said to react with the coating and substrate rather than
encapsulation as with organic binders. The inorganic film is strong, inert, adhesive and heat
resistant as well as being quite porous. This porosity allows for electrolyte to pass through before
barrier properties take effect.
PVC is less than CPVC PVC is greater than
PVC = CPVC CPVC
Pigment is totally
encapsulated Insufficient binder to
fill all inter-particle
Film is strong & Pigment is just interstices
adhesive encapsulated
Film becomes porous
High electrical Film is cohesive and with reduced cohesion and
resistance adhesive but will conduct adhesion
electrical current
No cathodic Electrolyte will
protection provided Cathodic protection penetrate the film
occurs and anode
consumption is controlled Cathodic protection
occurs and anode
consumption is rapid

Figure 24 Effect of PVC/CPVC ratio on electrical properties of zinc-rich primers

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