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Amine Blushing and Blooming of Epoxy Binder

Systems in Protective Coatings

February 9, 2006

Ing. Toine Dinnissen

When certain epoxy binder systems are applied under low-temperature and/or high-humidity conditions, a
side effect of the curing reaction may appear on the coating or ooring surface.1 This side effect can
manifest itself as grey cloudiness; gloss reduction; a greasy, waxy layer; or as white crystals or patches. In
some instances it may not be visible. However, on contact with high humidity or water, the coated areas
can display opaque white marks. The appearance of these marks can occur during cure or even after cure is
completed. Although the exudate is, in principle, water soluble it will in most cases not wipe off easily with
water, thinners or solvents. Often it can only be removed by dry or wet sanding after the binder has cured
completely.

What Are Blushing and Blooming?

Blushing and blooming are two slightly different processes. Blushing, sometimes referred to as water
spotting, occurs when moisture condenses on a coating surface during the curing process. Sometimes the
moisture originates from within the porous substrate. It manifests itself as white patches or a milky, hazy
effect in clear coatings and may cause lack of gloss in pigmented coatings.

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Blooming, or leaching, is somewhat different from blushing. Blooming occurs when the amount of
condensate causes water-soluble compounds to migrate from the body of the coating to the coating
surface. When the moisture evaporates, the leached components will appear on the surface as sticky
deposits.

Severe blush or bloom will also cause signi cant surface irregularities, and these defects are serious
enough to cause additional light scattering, resulting in an even more whitened appearance.2

Blushing and Blooming Effects

Blush and bloom are surface defects that need to be avoided in an epoxy coating. They affect the coating
performance, as they can result in poor gloss retention, discoloration over time (yellowing), poor
overcoatability and intercoat adhesion. The most important of these effects is the reduced overcoatability,
i.e., insuf cient adhesion of a subsequent coating layer to the system due to surface energy modi cation.
In the case of the nal layer (topcoat), the mechanical and chemical properties are altered and the visual
appearance is worse. A similar phenomenon to the surface effects described above can occur at the
coating-substrate interface. If moisture containing dissolved carbon dioxide diffuses out of a porous
substrate, e.g., concrete, it can cause incomplete cure at the interface. The incomplete cure affects the
nal adhesion, which can explain the occasional delamination of epoxy ooring compounds.
Blush and bloom can be removed, but this adds time and cost to the coating/ ooring job.

Blushing and Blooming Causes

Blushing, and in some cases, blooming are chemical reactions.3 The chemical component of the epoxy
binder system, which causes the blushing or blooming, is in the curing agent. Low-molecular-weight
(primary) amines are typically hygroscopic and tend to react with atmospheric carbon dioxide and
moisture to form an ammonium carbamate according to the following simpli ed equation.
The greasy layers that can appear on some epoxy binder systems are largely the salts of ammonium (bi-)
carbonate. Depending on the type and formulation of the binder system, amine compounds on the surface
combine to varying degrees with CO2 (carbon dioxide) and water in humid air to form hydrates of amine
carbonate.

The net result of the above side reactions is that amine (active hydrogen) compounds, which were intended
to react with the epoxide compounds, are being consumed. As a consequence, not all epoxide groups react
with the curing agent, the stoichiometry is compromised and the net result is under curing.

Which Factors Play A Major Role?

There are several factors that play a role in the appearance of blush or bloom. However, two major factors
in uencing the formation of carbamate or carbonate are the humidity and the reaction rate of the amine
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with carbon dioxide relative to the epoxy-amine reaction rate.
Humidity (Condensation)

The humidity in the air changes continuously and can vary from hour to hour, even within relatively small
areas such as within one warehouse. If the substrate temperature falls below the dew point, moisture in
the air will condense on the substrate. Upon coating application, air from the spray gun and solvent
evaporation can lower the surface temperature of the coating. This effect is accentuated when very fast-
drying solvents or an unbalanced solvent mixture is used. The condensed moisture will cause the blushing
reaction with the amine compounds.

It is generally accepted in the coatings industry that the minimum surface temperature should normally be
at least 3 °C above the dew point before painting. An exception to this is offered by coatings that are
speci cally designed to be "moisture tolerant".

Blooming or leaching can occur in systems containing water-soluble ingredients. This may include curing
agents and additives that are components of solvent- or water-based coatings. Upon exposure to high
humidity, components can migrate (leach) to the surface, dissolve in the moisture and leave a shiny or
oily-looking deposit. If still liquid, the deposit can typically be washed off with soap and water. However, if
the blooming is too severe and saturates the surface before it is thoroughly dried, the result can be
discoloration, uneven gloss, drips, runs and even destruction of the binder.

Reaction Kinetics (Rate of Cure)

Amine blush and bloom relate to the reaction of an amine curing agent with moisture and/or carbon
dioxide in the air. The amine in question should, in fact, react with the epoxy resin rather than with
moisture or carbon dioxide. It is obvious that blush or bloom may be intensi ed when the rate of the
epoxy-amine reaction is retarded.

Temperature

As the temperature decreases, the reaction rate of the amine and epoxy resin is signi cantly decreased. As
a rule of thumb, for every 10 °C reduction in curing temperature the reaction rate will be reduced by a
factor of approximately two. The reduction in the cure rate of the epoxy-amine reaction provides the
(primary) amines more time to migrate to the surface and undergo additional competing reactions. If,
during this period, the environment is damp and cold, the reaction of the amine with CO2 and water is
favored, resulting in the formation of blush and bloom.

Curing Agent Type

Another important factor that plays a role in whether blushing or blooming might occur is the type of
curing agent. The propensity for blushing or blooming to occur is related directly to the structure of the
amine. Low-molecular-weight (cyclo) aliphatic amines, typically used in combination with epoxy resins,
are mostly hygroscopic and have a high vapor pressure. These types of products are very susceptible to
blushing or blooming. Aliphatic amines are mainly used as raw materials to prepare "advanced" curing
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agents or in heat cure applications, but they are also used in room-temperature applications where
appearance is not so important. An example of such an application would be grouting compounds
(mortars) for anchoring heavy machinery. In priming/sealing applications aliphatic amine curing agents
may also be used. Although the initial coating will be affected, the application of a subsequent layer in due
time might overcome the problem of blushing (see the section on Repair).

In order to eliminate the formation of blush or bloom, a wide range of modi ed amine curing agents has
been developed. The two major categories are epoxy-amine adduct hardeners and a special class of adduct
hardeners called Mannich-bases.

The epoxy-amine adduct curing agents are the largest category of products designed to have a reduced
tendency to blush. Epoxy-amine adducts are reaction products of liquid epoxy resin with an excess of
primary amine. Although epoxy-amine adducts still contain a large excess of free amine, they are less
hygroscopic and have a lower vapor pressure compared to the neat amines. Epoxy-amine adducts are less
sensitive to blush formation and, as a result, are better suited for coatings/ oorings, which cure under high
humidity/low temperature. A disadvantage of epoxy-amine adducts is their relatively high viscosity. In
order to reduce the viscosity, epoxy-amine adducts are often modi ed with solvents or plasticizers, such as
benzyl alcohol.

Mannich-base curing agents are adduct-type hardeners formed by the condensation of (aliphatic) amines,
phenol (derivatives) and formaldehyde. The phenolic hydroxyl group present in these types of molecules
has an accelerating effect on the epoxy-amine reaction rate. Moreover, Mannich-bases show better
compatibility with liquid epoxy resins than unmodi ed alkylene amines, as well as reduced blush/bloom
tendency and improved early water spot resistance. Special grades of Mannich-bases are products using
Cardanol, a major constituent of cashew nut shell liquid, as the phenol component. These types of
products, often referred to as phenalkamines, are reference materials in low-temperature, high-humidity
cure applications.

Accelerators

These products increase the epoxy-amine reaction rate and subsequently reduce the possibility of the
undesired blushing or blooming reactions. Controlled use of the amount and type of accelerator ensures
minimal impact on the cured binder performance. Although there are numerous products capable of
accelerating epoxy-amine reactions, the most commonly used are: tertiary amines (e.g. DMP-30 = 2,4,6-
tris-[dimethylaminomethyl]-phenol), phenol derivatives (e.g., nonylphenol), alcohols (e.g., benzyl alcohol)
or acids (e.g., salicylic acid). Be aware that adding accelerator will signi cantly reduce the pot life of the
binder system.

Resin Type

Bloom or blush is less likely to be formed in systems that have a fast epoxy-amine cure rate. The epoxy-
amine reaction rate is not only determined by the reactivity of the hardener (amine) but also by the
reactivity of epoxy resin.
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In order to reduce blush/bloom, epoxy resin components that reduce the reactivity should be avoided. For
instance, it is well known that aliphatic mono-functional reactive diluents, frequently used in ooring
applications, are low in reactivity. An example of an epoxy resin containing such reactive diluent would be,
for instance, D.E.R.* 324 epoxy resin. Reduction of the amount (D.E.R. 325 epoxy resin), or complete
elimination (D.E.R. 331 epoxy resin), of this reactive diluent from the binder formulation will enhance the
overall epoxy-amine reactivity.

Prevention
The majority of epoxy coating systems will tolerate a certain amount of humidity without being affected.
In order to reduce the risk of blushing or blooming some guidelines are suggested below.
To promote the epoxy-amine reaction rather than carbamate/carbonate formation, the use of industrial
dehumidi ers or heating systems (hot-air blowers) might be considered in con ned spaces. Note that gas-
burning engines (fork-lift trucks, etc.) as well as direct- red gas or kerosene heaters ("salamanders") will
considerably increase the carbon dioxide content in the air, which is typically around 350-1500 ppm.
Moreover, such direct- red heaters also produce signi cant amounts of water vapor.

Most coating systems are sensitive to very high levels of humidity and should not be applied when
moisture levels in the air are too high. Typically, for standard epoxy binder systems, a relative humidity of
85% at 21 °C or 75% at 10 °C should not be exceeded. Again, in con ned spaces, the use of industrial
dehumidi ers and/or hot air-blowers may assist in creating correct curing conditions.

The substrate temperature has to be at least 3 °C (5 °C is better) above the dew point before a ooring or
coating can be applied. Condensate on the substrate or coating will otherwise result in blush or bloom.
Note that, for spray application, special care has to be employed because fast solvent evaporation can
additionally reduce the coating temperature to below the dew point. Consider also the temperature drop in
the late afternoon or early evening to avoid the formation of "shadow areas."

Before coating a mineral substrate, an assessment of the moisture content in the substrate is essential. For
concrete oors the residual moisture content should typically not exceed 4% for regular epoxy binder
systems. Special epoxy binder systems are available for humid or "green" concrete allowing higher
moisture content.

In case the curing conditions are just inside the limits, but it is thought that the chances of
carbamate/carbonate formation are still (too) high, an additional precaution can be taken. Once the curing
agent and resin component have been mixed together, the polymerization reaction starts. The further the
polymerization reaction has advanced, the lower the chances of a reaction between the amine, carbon
dioxide and moisture in the surrounding air. Thorough mixing of the individual components and then
leaving the binder to "rest" in the mixing container before application will accomplish this. The pre-
reaction time, often referred to as the induction time, will react away most of the free amine (typically the
most reactive) and improve the compatibility between the resin component and the curing agent. Care has
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to be taken that the reaction does not advance too far; suf cient time should remain for the application of
the whole batch.

Repair
If, after all the prevention and precautions mentioned above, there are still signs of blush or bloom, then
there is still a chance to "rescue" the coating before more intensive repair is required.
One of the rst measures to employ upon observing the formation of haze in or on the coating is to apply
heat to the affected area. Note that heat should not be applied directly to the coating. Under non-
controlled conditions (outside) this might be more dif cult to do than in con ned spaces, especially given
the limited time available.

Epoxy resin-based sealers/primers applied on mineral substrates, such as concrete, are prone to blushing,
as moisture from the porous surface can be absorbed immediately prior to curing. The primer can become
milky as a result of such moisture entrapment. Sometimes this phenomenon can be "repaired" by
immediately applying an additional coat of the same solvent-containing product or by saturating the
coating with solvent. The new layer of solventborne coating or the neat solvent will usually
soften/plasticize the coating suf ciently to allow the entrapped moisture to be released and the
microscopic water droplets causing the white haze to disappear.

In case a coating has been affected, it can still be possible to apply a second, lled layer without grinding.
The lled layer must be applied, however, before the rst affected coating has been allowed to thoroughly
cure. The new epoxy layer will "dissolve" the top layer of the "old" coat and fuse "chemically." Naturally it
must be ensured that the new coat will not also be susceptible to blushing or blooming. If the coating has
completely dried, minor blushing may be corrected by compounding or polishing. Repeated washing
operations may, in some cases, bring improvement. Whereas some applicators use water, others report
success with a citric acid solution or dilute vinegar.

Severe blushing, however, will require sanding and re nishing. Grinding the top surface of a coating
produces a lot of dust, which will require adequate worker protection. In some other cases the coating
must be removed entirely before recoating. This has a big impact on the time and amount of labor needed
to complete a painting job, making the application much more expensive than anticipated.

References
1 Croll, S.G. Atmospheric gasses and the hardening of an amine cured epoxy coating. J. Ctgs. Tech. 1980,
51, No 664, 65-69.
2 Lucas, P.A.; Clark, P.A.; Haney, R.J.; Kittek, M.R. Investigation of waterspot and blush resistance of epoxy
industrial oors. Air Products and Chemicals Inc., presented at the American Concrete Institute
Conference, 1997, Seattle, WA.

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3 Burton, B.L. Amine-blushing problems? No sweat! Huntsman Corp., presented at the Epoxy Resin
Formulators' meeting, The Society of the Plastics Industry, fall 2001.
References to "Dow" or the "Company" mean The Dow Chemical Company and its consolidated subsidiaries
unless otherwise expressly noted.

For further information, visit Dow's website at www.dow.com.

Ing. Toine Dinnissen, Technical Specialist, Epoxy Products

and Intermediates/Dow Deutschland GmbH & Co.,
Rheinmuenster, Germany

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