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Amine Blushing and Blooming of Epoxy

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By Ing. Toine Dinnissen
Dow Deutschland GmbH & Co. OHG
When some 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 flooring surface. 1 This side effect can mani-
fest itself as grey cloudiness; gloss reduction; a greasy,
waxy layer; or white crystals or patches. In some
instances, it may not be visible; however, in contact
with high humidity or water, the coated areas can dis-
play opaque white marks. These marks can appear
during or after cure. They are the results of two slight-
ly different processes, blushing or blooming. This arti-
cle will define blushing and blooming of epoxies,
explain the causes, describe their effects on coatings,
and provide preventive measures as well as remedies.
Amine blush. Courtesy of the author

This article will help you


understand, identify,
remedy, and avoid
amine blushing and
blooming on concrete
and other substrates.
Amine bloom. Courtesy of Fitz’s Atlas™ of Coating Defects

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Binder Systems in Protective Coatings
Blushing and Blooming
Defined Briefly
Blushing, sometimes referred to as
water spotting, occurs when moisture
condenses on a coating surface during
the curing process. Sometimes, the
moisture can originate from within
cause significant surface irregularities.
These defects are serious enough to
cause additional light scattering,
resulting in an even more whitened
appearance.2

How Do Blush and Bloom Affect


What Causes Blushing
and Blooming?
Blushing and blooming are chemical
reactions.3 The chemical component of
the epoxy binder system that causes
the blushing or blooming is the curing
agent. Typically, low molecular weight
the porous substrate. Blushing can Coating Per f o r m a n c e ? (primary-) amine curing agents are
manifest itself as white patches or it Blush and bloom are surface defects hygroscopic (that is, they readily
can have a milky, hazy appearance in that must be avoided when using an absorb moisture). These amines tend to
otherwise clear coatings. It may cause epoxy coating because they affect react with atmospheric carbon dioxide
lack of gloss in pigmented coatings. coating performance. They can result and moisture to form an ammonium
Blooming (or leaching) is somewhat in poor gloss retention, discoloration carbamate, as represented in the fol-
different from blushing. Blooming over time (yellowing), and poor over- lowing simplified equation.
occurs when the amount of conden- coating ability as well as poor inter-
sate causes water-soluble compounds
to migrate from the body of the coat-
coat adhesion. The most important of
these effects is the reduced overcoat-
R–NH2 + CO2 R–NH–C–O- +NH3–R
ing to the coating surface. When the ing ability, that is, insufficient adhe-
moisture evapo- sion of a subsequent coating layer to O
rates, the leached the system due to surface energy mod- The greasy layers that can appear on
components will ification. In the case of the final layer some epoxy binder systems are largely
appear on the sur- (an epoxy topcoat), the mechanical the salts of ammonium (bi-) carbonate.
face as sticky and chemical properties are altered, Depending on the type and formula-
deposits. Although and the visual appearance is poor. tion of the binder system, amine com-
the exudate A phenomenon similar to the sur- pounds on the surface combine to
(leachate) is, in face effects described above can occur varying degrees with CO 2 (carbon
principle, water at the coating-substrate interface. dioxide) and water in humid air to
soluble in most Moisture that contains dissolved car- form hydrates of amine carbonate.
cases, it will not bon dioxide can cause incomplete
wipe off easily
with water, thin-
cure. If this moisture comes out of a
porous substrate such as concrete,
R–NH2 + CO2 + H2O [R–NH3]2+ 2-CO3
ners or solvents. then the incomplete cure occurs at the The net result of the above side reac-
Often, the exudate coating/concrete interface. The tions is that amine (active hydrogen)
can be removed incomplete cure affects the final adhe- compounds are being consumed
only by dry or wet sion, which can explain the occasional instead of reacting with the epoxide
sanding after the delamination of epoxy flooring com- compounds as was intended. As a con-
binder has com- pounds. sequence, not all epoxide groups can
pletely cured. Blush and bloom can be removed react with the curing agent and the sto-
Severe blush or but this will add time and costs to the ichiometry is compromised. The net
bloom will also coating/flooring job. result is under-curing..

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What Factors Play Reaction Kinetics (Rate of Cure) affected, the application of a subsequent
A Major Role? Amine blush and bloom relate to the layer in due time might overcome the
Several factors play a role in the appear- reaction of an amine curing agent with problem of blushing (see the section
ance of blush or bloom. Two major fac- moisture and/or carbon dioxide in the below on repair).
tors influencing the formation of carba- air. The amine in question should, in fact,
mate or carbonate are humidity and the react with the epoxy resin rather than Formulation Remedies
reaction rate of the amine with carbon with moisture or carbon dioxide. Curing Agents
dioxide, relative to the amine-epoxy Therefore, blush or bloom may be inten- To eliminate the formation of blush or
reaction rate. A third factor is the type sified when the reaction speed of the bloom, a wide range of modified amine
of curing agent. epoxy-amine reaction is slowed. curing agents has been developed. The
Temperature affects the reaction rate. two major categories are epoxy-amine
Humidity (Condensation) As the temperature decreases, the reac- adduct hardeners and a special form of
The humidity in the air changes continu- tion rate of the amine and epoxy resin is adduct hardeners, Mannich-bases.
ously and can vary from hour to hour, significantly decreased. As a general The epoxy-amine adduct curing agents
even within relatively small areas such rule, for every 10 degrees C reduction in are the largest category of products
as a single paint shop. curing temperature, the reaction rate designed to have a reduced tendency to
If the substrate temperature falls will be reduced by a factor of approxi- blush. Epoxy-amine adducts are reaction
below the dew point, moisture in the air mately 2. The reduction of the cure rate products of liquid epoxy resin with an
will condense on the substrate. of the epoxy-amine reaction provides excess of primary amines. Although
During coating application, air from more time for the (primary-) amines to epoxy-amine adducts still contain a large
the spray gun and solvent evaporation migrate to the surface and undergo alter- excess of free amine, they are less hygro-
can lower the surface temperature of native reactions. If, during this period, scopic and have a lower vapor pressure
the coating. This effect is accentuated the environment is damp and cold, the compared to the neat amines. Epoxy-
when a very fast-drying solvent or an reaction of the amine with CO2 and amine adducts are less sensitive to blush
unbalanced solvent mixture is used. The water is favored, resulting in the forma- formation and, as a result, are better suit-
condensed moisture will cause the tion of blush and bloom. ed for coatings/floorings that cure under
blushing reaction with the amine com- high humidity, low temperature, or both.
pounds. Curing Agent T ype A disadvantage of epoxy-amine adducts
It is generally accepted in the coatings Another important factor, the type of is their relatively high viscosity. In order
industry that the minimum surface tem- curing agent, plays a role in whether to reduce their viscosity, epoxy-amine
perature should normally be at least 3 blushing or blooming might occur. The adducts are often modified with solvents
degrees C (5 degrees F) above the dew propensity for blushing or blooming to or plasticizers, such as benzyl alcohol.
point before painting. Paint specifically occur is related directly to the structure Mannich-base curing agents are
designed for moisture tolerance is an of the amine. adduct-type hardeners formed by the
exception to this rule. Low molecular weight (cyclo-) aliphat- condensation of (aliphatic-) amines, phe-
Blooming or leaching can occur in sys- ic amines, typically used in combination nol (derivatives), and formaldehyde. The
tems containing water-soluble ingredi- with epoxy resins, are mostly hygro- phenolic hydroxyl group present in these
ents. This may include curing agents and scopic and have a high vapor pressure. types of molecules has an accelerating
additives that are components of sol- These types of products are very suscep- effect on the epoxy amine reaction rate.
vent- or water-borne coatings. Upon tible to blushing or blooming. Aliphatic Moreover, Mannich-bases show better
exposure to high humidity, these compo- amines are mainly used as raw materials compatibility with liquid epoxy resins
nents can migrate (leach) to the surface, to prepare “advanced” curing agents or than unmodified alkylene amines; a
dissolve in the moisture, and leave a in heat-cure applications, but they are reduced tendency to blush/bloom; and
shiny or oily-looking deposit. If still liq- also used in room-temperature applica- an improved early waterspot resistance.
uid, the deposit usually can be washed tions where appearance is not as impor- Special grades of Mannich-bases are
off with soap and water. However, if the tant. An example of such an application products using cardanol, a major con-
blooming is too severe and saturates the would be grouting compounds (mortars) stituent of cashew nut shell liquid, as the
surface before it is thoroughly dried, the for anchoring heavy machinery. In prim- phenol component. These types of prod-
result can be discoloration, uneven gloss, ing/sealing applications, aliphatic amine ucts, often referred to as phenalkamines,
drips, runs, and even destruction of the curing agents may also be used. are reference materials in low-tempera-
binder. Although the initial coating will be ture, high-humidity cure applications.

42 JPCL / December 2005 / PCE www.paintsquare.com


Accelerators (“salamanders”) will considerably resin component have been mixed
These products increase the epoxy increase the carbon dioxide content in together, the chemical polymerization
amine reaction rate and subsequently the air, which is typically around 350- reaction starts. The further the polymer-
reduce the possibility of the undesired 1500 ppm,. Moreover, such direct-fired ization reaction has advanced, the lower
blushing or blooming reactions. heaters also produce significant amounts the chances of a reaction between the
Controlled use of the amount and type of water vapor, thereby increasing the amine and the carbon dioxide and mois-
of accelerator ensures minimal impact risk of a reaction between moisture in ture of the surrounding air. Thoroughly
on the cured binder performance. the air, carbon dioxide, and the amine to mixing the individual components and
Although many products can accelerate form carbamate or carbonate. (It should then leaving the binder to “rest” in the
amine-epoxy reactions, the most com- be noted that without proper safety mixing container before application will
monly used are tertiary-amines (e.g., measures in place, heaters can put work- accomplish this. During this pre-reaction
DMP-30 = 2,4,6-Tris ers at risk in confined spaces.) time, often referred to as the induction
[Dimethylaminomethyl]-phenol), phenol- Most coating systems are sensitive to time, most of the free amine will be
derivatives (e.g. Nonylphenol), alcohols very high levels of humidity and should removed by reaction (as these are typi-
(e.g., Benzyl alcohol), or acids (e.g. sali- not be applied when moisture levels in cally the most reactive) and thus
cylic acid). However, adding accelerator the air are too high. Typically, for stan- improve the compatibility between the
will significantly reduce the pot-life of dard epoxy binder systems, a relative resin component and the curing agent.
the binder system. humidity of 85% at 21 C or 75% at Care has to be taken that the reaction
10 C should not be exceeded. Again, in does not advance too far; sufficient time
Resin T ype confined spaces, the use of industrial should remain for the application of the
Bloom or blush is less likely to be formed dehumidifiers and/or hot air-blowers whole batch.
in systems that have a fast epoxy-amine may assist in creating correct curing con-
cure rate. The epoxy amine reaction rate ditions. Repair
is not only determined by the reactivity The substrate temperature has to be If, after all the prevention techniques
of the hardener (amine) but also by the at least 3 C (5 C is better) above the dew and precautions mentioned above, there
reactivity of the epoxy resin. point before a flooring or coating can be are still signs of blush or bloom, then
To reduce blush/bloom, epoxy resin applied. Condensate on the substrate or there is still a chance to “rescue” the
components that reduce the reactivity coating will otherwise result in blush or coating before more intensive repair is
should be avoided. For instance, it is well bloom. Note that for spray application, required.
known that aliphatic mono-functional special care has to be employed because One of the first things to do when you
reactive diluents, frequently used in fast solvent evaporation can further see the formation of haze in or on the
flooring applications, are low in reactivi- reduce the coating temperature to below coating is to apply heat to the affected
ty. Reduction of the amount or complete the dew point. Consider also the temper- area. Note: Do not apply the heat direct-
elimination of these reactive diluents ature drop in the late afternoon or early ly to the coating; heat only the environ-
from the binder formulation will evening; by not applying the coating dur- ment of the coating. Under non-con-
enhance the epoxy-amine reactivity. ing this time, the painter can avoid the trolled conditions (outside), applying heat
formation of “shadow areas.” might be more difficult to do than in
Prevention in the Field Before coating a mineral substrate, an interior spaces, especially given the limit-
The majority of epoxy coating systems assessment of the moisture content in ed time available.
will tolerate a certain amount of humidi- the substrate is essential. For concrete Epoxy resin-based sealers/primers
ty without being affected. Some guide- floors, the residual moisture content applied on mineral substrates such as
lines are suggested below to reduce the should typically not exceed 4% for regu- concrete are prone to blushing because
risk of blushing or blooming. lar epoxy binder systems. Special epoxy moisture from the porous surface can be
In order to promote the epoxy-amine binder systems are available for humid absorbed immediately before curing. The
reaction rather than carbamate/carbon- or “green” concrete, allowing higher primer can become milky as a result of
ate formation, the use of industrial dehu- moisture content. such moisture entrapment. Sometimes
midifiers or heating systems (hot-air In case the curing conditions are just this phenomenon can be “repaired” by
blowers) might be considered in confined inside the limits and the chances of car- immediately applying an additional coat
spaces. However, note that gas burning bamate/carbonate formation are still of the same solvent-borne product or by
engines (fork-lift trucks, etc.) as well as (too) high, an additional precaution can saturating the coating with solvent. The
direct-fired gas or kerosene heaters be taken. Once the curing agent and new layer of solvent-borne coating or

44 JPCL / December 2005 / PCE www.paintsquare.com


the neat solvent will usually soften/plas- Epoxy Coating,” Journal of Coatings Institute Conference, Seattle, WA.
ticize the coating sufficiently to allow the Technology, 51, No 664, 65-69 Burton, Bruce L, Huntsman
entrapped moisture to be released and (1980). Corporation, “Amine-Blushing
the microscopic water droplets that Lucas, P.A., Clark, P.A., Haney, R.J., Problems? No Sweat!,” presented at
caused the white haze to disappear. Kittek, M.R., Air Products and the Fall 2001 Epoxy Resin
In case a coating has been affected, it Chemicals Inc., “Investigation of Formulators’ meeting of the Society
can still be possible to apply a second, Waterspot and Blush Resistance of of the Plastics Industry.
pigmented layer without abrading the Epoxy Industrial Floors,” presented
surface. The pigmented layer must be at the 1997 American Concrete
applied, however, before the first affect-
ed coating layer has thoroughly cured.
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 com-
pounding or polishing. Repeated washing
operations may, in some cases, bring
improvement. Whereas some applicators
use water, others report successes with a
citric acid solution or dilute vinegar.
Severe blushing, however, will require
sanding and refinishing. Grinding the top
surface of a coating produces dust, which
will require adequate worker protection.
In some other cases, the coating must be
removed entirely before recoating. Total
removal 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.

Summary
Blushing and blooming of epoxy resin
binders can be identified in the field, pre-
vented through formulation or applica-
tion techniques, or remedied without
total coating removal. Understanding
blushing and blooming phenomena will
help in terms of prevention or repair,
although prevention is always better.
The formulation and the cure conditions
should be such that the probability of
blush and bloom formation is minimized.

References
Croll, S.G., “Atmospheric Gasses and the
Hardening of an Amine Cured

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