Truth & Consequences
Solvent Entrapment and Osmotic Blistering
W
ith coatings, the
emphasis always
seems to be on the
resin, curing agent, and pigment. One
generally chooses a polyamide epoxy,
an epoxy novolac, a coal tar epoxy, a
glass flake-filled epoxy phenolic, etc.
Little or no attention is given to the par-
ticular solvents that are employed. One
only sees solvents emphasized when a
coating is solventless or water-based.
Paint solvent controls application prop-
erties and so thinning decisions are gen-
erally left to the applicator. But small
amounts of retained solvent in dried
films can cause osmotic blistering. In
that regard, solvents are significant, and
some are bigger offenders than others.
For example, glycol ether solvents
are prime candidates for causing osmot-
ic blistering because they provide the
right combination of being slow and eas-
ily retained, with a very high if not infi-
nite water solubility. Ketones have suf-
ficient water solubility, approximately
26 g/100 ml for methyl ethyl ketone
(MEK), to present an osmotic threat, but
these are fast solvents that are not read-
ily retained. Aromatics such as xylene
are sufficiently slow (BP 144 C/291 F),
but the water solubility is much too low
to present an osmotic threat.
A tiny amount of retained glycol
ether solvent can cause blistering in
water immersion service. There is likely
to be no tangible evidence of the built-in
problem. The coating can be of correct
thickness and hardness. Adhesion test-
ing per ASTM D4541 wont identify the
problem. Solvent rubbing per ASTM
D5402 provides a crude assessment of
cure in terms of crosslinking, but it
24
By Mark Schilling, Consultant
Osmotic blistering
Courtesy of the author
doesnt indicate whether drying is com-
plete. Retained solvents in a dried film
can pose a problem for high-voltage hol-
iday testing but so little retained sol-
vent is required to cause blistering, and
HV holiday testing isnt discerning.
People have tried to be clever and
innovative in coming up with some
quick and practical methods for field
assessment of solvent retention. I have
seen a sniff test specified for tank lin-
ings, wherein one cups ones hands
against the coating and tries to smell
paint solvent. The specification cau-
Selected Glycol Ether Solvents
EM
CAS Number 109-86-4 110-80-5 2807-30-9 111-76-2 107-98-2 1569-01-3
Boiling point C/F 124/257 136/277 150/302 171/340 120/248
Evaporation rate 0.5
n-butyl acetate = 1.0
Vapor pressure 9.5
@ 25 C
(mm Hg)
Water solubility
Key: EM: ethylene glycol methyl ether; EE: ethylene glycol ethyl ether; EP: ethylene glycol n-propyl ether;
EB: ethylene glycol butyl ether; PM: propylene glycol methyl ether; PP: propylene glycol n-propyl ether
Note: Water solubility=Water in solvent
JPCL / February 2004 / PCE
tions, Be aware that your nose may
become sensitized to odors in the tank.
Another approach is the now legendary
butter test. Place a pat of butter in
direct contact with the coating under a
glass or some suitable cover for approx-
imately 15 minutes. Then take the pat
of butter outside of the tank and sniff it.
To be fair, these sniff tests are not com-
pletely without merit. But dont expect
them to show up in an industry consen-
sus standard any time soon.
Soluble salt contamination gets all the
attention because people are selling sol-
uble salt test kits, inspector time and
effort to do the testing, and of course,
proprietary rinse-aid treatments to
eliminate salts and prevent flash-rust-
ing. When it comes to solvent entrap-
ment, coating inspectors just dont have
anything in their tool box that enables
ready detection. Accordingly, the best
approach is prevention. Glycol ether
solvent is not a necessity, and so epoxy
coatings with little or no glycol ether
solvent content may be specified.
Thinner addition needs to be consid-
ered. Some epoxy coatings do not con-
EE EP EB PM PP
149/300
0.3 0.2 0.08 0.7 0.2
5.5 1.3 0.8 10.3 3.1
www.paintsquare.com
tain glycol ether but it may be added by
one of the manufacturers approved
thinners. The MSDSs will reveal the sol-
vent composition of the coating and
applicable thinners. The choice need not
be left strictly to the contractor, who is
thinning for applicability.
There are several coating application
factors that can come into play with
regard to solvent retention:
high paint film thickness,
low ambient or substrate tempera-
tures,
high relative humidity during paint
application and drying/curing,
inadequate air circulation inside a
confined space (tank or vessel) during
drying/curing,
using the wrong thinner or an
excessive amount of thinner, and
putting the lining in service too soon.
Any condition or combination of con-
ditions that hinder drying promotes sol-
vent retention. The thing to consider is
that epoxy coatings that contain glycol
ether solvent are more prone to osmot-
ic blistering. This is not to say that
epoxy coatings which contain glycol
ethers are in any way defective, and
therefore not fit for their intended pur-
pose. Rather, its simply to advise that
epoxies that do contain glycol ethers are
likely to be more problematic, more
prone to blistering. Its on the MSDS so
you can see it and plan accordingly.
Osmotic blistering is a common coat-
ing failure mode, but the mechanism
seems mysterious to most people
because the high pressure (which can be
several hundred psi) remains unseen.
When punctured, coating blisters dont
release pressure by violently spurting
out their liquid contents. Most coatings
simply do not have the elastic, rapid
relaxation response of a rubber band or
an exploding balloon. But there are
other reasons the pressure isnt obvi-
ous. Its not pressure in the simple and
familiar sense of hydraulics (although in
reverse osmosis, one does apply a pres-
Continued

www.paintsquare.com JPCL / February 2004 / PCE 25

 Truth & Consequences

sure to salt water to produce clean

water on the other side of the mem-
brane). As a coating failure mode,
osmotic blistering occurs via many
small steps, and the pressure is spent in
overcoming coating adhesion and in
permanently deforming the coating film
into blisters. The penetrating water that
causes blistering effectively dilutes the
hydrophilic substances (solvent or
salts), and the dilution lowers the pres-
sure. This explains what most all of us
have observedcoatings may blister
early but the process tends to slow
down and stabilize over time. Corrosion
of the steel is almost always negligible
as long as the blister caps remain intact.
If an epoxy coating fails by blistering
in a wet service environment such as a
potable water tank lining, the blister liq-
uid may have a faint, slightly sweet
odor of glycol ether solvent. The taste
and odor of the stored water need not
be affected. The amount of retained gly-
col ether solvent needed to cause
osmotic blistering of the coating is tiny,
and although some small amount may
be extracted from the coating into the
water, the resulting concentration
would be negligible. Solvent related
taste and odor in potable water is a
gross and immediate problem. Osmotic
blistering is a comparatively slow
process that occurs well below the
radar screen of the taste and odor
threshold for the stored water.
I do not advocate the specification of
sniff tests because I dont know how
to calibrate a nose. However, you can
detect the odor of glycol ether solvent
at a very low level in coating blister liq-
uid (<1%). If you have a suspicious blis-
tering failure of an epoxy water tank
lining, give it a try. Current wisdom, if
I can call it that, is that soluble salt con-
tamination is pretty much the only
cause of osmotic blistering. Dont be so
sure. The nose knows, and the presence
of glycol ether may be quickly and inex-
pensively confirmed in a laboratory by
gas chromatography.

26 JPCL / February 2004 / PCE www.paintsquare.com