Blisters

The blistering of gel coated, FRP structures has received much attention in recent years. The
defect manifests itself as a localized raised swelling of the laminate in an apparently random
fashion after a hull has been immersed in water for some period of time. When blisters are
ruptured, a viscous acidic liquid is expelled. Studies have indicated that one to three percent of
boats surveyed in the Great Lakes and England, respectively, have appreciable blisters. [4-29]
There are two primary causes of blister development. The first involves various defects
introduced during fabrication. Air pockets can cause blisters when a part is heated under
environmental conditions. Entrapped liquids are also a source of blister formation. Table 4-2
lists some liquid contaminate sources and associated blister discriminating features.
Table 4-2 Liquid Contaminate Sources During Spray-Up That Can Cause Blistering
[Cook, Polycor Polyester Gel Coats and Resins]
Liquid Common Source Distinguishing Characteristics
Catalyst
Overspray, drips due to leaks of
malfunctioning valves.
Usually when punctured, the blister has a
vinegar-like odor; the area around it, if in
the laminate, is browner or burnt color.
If the part is less than 24 hours old, wet
starch iodine test paper will turn blue.
Water
Air lines, improperly stored
material, perspiration.
No real odor when punctured; area around
blister is whitish or milky.
Solvents
Leaky solvent flush system,
overspray, carried by wet rollers.
Odor; area sometimes white in color.
Oil Compressor seals leaking.
Very little odor; fluid feels slick and will not
evaporate.
Uncatalyzed Resin
Malfunctioning gun or ran out of
catalyst.
Styrene odor and sticky.
Even when the most careful fabrication procedures are followed, blisters can still develop over
a period of time. These type of blisters are caused by osmotic water penetration, a subject that
has recently been examined by investigators. The osmotic process allows smaller water
molecules to penetrate through a particular laminate, which react with polymers to form larger
molecules, thus trapping the larger reactants inside. A pressure or concentration gradient
develops, which leads to hydrolysis within the laminate. Hydrolysis is defined as
decomposition of a chemical compound through the reaction with water. Epoxide and
polyurethane resins exhibit better hydrolytic stability than polyester resins. In addition to the
contaminants listed in Table 4-2, the following substances act as easily hydrolyzable
constituents: [4-30]
Glass mat binder;
Pigment carriers;
Mold release agents;
Chapter Four PERFORMANCE
197
Stabilizers;
Promoters;
Catalysts; and
Uncross-linked resin components.
Blisters can be classified as either coating blisters or those located under the surface at
substrate interfaces (see Figure 4-18). The blisters under the surface are more serious and will
be of primary concern. Some features that distinguish the two types include:
Diameter to height ratio of sub-gel blister is usually greater than 10:1 and
approaches 40:1 whereas coating blisters have ratios near 2:1;
Sub-gel blisters are much larger than coating blisters;
The coating blister is more easily punctured than the sub-gel blister; and
Fluid in sub-gel blisters is acidic (pH 3.0 to 4.0), while fluid in coating
blisters has a pH of 6.5 to 8.0.
Both types of blisters are essentially cosmetic problems, although sub-gel blisters do have the
ability to compromise the laminate's integrity through hydrolytic action. A recent theoretical
and experimental investigation [4-31] examined the structural degradation effects of blisters
within hull laminates. A finite element model of the blister phenomena was created by
progressively removing material from the surface down to the sixth layer, as shown in Figure
4-19. Strain gage measurements were made on sail and power boat hulls that exhibited severe
blisters. The field measurements were in good agreement with the theoretically determined
values for strength and stiffness. Stiffness was relatively unchanged, while strength values
degraded 15% to 30%, usually within the margin of safety used for the laminates.
198
Blisters Marine Composites
Figure 4-18 Structure Description for a Skin Coated Composite with: Layer A = Gel
Coat, Layer B = Interlayer and Layer C = Laminate Substrate [Interplastic, A Study of
Permeation Barriers to Prevent Blisters in Marine Composites and a Novel Technique for
Evaluating Blister Formation]
The fact that the distribution of blisters is apparently random has precluded any documented
cases of catastrophic failures attributed to blistering. The Repair Section (page 285) of this
document will deal with corrective measures to remove blisters.
As was previously mentioned, recent investigations have focused on what materials perform
best to prevent osmotic blistering. Referring to Figure 4-18, Layer A is considered to be the
gel coat surface of the laminate. Table 4-3 lists some permeation rates for three types of
polyester resins that are commonly used as gel coats.
Table 4-3 Composition and Permeation Rates for Some Polyester Resins used
in Gel Coats [Crump, A Study of Blister Formation in Gel Coated Laminates]
Resin Glycol
Saturated
Acid
Unsaturated
Acid
Permeation Rate*
H
2
O @ 77F H
2
O @ 150F
NPG Iso
Neopentyl
glycol
Isophthalic
acid
Maleic
anhydride
0.25 4.1
NPG Ortho
Neopentyl
glycol
Phthalic
anhydride
Maleic
anhydride
0.24 3.7
General
Purpose
Propylene
glycol
Phthalic
anhydride
Maleic
anhydride
0.22 3.6
*grams/cubic centimeter per day x 10
-4
Investigators at the Interplastic Corporation concentrated their efforts on determining an
optimum barrier ply, depicted as Layer B in Figure 4-18. Their tests involved the complete
submersion of edge-sealed specimens that were required to have two gel coated surfaces. The
conclusion of this study was that a vinyl ester cladding applied on an orthophthalic laminating
resin reinforced composite substantially reduced blistering.
Investigators at the University of Rhode Island, under the sponsorship of the U.S. Coast Guard,
conducted a series of experiments to test various coating materials and methods of application.
Table 4-4 summarizes the results of tests performed at 65C. Blister severity was subjectively
evaluated on a scale of 0 to 3. The polyester top coat appeared to be the best performing scheme.
199
Chapter Four PERFORMANCE
Figure 4-19 Internal Blister Axisymetric Finite Element Model [Kokarakis and Taylor,
Theoretical and Experimental Investigation of Blistered Fiberglass Boats]
Table 4-4 Results from URI Coating Investigation
[Marino, The Effects of Coating on Blister Formation]
Coating Scheme Surface Treatment
Blister
Initiation Time
(days)
Blister
Severity
Blisters
Present?
Epoxy top coat
none 5 3 Yes
sanding 5 1 Yes
acetone wipe 5 1 Yes
both 5 1 Yes
Polyurethane top
coat
none 5 2 Yes
sanding 14 1 Yes
acetone wipe ? 1 Yes
both ? 1 Yes
Polyester top coat
none - 0 No
sanding - 0 No
acetone wipe - 0 No
both - 0 No
Epoxy top coat
over epoxy
none 8 3 Yes
sanding 8 1 Yes
acetone wipe 8 2-3 Yes
both 8 2 Yes
Polyurethane top
coat over
polyurethane
none 7 1 Yes
sanding 7 1 Yes
acetone wipe 7 1 Yes
both 7 1 Yes
Polyester top coat
over polyester
none 8 3 No
sanding - 0 No
acetone wipe 8 2 No
both 8 1 No
Epoxy top coat
over polyurethane
none 8 3 Yes
sanding 8 2 Yes
acetone wipe 17 1-2 ?
both 19 2 Yes
Polyurethane top
coat over epoxy
none 11 3 Yes
sanding - 0 Yes
acetone wipe 11 1-3 Yes
both - 1 Yes
200
Blisters Marine Composites
Coating Scheme Surface Treatment
Blister
Initiation Time
(days)
Blister
Severity
Blisters
Present?
Polyurethane top
coat over polyester
none 6 3 Yes
sanding 6 3 Yes
acetone wipe 6 3 Yes
both 6 1 Yes
Epoxy top coat
over polyester
none 9 3 Yes
sanding 9 3 Yes
acetone wipe 9 3 Yes
both 9 3 Yes
Blister Severity Scale
0 no change in the coated laminate
1 questionable presence of coating blisters; surface may appear rough, with rare,
small pin size blisters
2 numerous blisters are present
3 severe blistering over the entire laminate surface
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Chapter Four PERFORMANCE