Technology

T
Microbiologically-Influenced
Attack of Coatings
By Clive H. Hare, Coating System Design, Inc.

aints and coating films are and water in the presence of sunlight.
T RO U B L E W I T H PA I N T
vulnerable to a range of bi- Fungi (mold and mildew) may be
ological attacks. These may range from the en- found widely both indoors and outdoors (particularly on
zymatic attack of primitive bacteria to the colonization of the north or sun-sheltered sides of structures). Algae are al-
larger, relatively advanced marine species such as barna- most always found outside, especially where sunlight is
cles, mussels, etc. Biological attack may be sub-catego- present.
rized by Wet Paint Infestation1,2
• the selective bacterial infestation of certain raw materi- As noted above, the in-can spoilage of latex paints, includ-
als of water-borne paints (before or after compounding); ing latex maintenance paints, is bacterial. It occurs in the
• bacterial and fungal attack on protective coatings lead- finished can of paint and in the paint plant where it may
ing to microbiologically-influenced corrosion of metallic destroy latex binders and other raw materials stored in
substrates and rot in wood; bulk. Attack is confined to water-borne systems because
• mold and mildew (fungus) growth, as
well as the disfigurement of applied films
” the gram negative bacteria (mainly
pseudomonas aeruginosa) that initiate
by algae in moist environments; and Given a supply of the attack cannot exist outside of the
• the affixation and growth of larger aqueous environment. (A minimum
species (both plants and animals) on sub- moisture, virtually moisture content of 35% is required.)
merged coated (and uncoated) surfaces If a bacterial inhibitor is not used,
in the marine environment (marine foul- any composition certain raw materials in water-borne
ing, as discussed in Trouble with Paint in paints are highly suited to the support
the June 2000 JPCL, pp. 50-65).
or any substrate of bacterial growth. In an environment
In all cases, the key to growth is mois- of suitable pH and temperature, fungal
ture; in the absence of water no micro-or-
is vulnerable to growth is supported at lower moisture
ganisms can grow. Given a supply of microbiologically- levels. Rarely does in-can attack in-
moisture, virtually any composition or volve fungi. The specifics of the envi-
any substrate is vulnerable to microbio- influenced ronmental conditions will, in large

”
logically-influenced deterioration. part, determine which microbe will in-
This month, we will discuss wet paint
deterioration. habit a particular environment and
infestation, the growth of fungi and algae, how fast it will grow.
the defacement and deterioration of painted and un-paint- The contaminating organisms that initiate the attack may
ed surfaces, and the more common control strategies. For come from the water used in the manufacture of the paint
the past 30 years or so, all appropriate control measures and the raw material. Although not usual, a new infesta-
against biological attack have been in a state of consider- tion may be traced to a prior infestation through poor
able flux because the general and scientific public have be- housekeeping practices. Aqueous tinting colors, surfac-
come more aware of the environmental, aquatic, and tants, and other additives not containing a biocide may
mammalian toxicity of many of the control measures. also introduce the bacteria.
Microbiological growth on, and the deterioration of, Once infestation occurs, the long-chain carbohydrates
coating films involve attack by either fungi or algae. Fun- and any proteinaceous-based raw materials that may be
gi, primitive spore-bearing filamentary species, are free of present in the paint and latex are vulnerable. These mate-
chlorophyll. They obtain nutrients from the substrate or rials are selectively broken down by the cellulase, an en-
their environment. Common nutrient sources are various zyme secreted from the bacteria itself. Most vulnerable are
kinds of hydrocarbons, including organic paint films and cellulosic polymers used in paint and latex (as thickeners
linings. Algae are an equally primitive plant species but and protective colloids). Stored solutions of these materials
they photosynthesize their nutrients from carbon dioxide Continued

Copyright ©2000, Technology Publishing Company JPCL September 2000 51

Technology
are particularly vulnerable. These cellulosics undergo ran-
dom enzymatic hydrolysis. Eventually, they yield the dou-
ble anhydroglucose unit, cellobiose, and, sometimes, the
single anhydroglucose unit. These products are most easi-
ly assimilated by the bacteria as nutrients.
One characteristic of all bacteria is their extremely high
metabolic rate. To maintain their growth, bacteria require
100-500 times their own weight in nutrients per hour. At
this rate, cellulosic components of the film are rapidly de-
graded. Bacteria also reproduce readily, every 20 minutes
under favorable circumstances. Complete hydrolysis of
such thickeners is not necessary before untoward effects
are noted in the paint. Bond cleavage in one or two loca-
tions along a cellulosic chain will severely inhibit the
thickening power of the substituted cellulose.
Defoamers, surfactants, and stabilizers may also be at-
tacked, although there is rarely any breakdown of the ac-
tual polymer itself. Microbial attack on other components
of the paint formulation inevitably lead to other untoward
effects. Degradation of the dispersants may result in di-
minished hiding, color shifts, pigment sedimentation, and
gelation. Attack on dispersed colorants may give similar
problems, including uneven color. Bacteria and yeasts can
cause discoloration by producing colored pigmentary moi-
52 JPCL September 2000
eties as a result of their metabolism. Degradation of the an-
tifoam agents leads to increased foaming and the deposi-
tion of porous films. Breakdown of the humectants (in-
cluded to increase wet edge time) and coalescing agents
will lead to reduced film properties and poor adhesion, re-
duced flow and leveling, reduced freeze/thaw stability, and
shifts in pH as well as loss of gloss.3
In addition to bacteria (pseudomonas aeruginosa), other
micro-organisms such as fungi (unicellular yeasts and mul-
ticellular molds) can and do attack these products (Table
1). Some bacteria are aerobic, growing only in the presence
of oxygen; others are anaerobic, growing more effectively
in the absence of oxygen.
Aerobic bacteria often begin the attack. They cause paint
to lose viscosity, and pigment sedimentation takes place.
These changes will accelerate with time as the bacteria
multiply. Within the pigment settlement, the environment
becomes relatively anaerobic, and the growth of other
types of bacteria is fostered. Sulfate-reducing bacteria
found under these conditions will produce hydrogen sul-
fide with objectionable odor and color. Odor was particu-
larly putrid when thickeners were based on proteinaceous
materials such as casein. Yeasts may also contribute to the
Continued
Copyright ©2000, Technology Publishing Company
Technology

development of gas (CO2) build-up and a highly discolored
(blackened) material. Gas build-up may cause the distor-
tion of cans, and, in certain cases, may explosively force
the lid off the can.
Aerobic fungi may also grow on the surface of the paint.
Since bacteria and fungi are to some extent symbiotic, the
bacteria can feed from the residues of fungal attack.4 Many
of the newer types of thickeners are far less sensitive to
bacterial degradation than are the cellulosics. As the use of
these materials has increased and the use of cellulosics has
decreased, the need for the most efficient bactericides has
diminished. Even where newer thickeners are used, how-
ever, cellulosics at much lower concentrations often re-
main in latex emulsions as well as in the paint itself. Both
require protection.
Bacteria thrive in diluted paint more readily than in the
fully-formulated composition. The practice of storing wash
water from one batch for use in future batches is prob-
lematic. (Wash water is water used to clean vessels in
which latex paint is made. The water is stored and used in
the next batch of latex paint instead of virgin water.) High-
er levels of effective biocides must be added to these wa-
ters if aerobic and, subsequently, anaerobic bacteria are to
be avoided. As is noted by Opperman and Goll, more ex-
amples of gassing and viscosity loss have resulted from the
practice of reusing such wash waters.4
Microbiologically-Influenced
Corrosion of Metals
Bacteria and fungi (including yeast) also thrive in fresh
and saltwater environments where there are available
sources of nutrients such as contamination, sedimentation,
or even suitable organic coatings on submerged structures.
As we will see, types of microbiological attack vary5 and
several types of microbes are prevalent6, including those
that can induce not only paint film degradation but also
metallic corrosion. These include sulfate-reducing bacteria,
which reduce sulfates to sulfides and depolarize cathodic
sites of corrosion cells by consuming hydrogen.7 Sulfate-re-
ducing bacteria are among the oldest types of organisms on
earth. They are widely distributed in soils and waters the
world over. Kobrin explains how iron- and manganese-
based bacteria accumulate in bulky deposits, creating met-
al ion or oxygen concentration cells.6 He shows that these
deposits foster the establishment of anaerobic conditions
beneath the colony (as do other poultices).
Other potentially damaging organisms include the hydro-
carbon feeders and acid producers. Sulfur-oxidizing species
may produce sulfuric acid. Other microbes can metabolize
hydrocarbons (including the hydrocarbon chains of paint
film binders and additives). These reactions produce low
molecular weight carboxylic acids. Both types of acid pro-
ducers will destroy acid-sensitive organic coatings, expos-
ing the metal to acid attack as well as attack by other sym-
biotic microbes. Like the iron and manganese microbes
(noted above), slime-forming fungi, algae, and bacteria can
form oxygen concentration cells on metal, increasing gal-
vanic corrosion.
Free swimming, planktonic, and fixed (or sessile) bacte-
ria are often found under localized conditions. They may
associate on the metal surface (coated or uncoated). Nu-
merous case histories that highlight microbiologically-influ-
enced failure in metals are available. These range from mi-
crobiological attack on aluminum alloy fuel tanks of jet
aircraft (and the consequent constriction of fuel lines) to
the pitting of the bottoms of ballast tanks and cargo holds
containing hydrocarbon/water sludges that feed the meta-
bolic processes of acid-producing microbes.8
In some cases, aerobic and anaerobic growth may coexist
Continued

Table 1:
Biological and Microbiological Agents Affecting Paint and Paint Films

Classification Example Effect on Paint Film and Substrates

Bacteria
Fungi (multicellular molds, mildew,
unicellular yeasts)
Algae
Marine growth
Animal species (submerged)
Plant species (submerged)
Pseudomonas aeruginosa
Flavobacterium marinum
Aureobasidium (Pullularia) pullulans
Penicillium citrinum, Cladosporium sp.
Aspergillus niger
Cyanophyta, Chlorophyta, Synechocystis sp.
Protococcus sp.
Barnacles, mussels, tube worms
Enteromorpha ectocarpus laminaria
Wet paint infestation, corrosion of metals,
paint film degradation
Disfigurement and degradation of applied paint
films, corrosion of metallics, rotting of wood
Disfigurement of applied paint films
Colonization of underwater surfaces of marine
structures (vessels)
Colonization of underwater surfaces of marine
structures (vessels)

54 JPCL September 2000 Copyright ©2000, Technology Publishing Company

Technology
symbiotically. Acid-producing bacteria scavenge oxygen
from water as they metabolize hydrocarbons to produce
acids. The deprivation of oxygen in turn helps establish
anaerobic conditions in which other species (such as the
sulfate-reducing species) may thrive. The latter microbes,
which depend on the availability of electrons to sustain
their own metabolism, associate adjacent to the metal.
There, they induce sulfidic conditions. Concentrations of
strongly acidic sulfide conditions can destroy protective
coatings and set up concentration cells that lead to micro-
biologically-influenced pitting. This type of attack in the
bottom of cargo holds is reviewed in some detail by Smart.8
Many types of coatings are ineffective under these condi-
tions because of the diverse nature of the attack. In spite of
their adhesion and overall corrosion resistance, for example,
epoxy polyamides may be severely deteriorated by hydrocar-
bon feeders that attack the polyamide backbone of the curing
agent. Conditions may become too acidic for the system, and
the coating rapidly degrades to mush. Amine-cured epoxies,
which do not contain the long hydrocarbon polyamide
chains, are often more acid resistant than the polyamides, and
are more resistant to such bacterial attack, as are coal tar
epoxies cured with aliphatic or aromatic amines. The pheno-
lic compounds of coal tar epoxies (and probably epoxy no-
56 JPCL September 2000
volacs) may also serve well against fungal/bacterial attack.
Again, coal tar hybrids of this type should not be crosslinked
with polyamides. Other sensitive coatings include wax-based
systems, and systems bearing sulfides or hydrocarbon-based
plasticizers, diluents, or additives.
Microbiologically-influenced acid attack is best con-
trolled by the use of coatings that are not bacteriologically
nutritious and that do not degrade. In designing systems for
contaminated oil cargo tanks, Smart8 recommends the local
application of topcoats that are most resistant to attack over
the most vulnerable areas of the tank interior (the bottoms
and lower sides). Such coatings include the amine-cured
coal tar epoxies as well as the coal tar polyurethane hy-
brids, epoxy novolacs, and polyurethane finishes. Aromat-
ic amine-cured epoxies and other systems properly maxi-
mized for acid resistance might also be used.
Microbiologically-influenced corrosion is a problem encoun-
tered in many other industries, including petrochemical (gas
and oil production and distribution), pulp and paper, chemical
processing, electrical power production (fossil fuel and nu-
clear), and sewage and water treatment. Scott and Davies9 list
a wide variety of relatively extreme conditions where microbi-
ological corrosion has been noted. These conditions include
immersion in fresh, salt, and brackish water (both stagnant
Copyright ©2000, Technology Publishing Company
 Technology
and free flowing), under oxidizing and reducing conditions,
and over a temperature range of zero to near boiling. All met-
als (except titanium and its alloys) seem vulnerable.

Microbiological Defacement and Degradation

of Applied Coating Films
Mold and Mildew
Mold and mildew are both forms of fungi. Conditions must
be suitable for mold and mildew to develop. The availability
of water is mandatory, and a minimum humidity of at least
70% is usually necessary for growth. Mildew growth is neg-
ligible below 5 C (41 F) and above 50 C (122 F). Mildew
grows best in a pH range of 4.5-6.5. Molds do not thrive un-
Fig. 1: Mildew infestation of a deeply grained wooden board
der alkaline conditions, though growth may occur up to a pH
Photos courtesy of the author.
of 8.5 (to 10.0 in the case of aureobasidium pullulans). Molds
will, however, grow readily on painted plaster under moist Fungal attack and disfigurement will also depend on the
conditions. Mildew growth is a much more serious problem morphological nature of the surface of both paint film and
in sub-tropical environments than in the more temperate ar- substrate. Paint systems on wooden substrates provide the
eas. Molds are not UV-resistant and grow best in darkened lo- high cellulosic content that supplies the mold with nutri-
cations. Mildew is widely noted in warm, moist interiors ents. This high cellulosic content will make control more
(breweries, canneries, dairies, etc.), as well as on films in difficult than when the same films are applied over metal
bathrooms and other damp, dark areas. In exterior locations, or masonry substrates (Fig. 1). Primer films that bear
mildew thrives in dark areas, especially those sheltered by fungicides in addition to those used in the finish coats are
excessive vegetation, where the films can retain moisture. Continued

Copyright ©2000, Technology Publishing Company JPCL September 2000 57

Technology
of value here. Contamination of both substrate and un-
dercoat will lead to re-infestation of newly applied finish-
es and even delamination. Mildew growth and dirt pick-
up occur more readily on matte, fissured, and uneven
films (especially softer surfaces) than they do on smooth,
hard surfaces. (Dirt pick-up is increased by the presence
of mildew.) Rough wooden surfaces painted with high
pigment volume concentration/critical pigment volume
concentration (PVC/CPVC) oil-based stains are very sus-
ceptible to growth. Intense growth often coincides with
cracks and fissures, especially on wooden surfaces with
heavily worn or weathered grain patterns. Latex paints
seem more vulnerable to attack than might be expected.
This tendency is probably related to moisture take-up by
the film. Hill and April10 postulate that given sufficient
moisture content, mildew control, even with relatively
powerful fungicides (such as the phenyl mercurials), is
very difficult.
Table 2:
Common Micro-organisms (Mildew) Isolated from
Oil- and Latex-Based Paint Films
Agent Type
Aureobasidium (Pullularia) pullulans* Fungus
Phoma glomerata* Fungus
Cladosporium sp.* Fungus
Flavobacterium marinum* Bacterium Universal (co-operating bacterium)
Alternaria sp.* Fungus
Aspergillus flavus** Fungus
Penicillium sp.** Fungus
* Isolated by Rothwell on oil paints and by Drescher on latex paints
** Isolated by Krumperman
Algae
Primitive plants that do not require paint film binders for
nutrients are frequently found to colonize on (and, there-
fore, deface) almost all substrates in moist, warm locations.
Whereas fungi tend to favor dark locations, algae require
plenty of sunlight and with few exceptions are found main-
ly outdoors. Unlike fungal infestation, algae is not inhibit-
ed by high pH. This is probably why algae grows predom-
inately on concrete and masonry substrates, which have a
higher pH. Such substrates are more hospitable to algae
than to fungi. Algae will itself produce little paint deterio-
ration, but it will increase moisture retention, which may
be problematic. Certain algae, visible as grayish-black or
bluish-green (sometimes green, orange, or pink) growths,
are certainly unattractive. More important, on walkways,
especially during the rainy season, algae growth may cause
58 JPCL September 2000
dangerous, slippery conditions. Drisko and Crilly report sig-
nificant growths of blue-green algae (cyanophyta) and green
algae (chlorophyta) disfiguring U.S. Marine Corps installa-
tions in Guam and elsewhere.11 In Australia, it has been re-
ported that the cleaning and repainting of buildings infested
with algae and fungal growth were estimated at between
$15 and 30 million annually.12
Susceptibility of Paint Films to Defacement
The defacement of mature latex and particularly oxidizing
films by fungi (molds and mildews) is still common. Fun-
gal attack on other films may have more important engi-
neering consequences, but defacement of trade sales paint
films is more widespread. Although oil paints are less wide-
ly used than they once were, alkyds and other oxidizing
species are also affected.
A similar phenomenon is seen, if less extensively, on inte-
rior and exterior latex paint films, especially those bearing oil
or alkyd modification for adhesion to
chalky surfaces. Hard, smooth amine-
cured epoxies, polyurethanes, vinyls,
and baked amino-formaldehyde finish-
es are less subject to the phenomenon.
Chlorinated rubber films modified with
Location linseed oil have become heavily de-
Universal, black, and most disfiguring faced with micro-organisms.13
West coast of U.S. only Polyamide-cured epoxies are vulner-
Eastern seaboard of U.S. able to attack because of the nutri-
tional value supplied by the fatty acid
Universal in the polyamide. After attack, the
Domestic, food processing plants, paint film may be incapable of main-
canneries, breweries, dairies taining the level of service that it was
Domestic, food processing plants, intended for. In other cases, while the
canneries, breweries, dairies binder itself may not be resistant to
micro-organisms, other moieties such
as plasticizers and additives may be
susceptible to microbes. Microbe at-
tack may severely deplete necessary properties (change me-
chanical properties, for example).
The effects of microbiological attack on paint films are
most apparent with oxidizing systems and latex paints be-
cause the fungi, as parasites, find these entire binders very
rich in potential nutrients. As was the case with the bacte-
rial in-can infestation, the fungi secrete enzymes that break
down portions of the film binder into components required
for their own biochemistry.
Organisms are varied. They can be specific to geographi-
cal location or the local environment, although not neces-
sarily to the nutrient (film) itself. Rothwell14 and Dresch-
er15, separately working with oil paints and latex paints
respectively, found the microbiological propensities of both
to be similar. Four fungi and one bacterium were common
Continued
Copyright ©2000, Technology Publishing Company
 to both types of paint (Table 2). Certain species seem to oc-
cur predominantly in one area of the country. While inves-
tigating film defacement in food processing plants and can-
neries, breweries, and dairies, Krumperman16 found many
species of aspergillis and penicillium not found in normal
exterior environments. Flavobacterium marinum was more
universal.
Vegetable oils are particularly vulnerable to attack by
molds and mildew. As was shown by Ross17, the infesta-
tion of the surface involves not only aesthetic loss but also
an actual degradation of the binder itself. Scission of the es-
ter linkages and aerobic oxidation of the fatty acids with
the eventual accumulation of short-chained acids also oc-
cur. The specific nature of the acid depends on the organ-
ism involved.
Flavobacterium marinum was found to produce oxalic
acid from linseed oil films. Pullularia pullulans produced
acetic and acetoacetyl acids, as well as oxalic acid from the
same films. Reaction pathways are probably similar to
those represented above for the microbiological degrada-
tion of hydrocarbon species that leads to metallic corro-
sion. Attack on latex paints again involves cellulosic
residues and does not involve the binder. The discoloration
is still quite objectionable, however. Microbiologically-in-
fluenced changes in the film structure will also lead to
changes in the mechanical and chemical properties of the
film. (These changes include adhesion loss and brittle fail-
ure, as well as increased water sensitivity.) On microbio-
logically-sensitive substrates such as wood, infestation will
often lead to loss of engineering properties (rot, etc.).

Controlling Microbiological
Growth with Biocides
To combat bacterial attack, paint, wash water, and the paint
raw materials—particularly the latex and cellulosic thicken-
er solutions—must be inoculated with a wide spectrum bio-
cide against bacteria. Perhaps to a lesser extent, they must
be inoculated against fungi, both yeasts and molds (Table 3).
A given biocide will not necessarily be effective against both
bacteria and fungi. In fact, specific bactericides may be se-
lectively effective against only gram negative or gram posi-
tive bacteria. Gram negative bacteria, most often found in
wet latex paint, have highly complex cell wall structures that
inhibit the penetration of bactericides. Unless very high lev-
els of bactericide are used, the additive becomes exhausted
before it can completely deactivate the species. Any poten-
tial bactericide should be easily incorporated within all sys-
tems in which it is to be used. It should also be effective over
as wide a pH range as possible. It should be environmental-
ly innocuous and have low mammalian toxicity.
Conformity with the latter requirement has grown in im-
portance over the last 30 years and has been difficult to
achieve. At one time, the phenyl mercurials were widely

60 JPCL September 2000 Copyright ©2000, Technology Publishing Company

 Technology
used and were very efficient against a broad range of bac- paint is not today easily reclaimed.
teria. These products, as well as other highly efficient bac- It was once common for latex manufacturers to preserve
tericides (the chlorinated phenolics), are now prohibited latex emulsions with additions of formalin- or formalde-
because of concerns about their toxicity. A va-
riety of wholly organic-based bactericides has
” hyde-producing biocides. Formaldehyde
has strong bactericidal properties.
been introduced. Many of these are often pro- Formaldehyde is released by the hy-
prietary combinations presumably designed to
A variety drolysis of materials such as 5-hydrox-
broaden the spectrum of their effectiveness. of wholly ymethoxymethyl-1-1 aza-3,7-dioxabicy-
One of the more effective classes of this type clo(3.3.0)-octane. This substance,
of materials appears to be 2-methyl-4-isothia- organic-based however, cannot be used with vinyl chlo-
zolin-3-one and its chlorinated derivative. ride-containing latexes because of toxic
Modes of microbiological attack5 are various bactericides gas generation.
and include enzyme inhibition (barium metabo- Again, because of toxicity concerns,
rate, tributyltin oxide); protein deactivation or
has been the use of formaldehyde has been dis-

inhibition (the phenyl mercurials, zinc oxide); introduced.
coagulation (the mercurials, copper (II) 8-quino-
linolate); and chelation with metals required for
bacterial growth and metabolism (2-mercaptobenzothiazole,
zinc 2-pyridinethiol-2-thione). Other biocides function
through electrophilic deactivation of nucleophilic areas of the
microbe’s cellular structure (1,2-benzisothiazoline-3-one).
While effective against bacteria, most modern bacteri-
cides do not neutralize the enzymes the way the phenyl
mercurials neutralized them. Thus, once contaminated, a
”
continued, and manufacturers now use
proprietary materials. Residual monomer
itself has some biocidal properties.
Fungi
Zinc oxide has long been favored in paints because of its
fungicidal properties. It was used in oil-based house paints
in loadings of more than 2 to 3 lbs/gal. (240 to 360 g/L).
These levels of zinc oxide caused embrittlement of the
Continued

Copyright ©2000, Technology Publishing Company JPCL September 2000 61

Technology
paint system. Two authors13 describe
good growth inhibition with levels of
zinc oxide of up to 3.5 lbs/gal. (419
g/L) in polyvinyl acetate latex paints
and alkyds. Zinc oxide is still widely
Fig. 2: Mildew on a scribed alkyd. Note freedom from infestation around scribe,
believed to be related to alkaline pH of cathodic area surrounding active anode (scribe).
Table 3:
Biocides Used in Paints as Preservatives and Mildewcides
Bactericide
5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one
4,4-Dimethyloxazolodine
2[(Hydroxymethyl]amino)ethanol
Diiodomethyl-p-tolyl suphone
1-(3-chloroalyl)-3,5,7,-triaza-1-azoniaadamantane chloride
1,2-benzisothiazolin-3-one
Fungicide
2-n-octyl-4-isothiazolin-3-one
2,4,5,6,-Tetrachloroisophthalonitrile
2-(4-thiazoyl)benzimidazole
Zinc oxide
N-(trichloromethyl) thiophthalimide
Bactericide and fungicide (wide spectrum biocide)
Phenylmercurials*
1-aza-3,7-dioxabicyclo(3.3.0)octanes
Tributyltin oxide*
2,2-dihydroxy-5,5dichlorodiphenylmethane
Barium metaborate
2,3,4,6- tetrachloro 4(methyl sulfonyl)pyridine
*Usage either has been banned or is being phased out.
62
used in latex paints for the same rea-
son. Fortunately, lower levels (<1
lb/gal. [<120 g/L]) have been found18
to be satisfactory, especially when
used in combination with some of the
JPCL September 2000
modern organic fungicides (Table 3).
This is fortunate because zinc oxide is
a reactive pigment. As such, it destabi-
lizes latex paints and reduces
freeze/thaw resistance. Specially de-
signed dispersant systems have been
developed to improve the stability of
zinc oxide in latex paints.
It may be in part the basicity of zinc
oxide that inhibits mildew growth.19 It
has also been claimed that calcium car-
bonate reduces such growth. Localized
growth inhibition has also been noted
by the author around the scribe of a
borosilicate-pigmented silicone alkyd
(Fig. 2). This inhibition of growth was
attributed to the effects of cathodic al-
kali alongside the corroding scribe (an
anode). Bacteria do not thrive at a pH
range of 10-11.7 Cathodic protection
will retard bacterial growth on sub-
mersed marine coatings when the po-
tential (with respect to a saturated
calomel electrode) is maintained more
negative than -1.024 volts.20
Fungicidal attack, especially nodular
growth, may often be mistaken for
dirt. Micelean growth is more obvious,
but it is often diminished in favor of
nodular attack where paint films are
inhibited. Differentiation between
nodular infestation and dirt can be
made using a 2% sodium hypochlorite
solution that will kill and bleach away
the infestation. This solution will not
affect dirt. The test area should always
be rinsed after de-infestation and be-
fore repainting. Before repainting an
infested surface in the field, a similar
hypochlorite solution may be used as a
preparatory wash. Rinsing and drying
the surface before painting are impor-
tant. Repainting the area with a prod-
uct (latex or oil) that is itself fully in-
hibited is crucial to avoid further
growth.
An important feature for controlling
microbiological attack of the dry film
is non-fugitivity. (Non-fugitivity is the
ability of the fungicides’ effectiveness
to last. Fugitive materials have short-
lived effectiveness.) All fungicides (in-
cluding zinc oxide) tend to leach from
Copyright ©2000, Technology Publishing Company
 Technology

the film, reducing their long-term ef- banned in some areas and regulated pigmented with barium metaborate
fectiveness. Loss via leaching is not strictly in others because of its toxicity had algicidal properties equal to those
the only mechanism by which mildew- to shellfish. Copper compounds with high levels of 2-(4 thiazolyl) ben-
cidal paints may lose effectiveness (cuprous oxide), effective as mildew- zimidazole.
with time. Vaporization of organic cides on wood, are not as effective •••
agents and loss due to chalking and by against terrestrial algae. Copper com- Next Month:
chemical change or reactivity (hydrol- pounds are, however, effective against Chemical Changes Occurring
ysis) are also possible. algae in the aquatic environment. within the Can
Gabriele and Iannucci21 showed that Drisko and Crilly11 found that paints Continued
most of these materials (including the
phenyl mercurials, organotins, and
chlorinated phenols) are sensitive to
light-induced degradation. Fortunately,
such loss of effectiveness may be com-
bated with combinations of hydrox-
yphenyl benzotriazole light absorbers
and piperidinyl-based hindered amine
light stabilizers (HALS). Biocidal com-
binations that do exceptionally well in
the short term but fall off in protection
after one to two years are less desir-
able than materials that remain in the
film for longer periods. In films that
chalk heavily, even zinc oxide may be
prematurely depleted. This effect re-
futes earlier beliefs that chalking is a
positive factor in mildew control.22
There may also be unexpected sensi-
tivities. The effectiveness of mercury
compounds is decreased in formula-
tions that also contain iron pigments
and sulfur compounds.1 1-(3-chloroal-
lyl)-3,5,7-triaza-1-azonia adamantine
chloride has been found to yellow
films. Sodium sulfite has been found to
reduce this effect.5 As one study con-
cludes, it is important to evaluate the
effectiveness of a biocide combination
after at least 24 hours have elapsed
since inoculation.18

Algae
Biocidal measures for preventing algae
growth are much the same as those for
fungi. Again, the most effective bio-
cides are generally those that have the
highest toxicity for higher life forms.
These include the phenyl mercurials
and tributyltin oxide. The latter has
been widely used in anti-fouling coat-
ings (as described in the June 2000
Trouble with Paint column). Now,
however, the use of tributyltin oxide is

Copyright ©2000, Technology Publishing Company JPCL September 2000 63

Technology
References
1. A.L. Eilender and R.A. Opper-
mann, “Biocides: Bacteriocides
and Fungicides,” Chapter 7 in
Handbook of Coatings Additives,
ed. L.J. Calbo (New York, NY: Mar-
cel Dekker, 1987), p. 177.
2. J.A. Tracey, “Preservatives,” in Sur-
face Coatings Vol. I, Raw Materials
64
and Their Usage, 3rd Edition (Lon-
don, England: Chapman and Hall,
1993).
3. R.A. Oppermann, “Presence and
Effects of Anaerobic Bacteria in
Water Based Paint II—Effect on
Paint Ingredients” Journal of Coat-
ings Technology (November 1985),
Vol. 57, #730, p. 33.
JPCL September 2000
4. R.A. Oppermann and M. Goll,
“Presence and Effects of Anaerobic
Bacteria in Water Based Paints I—
Effect on Paint Ingredients,” Jour-
nal of Coatings Technology (May
1984), Vol. 56, #712, p. 51.
5. V.M. King, “Bactericides, Fungi-
cides and Algicides,” Chapter 29 in
Paint and Coatings Testing Manu-
al, ed. J.V. Koleske (Philadelphia,
PA: ASTM, 1995), p. 261.
6. G. Kobrin, “Corrosion by Microbio-
logical Organisms in Natural Wa-
ter” Materials Performance (July
1976), p. 38.
7. C.A.H. von Wolzogen Kuhr, “The
Unity of the Anaerobic and Aerobic
Iron Corrosion Process in the Soil,”
presented at the Fourth National
Bureau of Standards Soil Corrosion
Conference, Washington, DC 1937.
8. J.S. Smart, “An Introduction to Mi-
crobiologically Influenced Corro-
sion in the Marine Industry” Jour-
nal of Protective Coatings & Linings
(February, 1997), p. 56.
9. P.J.B. Scott and M. Davis, “Micro-
biologically Influenced Corro-
sion—State of Art vs. State of
Mind” Materials Performance (Sep-
tember 1993), Vol. 32, #9, p. 8.
10. D.O. Hill and G.C. April, “Influence
of Moisture Transport on Fungal
Growth” Journal of Paint Technolo-
gy (September 1971), Vol. 43, #560,
p. 81.
11. R.W. Drisko and J.B. Crilly, “Con-
trol of Algae Growth on Paints in
Tropical Locations” Journal of
Paint Technology (August 1974),
Vol. 46, #595, p. 49.
12. E. Hoffman, Materials Research
Std. 10, #12, 21 (1970).
13. A. Saracz and E. Hoffman, “The
Evaluation of Paint for Fungus Re-
sistance—Zinc Oxide Latex Paints”
JOCCA (February 1968), 51, 2, 103.
14. F.M. Rothwell, “Microbiology of
Paint Films II—Isolation and Iden-
tification of Microflora on Exterior
Oil Paints” Official Digest (1958),
30, #399, 308.
15. R.F. Drescher, “Microbiology of
Copyright ©2000, Technology Publishing Company
 Paint Films IV—Isolation and Iden-
tification of Microflora on Exterior
Emulsion Paints” American Paint
Journal (1958), 42, #38, 80.
16. P.H. Krumperman, “Microbiology
of Paint Films V—Microorganisms
Found on the Interior Paint Films
of Food Processing Plants” Ameri-
can Paint Journal (1958), 42, #38,
72.
17. R.T. Ross, “Biodeterioration of
Paint and Paint Films” Journal of
Paint Technology (April 1969), Vol.
41, #531, p. 266.
18. R.C. Trueblood, et. al., “Three Year
Study of Mildew Growth on Coated
Surfaces” (Technical Committee of
the Columbus Dayton Indianapolis
Chapter of the Federation of Soci-
eties for Coatings Technology)
Journal of Paint Technology (March
1971), Vol. 43, #554, p. 76.
19. T.T. Broome and E.J. Lowrey,
“Mechanisms for Film Preservation
by Phenyl Mercurials on Wood
Substitutes” Journal of Paint Tech-
nology (April 1970), Vol. 42, #543,
p. 227.
20. H.P. Dhar in Electrochemical Meth-
ods for Prevention of Microbial
Fouling (New York, NY: Plenum
Press, 1986), p. 593.
21. P.D. Gabriele and R.M. Iannucci,
“Protection of Mildewcides and
Fungicides from Ultraviolet Light
Induced Photo-oxidation” Journal
of Coatings Technology (May 1984),
Vol. 56, #712, p. 33.
22. E. Hoffman and R.R. Couper, “The
Formulation of Fungus Resistant
Paints IX: Influence of the Primer
and Pigments Causing Chalking”
JOCCA (December 1970), Vol. 53,
#12, p. 1063.

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