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J. Coat. Technol. Res., 8 (5) 619–628, 2011
composition.7 Some paint components, such as cellu- paint to achieve the required colors, as shown in
loses, are nutrients for microbial cells, while others, Tables 3 and 4. The colors chosen are those most
e.g., some metals, are inhibitory.2 Pigments used to common on the Brazilian market. Acticide HF (an
give the coating its color may be inorganic or organic isothiazolinone/formaldehyde based, broad spectrum
and the latter may be more likely to act as microbial biocide) was used as the in-can preservative in all
nutrients. Impurities in the pigments, such as phos- paints and 2% Acticide EPW (a mixture of carbenda-
phates and potassium salts, may also act as essential zim, octyl isothiazolone, and diuron) was added to a
nutrients, increasing paint susceptibility,8,9 while other portion of the paint to inhibit fungal and algal growth
components, such as heavy metals, inhibit microbial on the dry film, acting as a control.
growth.
There has been no recently published work on the
effect of pigments on susceptibility of paints to Paint and pigment analysis
biodeterioration. Turner9 cites Gardner (1939),
Findlay (1940) and Dooper and Hermann (1948), The pigments supplied by Clariant were applied, each
who stated that paints containing zinc oxide were as a single layer, on Whatman 40 8 lm filter paper and
more resistant to fungal growth than those containing inorganic components analyzed by EDS and X-ray
lead white, lithopone, or antimony oxide, and that the fluorescence spectrometry (Shimadzu model EDX-
most susceptible white pigments were titanium dioxide 700). The same analysis was carried out on the paints.
and lead–titanium. However, many of these pigments Pigment volume content (PVC%) of the colored paints
are no longer used because of their environmental was calculated as follows:
toxicity, a similar situation to that occurring with
chromium, which is also biocidal. VP 100
Zinc oxide is one of the antimicrobial substances PVC% ¼
VP þ VR
still used in paint pigments. At a level of 3.4% it
conferred resistance to fungal attack on painted where VP = total pigment volume and VR = volume
surfaces in France10 and 2% in oil-based paint showed of resin.
fungicidal activity (Meier and Schmidt, 1952, cited in
reference (9)).
Of the organic pigments, Victoria Blue and methyl Test panels
violet were shown to be the most susceptible to fungal
growth, probably because of the presence of dextrin Fiber cement board (BrasiPlac, Brasilit) was cut into
(a nutrient sugar) in the formulation.9 This author panels 30 cm x 10 cm x 6 mm. A hole was drilled at
found that Monastral Blue was one of the few blue each end for the fixing screws and the sunken heads of
pigments that were completely resistant. these zinc screws were sealed with a mixture of
A recent literature search revealed no scientific powdered fiber cement and acrylic plaster. After
publications on microbicidal activity of modern pig- 7 days for drying, panels were painted with a white
ments and so we decided to undertake this project to acrylic sealant, left to dry for a further 7 days in the
determine the ability of paint pigments to inhibit horizontal position in a dust-free environment, as
biofilm formation on painted surfaces, with the final recommended by Brazilian standard NBR
aim of reducing the need for dry film biocides. 13006/1993, and then roller-painted with one coat of
Florianópolis, in the South of Brazil, is a suitable site the requisite pigmented paints to give a dry film
for such testing because of its climatic characteristics, thickness of 50–60 lm. For each color, six panels were
which encourage the growth of microorganisms. It is a painted without dry film biocide and two with biocide,
coastal city with exuberant subtropical flora and fauna. the latter intended as controls. After a further 7 days
The meteorological parameters measured during the for drying, the panels were fixed to wooden racks,
exposure period are given in Table 1. using PVC tubes to protect the metal screws and
distance the panels from the wooden slats of the rack,
thus avoiding interactions between the wood and the
Materials and methods painted panels.
Paint formulation
A basic acrylic matt paint, of the type typically used for Exposure regime
external surfaces in Brazil, was produced (Table 2).
Solid content was 48.6% and performance, for a Duplicate racks were prepared, each bearing 40 vertical
50–60 lm dry film, was 12.50 m2/L. Ten predispersed panels in 10 rows (Fig. 1). Each row held three non-
pigments (Colanyl) were donated by Clariant, Sao biocide and one biocide-containing panel of a given
Paulo, Brazil. They were presented dispersed in a color. The racks were placed on the roof of the Civil
binder-free, aqueous solution containing wetting and Engineering building of the University of Santa Catarina,
dispersing agents. Pigments were mixed into the basic in Florianópolis, on the Island of Santa Catarina,
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Table 1: Meteorological data for the period of the test
Month/2006 Jan Feb March April May June July Aug Sept Oct Nov Dec Average
Ave temperature – 33.0 18.0 36.0 16.0 31.0 14.0 27.0 10.0 28.0 9.0 29.0 5.0 29.0 5.0 33.0 4.0 32.0 14.0 30.0 22.0 33.0 18.0 31.0 12.3
(max min)°C
Rainfall/month – 36.0 70.0 70.0 50.0 40.0 45.0 60.0 45.0 90.0 240.0 80.0 75.09
(mm)
Insolation – 164.5 209.5 213.5 197.5 148.5 180.5 172.5 166.5 164.5 144.5 203.5 178.68
(h/month)
Month/2007 Jan Feb March April May June July Aug Sept Oct Nov Dec Average
Ave temperature 31.0 17.0 34.0 17.0 33.0 17.0 33.0 15.0 33.0 5.0 30.0 6.0 31.0 3.0 29.0 4.0 26.0 11.0 32.0 15.0 32.0 13.0 34.0 16.0 31.5 11.1
(max min)°C
Rainfall/month 90 140 210 40 140 10 175 90 140 150 100 140 118.75
(mm)
Insolation 201.0 177.5 224.0 186.5 120.0 154.0 142.5 97.5 165.0 149.1 189.0 195.3 166.79
(h/month)
Month/2008 Jan Feb March April May June July Aug Sept Oct Nov Dec Average
Ave temperature 33.0 17.0 33.0 17.0 32.0 16.0 32.0 10.0 33.0 5.0 30.0 4.0 30.0 9.0 28.0 8.0 31.0 9.0 30.0 14.0 30.0 13.0 31.0 15.0 30.9 10.9
(max min)°C
Rainfall/month 350 420 250 210 80 80 10 70 250 290 610 290 242.50
(mm)
Insolation 175.0 193.5 171.1 173.0 232.5 161.5 218.6 138.5 152.0 80.5 104.0 215.2 167.95
(h/month)
J. Coat. Technol. Res., 8 (5) 619–628, 2011
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Azoyl-b naphthol
Table 2: Components of the basic paint
Concn (%w/w) Material Weight (kg)
GG
5.50–8.00
42.50 Water 0.594
0.36 Hydroxyethylcellulose 0.006
1.33
Red
50
0.14 Ammonia 0.002
0.36 Disaspers-T Conc 0.005
0.18 Disafoam 969-T 0.002
Copper phthalocyanin
0.26 Acticide HF—THOR 0.004
8.08 Titanium dioxide 0.113
12.14 Calcium carbonate ppt 0.170
3GLS
13.20 Calcite #400 0.185
5.50–8.00
3.60 Micronized talc 0.050
Green
7.24 Micronized Caulim 0.101
1.47
10.33 Acrylic resin 0.144
50
0.46 Propylene glycol 0.006
0.83 White spirit 0.012
Lamp black
0.32 Gapcoat MGK 0.004
5.50–8.00
100.00 Total 1.398
PRQ
Black
1.27
35
South Brazil, with one rack with panels facing north and
the other south. Although it is more usual to incline
Titanium dioxide
panels for biodeterioration testing at 45°,2 we used
vertical panels to better mimic the façades of buildings.
8.00–10.00
TQ
This strategy was also adopted by Stanley Buckman,
who investigated phenylmercury compounds for the
White
1.80
N/D
reduction of paint film biodeterioration in the 1940s and
1950s,11 and by Springle et al.12 at the Paint Research
Association in the UK. Temperature at the exposed
Codes are those given by the pigment producer (Clariant). N/D = not determined
Copper phthalocyanin
surface of each panel was measured between 11:00 am
and noon, 245 days after initial placement (i.e., in
October) to check possible differences between north
and south faces. Ambient temperature and relative
SH
1.26
Table 3: Characteristics of pigments used in the paints
50
Yellow
Color
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J. Coat. Technol. Res., 8 (5) 619–628, 2011
Table 4: Quantities in mg of pigments added to the biodeterioration is well accepted, but gives only
basic paint approximate degree of cover of the painted surface
by the biofilm (fouling). The same two investigators
Paint color/ MG BR R BR SH TQ PRQ 3GLS GG graded the panels every time, adapting the British
weight of basic Standard Method to note percentage cover as 5, 10, 20,
paint (mg) 40, 60, 80, or 100%. These values were averaged for
each set of three panels. Since readings are not, by
Blue/395 0 0 4 0 1.5 0 0
their nature, precise, fractional means were converted
Marble/500 0 5 0 0 0 0 0
to the nearest whole figure.
Peach/420 0 5 0 0 0 0 1
One of each color test of south-facing panels was
Ceramic/400 0 7 0 0 2 0 10
sent to the University of Portsmouth after 20 months
Ice/420 0 0.4 0 0 2 0 10
of exposure and the biofilm studied under an inverted
Red/300 0 0 0 0 0 0 0
metallurgical microscope, by environmental scanning
Green/440 0 10 0 0 7 12 2
electron microscopy (ESEM; JOEL JSM-6060, 25 kV),
Yellow/500 2.5 10 0 0 0 0 0
without prior treatment, and by direct light microscopy
Straw/450 0 2 0 0 1 0 0
examination and culture on MKM medium of adhesive
Suede/480 0 12 0 0 3 0 2
tape samples.4 Only one set of panels was used so as to
Codes as for Table 3 retain as many samples as possible for final evaluation
of soiling.
1. SUEDE
2. RED Results
3. STRAW Biodeterioration testing
4. YELLOW
Thor Brasil Ltda, São Paulo, using standard microbio-
5. GREEN logical culture and microscope techniques, identified
only the fungus Aspergillus and Gram positive bacilli,
6. ICE
typical air contaminants, in the samples taken from the
7. CERAMIC
parapet surrounding the exposure site. As macroscopic
observation of red staining suggested that the alga
8. MARBLE Trentepohlia was certainly present, we assume that the
standard media used by Thor were not suitable for the
9. BLUE growth of all microorganisms, and especially not for
10. PEACH
algae. Those reported (bacteria and a filamentous fun-
gus) are fast-growing organisms that are readily detected.
Since this information was not important for the inter-
pretation of our results, no further tests were done.
Results of the macroscopic analysis of surface soiling
Fig. 1: South-facing rack showing 10 rows, each contain- are shown in Table 5. Test panels (without film
ing four panels painted in a similar color biocide) began to show discoloration after the ninth
month, when temperatures began to rise again after the
winter (Table 1). Control, biocide-containing panels
occurred. Slides were prepared from this growth and remained unattacked. There was no correlation
examined under an optical microscope. In the case of between temperature at the surface of the panels,
filamentous fungi, cellular structures were compared measured after 245 days, and the degree of surface
with those of known species. In the case of bacteria, no soiling (Table 6).
further tests were carried out. Examples of disfigured yellow-painted panels are
shown in Fig. 2. It is obvious that the degree of cover
by biofilm increased with time. Microorganisms de-
Evaluation of biodeterioration tected on the painted surfaces after 20 months of
exposure to the south are shown in Table 7 and Figs. 3
At intervals up to 34 months (see ‘‘Results’’ section), and 4. Many of the microorganisms detected were
panels were examined macroscopically and the degree darkly colored because of the presence of intracellular
of biofilm formation assessed according to British pigments,13,14 increasing the apparent soiling of the
Standard BS 3900/1989 G6, in which the percentage of paint surface. Fungi were detected on all samples,
cover of the panel by soiling (biofilm growth) is confirming the results of Gaylarde and Gaylarde,15 that
assessed by the naked eye. Digital photos were taken fungi are the major biomass on painted surfaces in Latin
each month. The grading system used to assess America. The same authors state that cyanobacterial
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J. Coat. Technol. Res., 8 (5) 619–628, 2011
Table 5: Mean biodeterioration scores (% cover) for various colored paints exposed to the north (N) or south (S) in
Florianópolis, Brazil, for up to 34 months
Color 12 months/N 20 months/N 34 months/N 12 months/S 20 months/S 34 months/S
genera are mainly the coccoid types and this was also and 2% or less in all others. Highest among the minor
confirmed by our results. oxides was CuO in the blue paint, at almost 0.4%.
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J. Coat. Technol. Res., 8 (5) 619–628, 2011
Fig. 2: Yellow north-facing panels at beginning (a), 14 months (b), and 24 months (c) of exposure
the north of Brazil, where the climate is tropical,18 decrease time of wetness, an important factor in
suggesting that high temperature and humidity are biodeterioration (see, for example, reference 19).
more important than orientation for microbial coloni- The aim of this project was to determine the paint
zation. Temperatures measured at the surface of the pigments most resistant to fouling and the results are
paint films in Florianópolis varied from 28.8 to 31.9°C quite clear in this respect. Blue was obviously the most
for north-facing and from 25.95 to 28.7°C for south- resistant color, with a total score of 102 out of a
facing panels; warmer north-facing surfaces would possible 600, compared to the following colors: red at
promote microbial growth without being so hot as to 180 and ceramic at 233.
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J. Coat. Technol. Res., 8 (5) 619–628, 2011
Table 7: Microorganisms detected by direct microscopy and culture on the south-facing painted surfaces after
20 months’ exposure
Color Bacteria Cyanobacteria Fungi Algae
Ceramic + +
Red + +, including dark-pigmented
Ice +++ + green coccoid, +++ including dark-pigmented
including Gloeocapsa
Suede ++ + green coccoid ++
Marble +++ including + green coccoid ++ including dark-pigmented (+) coccoid
actinomycetes
Yellow ++ + including brown coccoid ++
Blue (+)
Straw ++ including + including brown coccoid ++ including Fusarium
actinomycetes
Green ++ ++ (+) coccoid
Peach ++ +++ coccoid, including green, red, +++ including dark-pigmented
brown Gloeocapsa, green, brown,
blue Synechocystis, brown filamentous
Scytonema
(+), +, ++, +++ = increasing numbers detected
= not detected
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J. Coat. Technol. Res., 8 (5) 619–628, 2011
Table 8: Oxides in the pigment pastes, as a percent of total oxides, analysed by X-ray fluorescence spectropho-
tometry
Oxide Paint pigment
Blue MG BR Yellow R BR Yellow SH White TQ Black PRQ Green 3GLS Red GG
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Cl levels and increased PVC% (red was the paint with 4. Gaylarde, CC, Gaylarde, PM, ‘‘A Comparative Study of the
the highest pigment content of 16.1% w/v giving a Major Microbial Biomass of Biofilms on Exteriors of
PVC% of 67). Ceramic paint, which showed the third Buildings in Europe and Latin America.’’ Int. Biodet.
Biodegrad., 55 131–139 (2005)
best performance, could have been influenced by its
5. Morton, LHG, Gaylarde, CC, ‘‘Deteriogenic Biofilms on
content of SO3, which can lead to acid conditions on Buildings and Their Control.’’ Biofouling, 14 59–74 (1999)
the paint surface, inhibiting growth of some microor- 6. Schoknecht, U, Gruycheva, J, Mathies, H, Bergmann, H,
ganisms, notably cyanobacteria. Burkhardt, M, ‘‘Leaching of Biocides Used in Façade
In conclusion, these results demonstrate that pig- Coatings Under Laboratory Test Conditions.’’ Environ. Sci.
ments affect the timespan of fouling development on Technol., 43 9321–9328 (2009)
the surfaces of painted buildings. A suitable selection 7. Guillitte, O, ‘‘Bioreceptivity: A New Concept for Building
of paint color could reduce the need for dry film Ecology Studies.’’ Sci. Total Environ., 167 215–220 (1995)
biocides, with their accompanying adverse environ- 8. Kappock, PS, ‘‘Biocides: Wet State and Dry Film.’’ In:
mental effects. The possible environmental problems Florio, JJ, Miller, DJ (eds.) Handbook of Coating Additives,
Chapter 8, p 271. Marcel Dekker, NY, 2004.
associated with leaching of the pigments themselves
9. Turner, JN, The Microbiology of Fabricated Materials. J. &
are, of course, another factor that should be consid- A. Churchill, London, 1967
ered, especially where color depends on the presence 10. Boulon, G, Paint Coatings Biodeterioration, 2004. http://
of potentially damaging compounds. Nevertheless, the www.specialchem4coatings.com/resources/articles/printarticle.
option of avoiding, or at least reducing the levels of aspx?id=250. Accessed 24/02/2008
biocides in the paints is attractive, especially in view of 11. Weinert, L, Conflicting Fungal Resistance Data. http://www.
the new regulations being introduced in Europe. pcimag.com/copyright/5b3897a0a66a7010VgnVCM100000f
932a8c0. Accessed 09/08/2010
12. W.R. Springle, R.J. Holman, R.J. Kennedy, Test Methods to
Predict Microbial Attack of Water-Based Coatings, 2000.
Conclusions Available http://www2.pra-world.com/research/projects/
mawc.htm. Accessed 09/08/2010.
1. After 20 months of exposure to the sub-tropical 13. Gorbushina, AA, Krumbein, WE, Hamman, CH, et al.,
environment of Florianópolis, Brazil, sealed fiber ‘‘Role of Black Fungi in Colour Change and Biodeteriora-
cement panels painted with 10 differently pig- tion of Antique Marbles.’’ Geomicrobiol J, 11 205–220
mented acrylic paints became colonized mainly by (1993)
bacteria and fungi, with some cyanobacteria and 14. Gaylarde, CC, Ortega-Morales, O, Bartolo-Perez, P, ‘‘Bio-
genic Black Crusts on Buildings in Unpolluted Environ-
few algae.
ments.’’ Curr. Microbiol., 54 162–166 (2007)
2. The least affected color at all times was blue, which 15. Gaylarde, CC, Gaylarde, PM, ‘‘A Comparative Study of the
showed a maximum of 30% soiling on south-facing Major Microbial Biomass of Biofilms on Exteriors of
panels after 34 months. Buildings in Europe and Latin America.’’ Int. Biodet.
3. North-facing panels were generally more fouled Biodegrad., 55 131–139 (2005)
than south-facing. 16. Sato, NMN, Nakata, NM, Uemoto, KL, Shirakawa, MA,
4. Blue, red, and ceramic colors always performed Sahade, RF, ‘‘Condensação de vapor de água e desenvolvi-
best. mento de microrganismos em fachada de edifı́cios: estudo de
5. Resistance to fouling may have been due to copper caso [Condensation of Water Vapour and Growth of
in blue and acidity from sulfur oxides in ceramic Microorganisms on the Facades of Buildings: A Case
Study].’’ Annals of Encontro Nacional de Tecnologia do
pigments.
Ambiente Construı́do 9 ANTAC, Rio de Janeiro, 2002,
6. A suitable choice of pigments may prolong paint pp. 1191–1198
film life and reduce the need for biocides. 17. Sato, NMN, Shirakawa, MA, Loh, K, John, VM, ‘‘Influ-
ence of Thermal Properties of Materials in Condensation
and Microorganism Growth on Building Façades.’’
Acknowledgments We wish to thank Clariant, São
11DBMC International Conference on Durability of Build-
Paulo, Brazil, for providing the pigments. Biocides ing Materials and Components, May 11–14, 2008, Istanbul,
were kindly provided by Thor Brasil Ltda, São Paulo. Turkey
18. Shirakawa, MA, Tavares, RG, Gaylarde, CC, Taqueda,
MES, Loh, K, John, VM, ‘‘Climate as the Most Important
Factor Determining Anti-Fungal Biocide Performance in
References Paint Films.’’ Sci. Total Environ., 408 5878–5886 (2011)
19. Barberousse, H, Lombardo, RJ, Tell, G, Coute, A,
1. Banov, A, Paints and Coatings Handbook, 2nd ed. Structures ‘‘Factors Involved in the Colonisation of Building Façades
Publishing Company, Farmington, MI, 1978 by Algae and Cyanobacteria in France.’’ Biofouling, 22
2. Allsopp, D, Seal, K, Gaylarde, C, Introduction to Biodeteri- 69–77 (2006)
oration, 2nd ed. Cambridge University Press, Cambridge, 2004 20. Castro, A, Labiki, C, Caram, L, Basso, A, Fernandes, M,
3. Shirakawa, MA, John, VM, Gaylarde, CC, Gaylarde, PM, ‘‘Medidas de refletância de cores de tintas através de análise
Gambale, W, ‘‘Mould and Phototroph Growth on Masonry espectral [Measurement of Reflectance of Paint Colours by
Facades After Repainting.’’ Mater. Struct., 37 472–479 (2004) Spectral Analysis].’’ Revista da ANTAC, 3 69–76 (2003)
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