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Abstract
Research studies were carried out using AISI 1010 (UNS G10100) steels, treated with
tannin primers formulated with natural tannins extracted from Chilean radiata pine species
and from Brazilian black acacia. Steels were previously blasted, followed by a surface
chemical reaction with tannin solutions free from glues, yielding reaction products of 5 mm
thickness. Afterward, conventional anticorrosive paints were applied on triplicate probes
which were evaluated in a salt fog chamber according to ASTM B 117-73 and ASTM D
714-56 standards, and in potentiodynamic scanning tests. The results indicated that pine
tannins present better reactivity than acacia tannins, with better corrosion inhibition and
better adherence to metallic substrates. It is generally demonstrated that conventional
anticorrosive paints or the painting schemes applied on steel previously treated with a
primer formulated with pine tannins, extend the duration of painting schemes in more than
50% than without this chemical treatment. 7 2000 Elsevier Science Ltd. All rights
reserved.
0010-938X/00/$ - see front matter 7 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 9 9 ) 0 0 1 3 7 - 7
1352 G. Matamala et al. / Corrosion Science 42 (2000) 1351±1362
1. Introduction
2. Methodology
Painting schemes were applied by spraying alkydic, vinylic and epoxy paints
over plain or shot-blasted plates of AISI 1010 steel (UNS G10100). Painting of 10
15 cm steel plates was carried out in one or more coats, over steels without or
with previous treatment with tannins primer. Probes were exposed in triplicate in
a salt fog chamber tests, according to ASTM B117-73 standard, and sprayed with
a 5 wt% solution of NaCl at 388C during 5 min/h exposure.
Probes were assessed by rusting, blistering and adherence. Rusting grade was
determined by direct quanti®cation of the probes by means of a transparent 2 2
mm plastic template, complementing the ASTM D610-68 standard estimation.
Blistering was evaluated according to ASTM D714-56 standard. Adhesion was
measured using a strength coat adhesion instrument, ®xing an aluminum metallic
probe with epoxy adhesive to the painted surface, obtaining an average of several
measurements in order to evaluate the results in kg/cm2.
To complement the salt fog chamber tests, steel electrodes of 1 cm2 were treated
with tannin primer of acacia and pine primer, obtaining 5 mm thickness of
reaction products. The electrodes were subjected in triplicate to electrochemical
potentiodynamic scanning at 250 mV, using scanning rates of 0.25 mV/s, in an
aerated 3 wt% NaCl solution. The potentials and current corrosion were
determined by Tafel techniques using a computer controlled Princeton Applied
Research model 273 potentiostat.
The tannin solutions used have 12% of solids considering the polyvinyl butyral
which acts as a ligand in a solvent mixture of water, ethanol and n-butanol. The
solutions react with steel or with the remnant oxides after a mechanical cleaning
process. Glues are eliminated from tannins previous to the preparation of the
solutions by means of patented processes [21].
3. Results
3.1. Rusting tests in salt fog chamber with one coat of anticorrosives
Clean AISI 1010 steel plates were treated by alkydic, vinylic and epoxy
anticorrosive systems. These anticorrosive paints were applied over steel plates
with or without previous chemical reaction with a primer, formulated with black
acacia or pine tannins, keeping a 5 mm ®lm of reaction products.
Fig. 1. Eect of tannin passivation on alkydic anticorrosive protected steel. Salt fog chamber test
according to ASTM 117-73 standard.
appreciated in steels with pine tannin. The dierence in the inhibitor corrosion of
tannin pine compared with acacia is notable, which can be estimated in 100%,
and it can be appreciated by tracing a parallel to the ordinate of the graph at
dierent oxidation percentages.
The blistering degree, quanti®ed according to ASTM D714-56 standard in the
same alkydic coated plates, is summarized in Table 1. The inhibitor corrosion
Table 1
Blistering of alkydic anticorrosive (14 mm) applied over plain AISI 1010 steel, with or without 5 mm of
tannin passivation products, results after exposure in a salt fog chambera
Exposure time (h) Alkydic anticorrosive Pine primer + alkydic Acacia primer + alkydic
100 8M 10 8 F
200 8 MD 8F 8 M
300 8M 6 M
400 8M 6 MD
a
ASTM D714-56 standard has a numerical scale from 10 to 0, in which 10 represented no blistering
and 8 represented the smallest blister. Letters indicate blistering frequency, designated as: D = dense;
MD = medium dense; M = medium; and F = few.
G. Matamala et al. / Corrosion Science 42 (2000) 1351±1362 1355
capacity that tannin passivation possesses, especially the great dierence that both
tannins show, is appreciated, corroborating the results quanti®ed by the oxidation
of the plates.
Fig. 2. Eect of steel passivation with tannins and vinylic anticorrosive. Salt test according to ASTM B
117-73 standard.
1356 G. Matamala et al. / Corrosion Science 42 (2000) 1351±1362
Table 2
Blistering of vinylic anticorrosive (22 mm) applied over shot-blasted AISI 1010, with or without 5 mm of
tannin passivation products, results after exposure in a salt fog chamber
Exposure time (h) Vinylic anticorrosive Pine primer + vinylic Acacia primer + vinylic
200 8F 10 10
400 8 MD 8F 8M
600 8D 8F 6M
800 8F 6 MD
Fig. 3. Eect of combined tannin primer with epoxic anticorrosive ®lm. Test in salt fog chamber
according to ASTM B 117-73 standard.
G. Matamala et al. / Corrosion Science 42 (2000) 1351±1362 1357
Table 3
Blistering of epoxy anticorrosive (25 mm) applied over shot-blasted AISI 1010, with or without 5 mm of
tannin passivation products, results after exposure in a salt fog chamber
Exposure time (h) Epoxy anticorrosive Pine primer + epoxy Acacia primer + epoxy
250 8 F 10 10
450 6 M 10 10
650 6 MD 10 8F
850 6 D 10 8F
until 850 h. The dierence between both tannins is also corroborated with respect
to the inhibiting corrosion ecacy.
The same test methodology used for the anticorrosives in salt fog chamber, was
used for painting schemes of higher thickness. These schemes were evaluated by
blistering, whose results are given therein after.
Table 4
Blistering of plain AISI 1010 steel, passivated with 5 mm iron tannate ®lm until reaching 59 mm
thickness with alkydic ®nishing paint (results after salt test)
500 10 10
1000 10 8F
1500 8F 8F
2000 8F 6F
1358 G. Matamala et al. / Corrosion Science 42 (2000) 1351±1362
Table 5
Blistering results of epoxy schemes over steel with or without passivation with tannins tested during
3000 h in a salt fog chamber
Schemea 1±173 mm 10 6F 6M 6 MD
Schemeb 2±179 mm 10 10 10 8 F
Schemec 3±176 mm 10 10 8F 8 M
Schemed 4±147 mm 10 10 8F 8 F
a
Scheme 1: Epoxy anticorrosive + 2 ®nishing layers.
b
Scheme 2: Pine primer + epoxy anticorrosive + 2 ®nishing layers.
c
Scheme 3: Acacia primer + epoxy anticorrosive + 2 ®nishing layers.
d
Scheme 4: Pine primer + 2 epoxy ®nishing layers.
without passivation, behaves worse than the scheme where epoxy anticorrosive
was not used (Scheme 4), thus having a less thickness (26 mm). This proves that
the epoxy anticorrosive possesses inferior anticorrosive qualities compared with
the tannin primer. Table 5 also con®rms a better inhibiting corrosion ecacy of
pine tannins than those from black acacia.
Table 6
Adherence of anticorrosives over plain AISI 1010 steel, with or without tannin passivation (probes
without previous aging)
3.4. Polarization results of AISI 1010 steel passivated with pine and acacia tannins
Table 7
Eect of drying temperature on the adherence (kg/cm2) properties of primer tannins over plain AISI
1010 steel
21 15.0 10.0
40 17.3 13.0
66 16.0 11.0
80 15.5 10.3
100 14.3 9.3
125 12.0 8.8
150 9.3 8.3
175 8.8 7.8
1360 G. Matamala et al. / Corrosion Science 42 (2000) 1351±1362
Fig. 4. Corrosion current evolution of AISI 1010 steel covered with 5 mm dry base of equivalent
composition primer formulated with acacia tannins or radiata pine, exposed to aerated 3% NaCl
solution.
Iron tannates, produced by direct reaction of steels and their oxides with pine
or black acacia tannins previously re®ned, demonstrated a great insolubility in
water. Iron tannates maintained in distilled water for one week yielded only iron
traces by direct chemical analysis of the water. The primers used had no ligands
to facilitate the detaching of iron tannates from the metallic substrate.
4. Discussion
The experimental results of this work and those already published [19], reveal
the advantages that steels passivated with natural tannins have, after a mechanical
elimination of oxides. The great inhibiting corrosion capacity of tannins extracted
from radiata pine barks is demonstrated, in comparison to those from black
G. Matamala et al. / Corrosion Science 42 (2000) 1351±1362 1361
5. Conclusions
Acknowledgements
The development of this work was possible thanks to the ®nancial support of
the Research Council of the Universidad de ConcepcioÂn.
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