Effective acid pre-treatments for
galvanised steel
:or correspondence conla~
R Romagnoli
OIDEPINT - Oentro de Investigaci6n y Oesarrollo en Tecnologfa
de Pinturas (CIC-CONICET), Cal le 52 e/121 y 122, (1900) La
Plata, Argentina
Tel: +54 221 4831141
Fax: +54 221 427 1537
Copyright OCCA2003
Surface Coatings International Part B: Coatings Transactions
Vol.86, B4, 247-328,
R Romagnoli, ~,~ V F Vetere ~ and B del A m o ~
1 Professor UNLP
2 CONICET Researcher
CIDEPINT - Centro de InvestigaciOn y Desarrollo en Tecnologi'a de
Pinturas (CIC-CONICET)., Calle 52 e/121 y 122., (1 900) La Plata.,
Argentina
Summaries
Ellective acid pre-treatments lor galvanised steel
Galvanised steel is wide,ly use,d as structural ste,e,I lot different te,chnological applications be.cause, ol its highe,r
corrosion resistance with respect to bare. steel. The protective, abilities ol zinc may be enhanced by employing
thicker coatings (610g/m 2) of by painting the. metallic surlace with an adecluate, syste,rn, originating the. so-calle,d
duplex systems.
The main problem conce,rning zinc painting is ach ie,ving a good adhe,re,nce,ol the. paint system to galvanise,d ste,el.
Ade,quate p re-treatme,nts may e,nhance,tile adhesion ol the. comple,te system and lacilitate, lufther painting.
The. object ol this paper was to lormulate, dillere,nt acid pre-tre,atments lot galvanise,d steel and testtheir pe,dor-
mance with respect to tile adhesion ol a given binder: Tile perlofl-nance ol dillerent non-priming pre,-treatrne,nts lot
galvanise,d steel was evaluated through ele,ctroche,rnical tests and surlace roughness rne,asureme,nts. The. adhesion
ol dillere,nt binde,rs on treated galvanise,d steel was also asse,sse,d ove,r time by e,mploying suitable, standardised
adhe,sion te,sts. The. characteristics ol the conversion coating were studied by scanning e,lectron microscopy (S EM)
and the surlace composition was de,te,rrnine,dby energy dispersive x-ray analysis (EDAX). For tile sell-priming pre-
treatments only changes in adhesion were. determined over time..
The adhesion ol binders on to the. pre,-treate,d galvanised steel strongly depended on tile, nature, ol tile conversion
layer: In e,ve,ry case, adhe,sion tests le,d to good results even alter six months. The. se,ll-priming lorrnulations,
e,xce,ptthat containing vinyl re,sin, also showed good adhe,re,nce,to the. substrate alter six months ol testing.
Pr~traitements ~ I'acide efficaces pour I'acier galvanis~
L'aeier gaivanis@ est beaucoup utilisd comme acier structural pour des applications technologiques diverses a cause
de sa borne r@sistance,corrosion a I'acier non rev~tu. Le,s propridtds protectrice,s du zinc pe,uvent ~tre am@lior@e,s
par rapplication de couche,s plus ~paisses (610g/m 2) ou par le, rev~tement de la surlace, mdtallique selon un sys-
throe, ad~quat, ce, clui donne naissance, ~ ce, clue I'on appelle, les systbme,s duplex.
Le probl~me, principal conce,rnant le, re,vStement du zinc e,st de r~aliser une, bonne adh~re,nce du systbme de re,vSte-
me,nt ~ I'acie,r galvanism.. Des prdtraitements ad~.quats pourraie,nt amdliorer I'adh~.sion du syst~.me,e,ntier et lacilite,r
I'application de. re,v~.tements suppl~.me,ntaires. Le but de ce,t article ~.tait de. lormule,r plusie,urs prdtraitements
rae,ide, pour rae,ie,r galvanis@ et d'e,ssaye,r leur perlormane,e, e,n ce qui concerne, radhdrene,e, d'un liant donn@. La
perlormance, de divers pr~traite,me,nts clui n'~taient pas des apprSts pour I'acier galvanisd a dt~ dvalude au moye,n
d' essais dle,ctrochimiques e,t de mesures de n.Jgosit~ sudacique,. L'adhdrence de divers liants a I'acie,r galvanisd a
aussi dt~ ~valu~e, pendant un [certain] temps par le, moye,n d'essais d'adhdrence, normalisds appropri~s. Les car-
ae,tdristiques du rev~tement de, e,onve,rsion dtaie,nt @tudide,spar mie,roscopie @lectronique a balayage, (MEB/SEM)
e,t la composition sL~rlacique, @tait d@terminde par analyse, x en dispe,rsion d'dne,rgie, (EDAX). En ce qui concerne,
les pr~traite,rne,nts clui s'apptgtaie,nt automaticluement nous avons ddte,nnind se,ule,rne,ntdes change,rne,nts d'ad-
hdrence pendant un [ce,ltain]te,mps. L'adhdrence des liants a racier galvanis~ prdtraitd ddpendait be,aucoup de la
nature de la couche, de conversion. Dans tous le,s cas le,s e,ssais d'adhdrence, ont mend ~ de bons rdsultats, rn~rnes
aprbs six tools. Les lormulations qui s'appr~taie,nt automatique,me,nt, ~ rexception de. ce,lles qui conte,naie,nt de. la
r@sine,vinylique, ont aussi montrd une borne adhdrene,e, au substrat aprbs si::Emois d'essais.
Wirkungsvolle S~urevorbehandlungen lilt galvanisierten Stahl
Galvanisie~te.r Stahl wird gerne, als Stluktu re,leif~ent l(Jr verschie.dene te.chnische Anwendungen ve.~,~ende.t,we.il e.s
ve,rgliche,n m it nacktem Stahl se,hr ko rrosionsre,sistent ist. Die, schQtzende, Wirkung yon Zink kann durch die. Ver-
we,ndung yon die,ke,re,nBeschichtungen (610g/m 2) oder dure,h die. Behandlung mit e,ine,m ande,re,nangemessene,n
Schutzsyste,m wie e,ine,rn Duple,x-Syste,rn velbesse~t we,rden.
Das Hauptproblem mit Zinkanstrichen ist, e,ine,gute Haltung zwische,n de,m Anstrich und dem Stahl zu e,~ziele,n.
Angemessene Vorbe,handlung kann hier he,llen, und we,ite,re,sStre,iche,n e,rleichtem.
Die. Absicht dieser Arbe,it war, ,,~erschie,de,neSgure,vorbe,handlungen lLir gal,,~anisie,~te,nStahl he~zustelle,n und ihre,
Leistung im Vergle,ich mit e,ine,m vorgege,bene,n Binde,mitte,I zu LiberprLile,n. Die Le,istung ve,rschiede,ne,r Vorbe-
handlunge,n wurde durch elektroche,mische, Tests und die. Me,ssung der Obe,rflgche,nrauheit ge,me,sse,n.Die. Haitkralt
ve,rschie,nde,ner Bindemittel m it galvanisie,lten Stahl wurde, durch standardisie~te Adhgsionste,sts Libe,rprLilt.
Die. Eigenschalten de,s Konve~tie,rlackes wurde ermitte,lt dutch Raste.re,lektrone,.nrrfikroskopie, (SEivl) und die.
Zusammense,tzung de,r Obe,rflgche wurde, dutch ene,rgie,dispersive, R(Jntge,naulnahrne,n (EDAX)] studielt. FLit Vor-
behandlunge,n m it se,lbst-prim ing ,,~u~de,nnur die Vergnderungen in de r Adhgs ionskralt ge,me,ssen.
Email: estelectro@cidepint.gov.ar
Die, Adhesion yon Binde,m itte,ln an die. Obe,rflgche, yon vodDe,hande,ltengalvanisie,lten Stahl hing stark yon de,r A~t
der Llbergangsschicht aiD. In lede,m Fall ergaben die. Adh~sionste,st gute Resultate, selbst nach sechs Monate,n.
Se,lbst-priming Forrr~ulierungen zeigten auch gute, Haltkralt nach sechs ivlonaten, mit de,r Ausnahme, yon Formi-
lierungen mit Vinylha~z.
301
December 2003

Introduction
Calvanised steel is widely employed in
different industries as structural steel. It
is also employed in different construc-
tions such as bridges, pipelines, cooling
towers, home appliances, railroad elec-
trification works, highways, etc. In brief,
whenever steel is exposed to corroding
environments, a zinc coating deposited
by hot-dip galvanising is recommended
as an effective and economic means to
protect the steel substrate from corro-
sion.
The high corrosion resistance of gal-
vanised steel with respect to bare steel is
due to the fact that zinc forms a barrier
between steel and the aggressive envi-
ronment. The corrosion rate of zinc is
lower than that of steel, thus improving
the durability of tile system. Zinc corro-
sion is also restrained by its own corro-
sion products which tend to block active
sites hi nderi ng the electrochemical reac-
tions.
The protective ability of galvanised steel
may be enhanced by employing thicker
zinc coatings (610~/m 2) or by painting
the metallic surface with an adequate
system, originating the so-called duplex
systems. Painting ,galvanised steel is
desirable for aesthetics, for camouflage,
and for warning or identification marks,
to prevent bimetallic corrosion, etc. Zinc
painting may be avoided in rural areas,
but it is mandatory in industrial and
marine environments, not only for aes-
thetic reasons, but also because of the
poor resistance of these materials to
such corrosive environments. 1
Zinc coatings prevent steel rusting by
acting as a barrier against the environ-
ment and sacrificially corroding them-
selves to provide cathodic protection. In
the case of the duplex system, paint
extends the surface life of tile underlying
zinc coating because tile barrier proper-
ty of the paint delays tile reaction of zinc
with environmental agents. Cracks and
voids occurring in the paint are sealed
by zinc corrosion products. In addition,
zinc corrosion products occupy a vol-
ume only slightly greater than zinc (20 to
25%) while rust occupies a volume sev-
eral times greater than steel. Expansive
forces are, therefore, decreased in the
zinc/paint interface with respect to the
steel/paint. 1,2
Tile main problem concerning zinc
painting is achieving ,good adherence of
the paint system to galvanised steel. Tile
zinc surface is non-porous and does not
allow mechanical adhesion of the paint,
although coatings can be successfully
applied after galvanising or after extend-
302
ed weathering. 1,s The adherence may be
satisfacto~' immediately after painting,
but it may be lost as time goes by, and
water, oxygen etc will permeate through
the coating. The failure of the duplex
system is complex and depends oil sev-
eral factors such as surface brightness,
grain size, crystallographic orientation of
the zinc ,grains, surface roughness, and
contaminants present oil the surface,
etc.1,2,4
Several pre-treatments were developed
to improve the adhesion of coatings, s As
a general rule, it can be said that pre-
treatments for galvanised steel surfaces
have a catalysing function in forming
vep/ stable passive films or preventing
the formation of unstable ones.1..2 The
most impoltant of these pre-treatments
are concerned with surface chemical
conve rsio n : p hosp hati n g,1,2
chromating, ~-~ application of wash
primers, 9 organosilane-based pre-treat-
ments 1~ etc. Other pre-treatments are
concerned with the development of an
adequate surface roughness by mechan-
ical means which carl provide a good
surface for painting. 1
Chemical etchants, such as acid or cop-
per sulphate, should not be used. The
actions of these chemicals are difficult to
control, surface preparation may be
non-uniform, and tile galvanised coating
could be damaged if allowed to remain
in extended contact with these chemi-
cals. Although initial adhesion may be
obtained, long-term adhesion could be
impaired with this type of pre-treat-
ment. 1
Pre-treatments can be either priming or
non-priming. Priming formulations must
have the abilib' to form adherent films
which, in turn, must resist the action of
salt spra,~ water and humidit,~ and
increase thermal and mechanical resis-
tance.
Tile object of this paper was to formu-
late different effective acid pre-treat-
ments for ,galvanised steel. These pre-
treatments were either non-priming or
self-priming in nature. In the case of the
non-priming formulations, their effec-
tiveness was accomplished by spreading
a limited amount of the pre-treatment,
by carefully selecting the acids
employed in the formulation, and limit-
ing the reaction time in order to avoid
damaging the zinc coating. The perfor-
mance of the different non-priming pre-
treatments for galvanised steel was eval-
uated through electrochemical tests,
surface roughness and adhesion mea-
surements. The characteristics of the
conversion coating were studied by
scanning electron microscopy (SEM) and
Surface Coatings International Part B: Coatings Transactions
Vol.86, B4, 247-328, December 2003
Effective acid pre-treatments for galvanised steel
R Roma~noli, V F Vetere and B del Amo
the surface composition determined by
ener~ dispersive x-ray analysis (EDAX).
The adhesion of different binders on gal-
vanised steel was assessed over time by
employing suitable standardised adhe-
sion tests. Self-priming pre-treatments
were evaluated with respect to the
adhesion of the organic coatings.
Experimental
As previously stated, two groups of acid
pre-treatment procedures were devel-
oped in this research and their efficiency
checked by different techniques, select-
ed according to the nature of the pre-
treatment. In all cases the adhesion of
different binders was assessed over time.
The first ,group comprised a set of non-
priming pre-treatments; tile other a set
of priming pre-treatments. Both includ-
ed phosphoric acid in tile formulation.
N o n - p r i m i n g pre-treatment (N P)
systems
In all cases, prior to the application of
pre-treatment formulations, samples
were degreased by two procedures.
After each degreasing operation, the effi-
ciency of the cleaning process was
checked by observing if water spread
uniformly over the treated surface. C)ne
of the procedures was carried out by
dipping galvanised steel panels (7.5 x
15cm) into a 5% Na2CO 3 solution and
boiling for ten minutes. Then, they were
washed thoroughly with distilled water
and dried. In tile second procedure,
panels were submerged into a 5%
Na2CO s solution and degreased by
applying a 1A/din 2 current density for 15
minutes at 20~ the panel was used as
the cathode and the anode was a plat-
inum mesh. In this research, a third
option, which will be described below,
was employed which consisted of
degreasing and surface conversion in
only one stage.
Four non-priming acid solutions were
employed to chemically etch tile surface
of each panel. The composition of each
formulation may be seen in Table 1.
Nickel or ferric cations were added to
accelerate zinc dissolution. According to
previous investigations, the rate of zinc
dissolution was found to depend on the
diffusion rate of ferric cation. 11 Zinc
oxide was added to react with phos-
phoric acid to form zinc phosphate
which may precipitate on the metal sur-
face after the decrease of the hydrogen
ion concentration. In evep/ case, the
etching solution was brush-applied on
tile panel and allowed to act for ten m i n-
utes; then it was washed off and dried.
The nlininlLim volLime to be spread by
 Effectiveacid pre-treatmentsfor galvanisedsteel
R Romagnoli,V F Vetereand Bdel Amo

Table 1: Non-priming pre-lreatment systems monitored after six months of exposure

(see Table 2). Another set of panels was
Name Composition % of lost zinc Surface roughness (gm)
placed in the salt-sprav cabinet (ASTM 8
Rt Ra 11 7) and the loss of adherence was also
NP1 O' ~ n/n
HoPO,20 ~'o;ZnO ,:~;.; HNQ 22%; 0.73 19.8 2.23 monitored for six months.
N~(CI~CHO0)20i5%
Self-priming pre-treatment
NP 2 H~PO4 15%; Fe(N03)3.9H20 5% 2.02 7.36 0.63
systems
NP 3 H~PO4 15%; Fe(N03)3.9H20 ,.5~ 1.22 7.07 0.95
Zn(N03)2.6 H20 5% The priming pre-treatment systems
NP 4 H~PO4 24%; NH~8% 2.91 5.90 0.34 employed in this research are described
Note:All percentagesare byweight.Thesolventwasdistilledwaterin evmycase. in Table 3. A classical wash primer con-
Rt:nlaxinlumpeak-to-valleyheight. taining chromates was chosen as a refer-
Ra:arithmeticmeanroughnessvalue,determinedfrom deviationaboutthe centreline,within the evaluatedlength ence; its composition was that of the
SSPC-PT 3-64 standard specification
(see Table 4). The active components of
Table 2: Binder adhesion on galvanised steel pre-lreated with non-priming Iormu-
the primer were basic zinc chromate
lations (ASTM D 3359 lest method) and phosphoric acid, and the film-form-
Non priming Alkyd resin Vinyl resin Epoxy Water-basedepoxy ing material was pol,~%'inyl butvral resin.
pre-treatment 7 6 7 6 7 6 7 6 The other primers were formulated bv
days months days months days months days months adding small amounts of phosphoric
NP1 5B 5 5B 4 4 3 1 1 acid (3%) to a resin previouslv dissolved
in the adequate solvent. Two solvent-
NP2 5 5 5 5 2 5 4 5
borne resins (alkyd and vinyl) and a
NP3 5 5 5 5 2 5 4 5 water-borne binder were employed to
NP4 5 5 5 5 4 5 3 5 formLIlate the self-priming compositions.
The alkyd resin was a medium oil with
square metre of galvanised steel was version laver was then studied bv SEM 52% of linseed oil. The vinyl resin coll-
7Oral. The pre-treatment solution must and its composition bv EDAX. tained carboxvlic groLIpS and its compo-
be spread uniformly, avoiding local sition was as follows: vinyl chloride 83%,
In eve~' case, after the application of the vinyl acetate 1 6%, and maleic acid 1%.
accumulations. The addition of 0.1% of
pre-treatment formulation, different The incorporation of maleic acid made it
a nonionic surfactant improved the
binders were brush-applied up to a compatible with phosphoric acid. The
spreading of the pre-treatment solution
thickness of 12 to 15pro. The panels water-borne resin was an acrylic-styrene
on the substrate.
were allowed to stand for seven days copolvmer and was obtained by a pro-
System NP4 is a combined (degreasing before testing the adherence of the cedure previouslv described/2 The
+ surface conversion) non-priming pre- organic coating bv the ASTM D 3359 water-borne primer was added to the
treatment and was conducted as fol- method. Changes in adherence were
lows: the galvanised steel panel was
placed for five minutes in a bath con- Table 3: Binder adhesion on galvanised steel coaled wilh self-priming formula-
taining 24% H3PO4 + 8% NH3, bv
tions (ASTM D 3359 lest method)
weight. Phosphoric acid was paltiall v
neutralised with ammonia to avoid Identification Composition Adhesion Adhesion
excessive attack oil the zinc coating. 7 days 6 months
Degreasing was achieved bv hydrogen WP (wash primer) Classical wash primer according to 5B 4
bubbling. Hydrogen bubbles were gen- SSPC-PT3-64 standardspecification
erated as a consequence of a proton
AA (alkyd + phosphoric acid) Alkyd resin + 3 % HsPQ 5B 5B
reduction oil the metal surface. Phos-
phoric acid was employed to facilitate WE (water-b0rne resin A water-b0rne acrylic-styrene c0p01ymer 5B 5
the formation of the conversion coating. + phosphoric acid) + 3% HsP04
AV (vinyl resin Vinyl resin + 3 % HsP04 0 0
The dissolution of the zinc coating was + phosphoric acid)
studied bv polarisation measurements.
The electrolytic cell had three elec-
trodes: the working electrode was made Table 4: Chromate-based wash primer pre-treatment according to SSPC-PT 3-64
from high puritv zinc (area 0.29cm2); standard specification
the counter-electrode was a platinum Part A Part B
wire; and the reference was the saturat-
ed calomel electrode (SCE). The scan Component Percentage Component Percentage
rate was 4mVs -1 and the voltage scan Polyvinyl butyral resin 9.2 Phosphoric acid (85%) 18.5
was -+300mV with respect to the corro- Basic zinc chromate 8.8 Isopropanol 16.2
sion potential. Each electrolyte was one
Magnesium silicate 1.3 Water (maximum) 65.0
of the non-priming solutions.
Carbon black 0.1
In each case the dissolved mass of zinc n-butanol 20.5
was determined from weight loss mea- Isopropanol 57.7
surements, the morpholo 9 the coil-
Water (maximum) 2.4
Mixing ratio: 4 partsof A byweight+ 1 partof B

Surface Coatings International Part B: Coatings Transactions 303

Vol.86, B4, 247-328, December 2003

same amount of phosphoric acid. It is
interesting to point out that all the treat-
ment formulations were tolerant to small
amounts of phosphoric acid which was
useful both to etch and passivate the
metal surface.
Primed panels were allowed to stand for
seven days before testing the adherence.
Adhesion tests were conducted in tile
same way described for non-priming
pre-treatm ent systems.
Results and Discussion
N on-pri rning pre-treatrnent (N P)
systems
All the degreasing procedures outlined
in this paper led to good results. Among
the non-priming systems listed in Table
1, the system containing nickel acetate
in its composition (NP 1) produced tile
deepest attack on the zinc coating, thus
leading to the highest surface roughness.
It is thought that tile redox reaction
between Ni (11)ions and metallic zinc
was responsible for the intense reaction
between the substrate and the solution.
The lowest surface profile was obtained
with system NP 4. However, the addi-
tion of Ni (11) ions to the formula
increased the attack oil the surface. The
other two pre-treatments developed a
similar roughness profile.
In evel}~ case, tile mass of zinc lost by tile
acid etching was lower than 3%. Tile dis-
solution of the zinc coating was limited
because the volume of liquid spread oil
the galvanised steel was small and tile
conversioll coating was prevented from
further attack.
The al~'d resin, as well as the vinyl resin,
showed good adherence oil galvanised
steel after seven days, independent of
the applied NP system. The epoxy resin
showed good adherence only on panels
treated with the non-priming NP1 and
NP4 systems. The water-borne vehicle
only showed good adherence with sys-
tems NP2 and NP3. No correlation was
found between adherence and surface
roughness. It is therefore suggested that
adherence was achieved by specific
interactions between the pre-treatment
formulation and the conversion layer oil
the substrate.
All pre-treatment formulations showed
excellent adherence even after six
months of exposure. The epoxy coating
on panels treated with systems NP2 and
NP3 increased its adherence after six
months of exposure. This may be attrib-
uted to the increased cross-linking as
time elapsed. Tile exception must be
made with formLilation NP1 and tile
304
Table 5: Wet adhesion of differenl binders on galvanised sleel, pre-lreated with
non-priming Iormulalions, as a function ol the exposure lime in the salt-spray tesl
(ASTM B 117)
Non-priming Applied vehicle
pre-treatment
NP1 Alkyd
Vinyl
Epoxy
Water-b0me resin
NP2 Alkyd
Vinyl
Epoxy
WateFb0rne resin
NP3 Alkyd
Vinyl
Epoxy
Water-b0rne resin
NP4 Alkyd
Vinyl
Epoxy
Water-borne resin
(-) Panelsweretakenout 0f the salt-spraychamberdue to the 10ssof adhesion
water-based epoxy resin which failed
fi'om the very beginning of the test (see
Table 2). It was also noticed that the
adherence of the epo.'~ binder to tile
zinc substrate increased over time when
formulations NP2, NP3 and NP4 were
employed to prepare the metallic surface
for painting.
The wet adhesion of different binders on
galvanised steel depended oil the pre-
treatment formulation. The NP1 formu-
lation was incompatible with all tile test-
ed resins. Tile NP2 formulation
produced good surface finishing for
painting with the vinyl and the water-
borne binders. NP3 gave good adhesion
with almost all binders except with the
epoxy' binder. The NP4 system showed
an acceptable behaviour only with the
vinyl resin (see Table 5).
The examination of the treated surface
by SEM revealed that system NP1 devel-
oped a layer of large and small c~'stals
(see Figure 1a). The average composition
of both types of crystals, expressed as a
percentage of the oxide of the element,
was P2Os (,42.4%) and ZnO (55.8%).
This composition was close to the theo-
retical composition of zinc phosphate:
P2Os (36.8%) and ZnO (63.2%). Small
amounts of NiO (0.84%) and iron oxide,
Fe20 s (0.96%), were also detected. It
was therefore concluded that the pres-
ence of ZnO in the pre-treatment for-
mulation induced the formation of zinc
phosphate, as previously suggested.
Tile presence of an accelerator such as
ferric cation in the non-priming system
Surface Coatings International Part B: Coatings Transactions
Effective acid pre-treatments for galvanised steel
R Romagnoli, V F Vetere and B del Amo
Time (days)
1 2 3 7 9 14 17
1 0
4 5
0 0
1
5 0
5 5 5 5 5 4 4
2 1 1
5 5 5 5 4 4 4
5 5 5 5 5 5 5
5 4 5 5 3 0
2 1
5 5 5 5 3 4 3
2 1
5 5
0
1
formulation NP2, led to the formation of
amorphous compounds with the appear-
ance of cracked plates (see Figure l b).
Tile average composition of tile plates
was found to be equal to: P2Os (41.1 %);
ZnO (53.1%); and Fe2C)3 (5.80%). In this
case, probably because the higher zinc
dissolution rate, amorphous compounds
instead of crystals were formed. Amor-
phous materials, with the closest struc-
ture and enriched ill ZnO (--79.4%), was
foLInd to be formed on certain zones,
probably due to tile precipitation of
Zn(OH) 2.
Tile non-priming formulation NP3 origi-
nated a sLirface structLire in which small
grains alternated with gel-t~zpe spots (see
Figure 1c). The composition of the small
grains P2Os (21.3%); ZnO (76.1%); and
Fe203 (2.60%) was quite similar to that
of the gels P2C)s (28.8%); ZnO (68.6%);
and Fe203 (2.60%).
Finall,~, the formulation NP4 which did
not contain either accelerators or zinc
compounds, generated a continuous and
amorphous layer with a certain porosity
(see Figure ld). Tile main component of
the layer was ZnO (99.2%).
From the polarisation curves, it may be
seen that the current was always positive
due to metal dissolution originated by a
proton reduction reaction in the acid
medium (see Figure 2). Metal dissolution
could not be suppressed by the applica-
tion of a cathodic overpotential. It
increased linearly when the potential
was scanned in tile positive direction as
if an ohmic control would be coupled
Vol.86, B4, 247-328, December 2003
 Effectiveacid pre-treatmentsfor galvanisedsteel
R Romagnoli,V F Vetereand B dd Amo
Figure 1: SEM micrograph (magnification 2000X) of a galvanised steel panel pre-treated with the different non-prirning systems:
with the chemical redox reaction which
caused metal dissolution. The ohmic
behaviour could be attributed either to
the formation of hydrogen bubbles or to
the formation of a conversion layer on
the metallic surface.
Tile dissolution current at the open cir-
cuit potential was higher for tile pre-
treatment solutions NP1 (170mA) and
NP3 (110mA) (see Figures 2a and 2c),
and was lower for formulations NP2
(66mA) and NP4 (62mA) (see Figures 2b
and 2c).
The open circuit potential for formula-
tions NP1 (-0.027V) and NP3 (-0.012V)
was found to be close to 0 volts while
the corrosion potential of zinc in contact
with NP2 and NP4 formulations was
-0.300V. FormLIlations NP2 and NP4
not only presented the lowest dissolLI-
tion current, but also the conversion
layer diminished the cLIrrent in tile
anodic zone as if a plateau was to be
formed (see Figures 2b and 2d).
The mass of zinc lost during the applica-
tion of the pre-treatment solutions did
not correlate with data derived from
Surface Coatings International Part B: Coatings Transactions
Vol.86, B4, 247-328, December 2003
Table 6: Wet adhesion of differenl binders on galvanised sleel, pre-lreated with
sell-priming Iormulalions, as a function ol the exposure lime in the humidily cahi-
nel (ASTM B 117)
Self-priming pre-treatment Time (days)
1 2 3 7 9 14 17
WP (wash primer) 5 5 5 5 5 5 5
AA (alkyd + phosphoric acid) 5 5 5 5 5 4 4
WE (water-borne resin + phosphoric acid) 1 0
AV (vinyl resin + phosphoric acid) 1 -
(-) Panelsweretakenout of tile salt-spraychamberdue to the lossof adhesion
electrochemical measurements. More- The behaviour of the other two priming
over, it was very similar for all pre-treat- systems were even better than that of the
ment systems, except for system NP1. It conventional formulation containing
was therefore concluded that zinc disso- chromates. The presence of phosphoric
lution was mainly governed by the acid improved the adhesion of the water
nature of the conversion layer formed on resin by reacting with the metallic sub-
it. strate.
Self-priming p r e - t r e a t m e n t Tile wet adhesion of self-priming formLI-
lations on galvanised steel was, as a gem
systems
eral rule, poor, except for formulation
The self-priming formulations also AA which showed very good wet adhe-
showed ,good adherence to the substrate sion during almost the whole test period.
after six months of testing, except for tile The performance of WP formulations
formulation containing the vinyl resin. during this test was also very good (qual-
305
 Effective acid pre-treatments for galvanised steel
R Romagnoli, V F Vetece and B del Amo

a 0.24] 90

0.22] 80

60

0.12]
40
O.lO 1
0.08] 30

. . . . o14 20 . . . . . .

c 0.13I 80-

0.12-
70-
0.II

60-
0.I0

I=

0109I
50-

0108I

40-
0,07I

0.06 3O
-0.4 '
-0.3 '
-0.2 -o'.l 0' 0:i '0:3
0.2 0:4 -O.Z -o'6 -0.5
' -0.4
' -0.3
' -0'.2 -0.1
' 0'
Eft {SEE) ~V (SEE)

Figure 2: Polarisation curves of the zinc electrode in each of the non-priming pre-treatment formulations:
a) NP1; b) NP2; c) NP3; d) NP4
Scan rate 4mVs-1, voltage scan: _+300mVwith respect to the open circuit potential

ification 5), and only slightly better than formulation AA (quali-
fication 4). However, formulation AA is much more pollutant
than formulation WP.
Electrochemical tests were not performed on coated panels
because of the barrier properties of the organic coatings.
Conclusions
1. It is possible to develop effective acid pre-treatments for
galvanised steel by a correct formulation and an adequate
application.
2. Excessive damage of the zinc coating can be avoided by
limiting the reaction time with the non-priming formula-
tions or by employing small amounts of phosphoric acid in
the case of the self-priming pre-treatments.
3. The different non-priming pre-treatment systems originated
different conversion layers. The adhesion of binders strong-
ly depended on the nature of the conversion layer In
ever/case, adhesion tests (ASTM D 3354)1ed to good
results even after six months. The differences between the
various pre-treatment systems were found in wet adhesion
tests.
4. The self-priming pre-treatment formulations, except that
containing the vinyl resin, also showed good adherence to
the substrate after six months oftesting.
5. The wet adhesion of self-priming pre-treatment formula-
tions on galvanised steel was, as a general rule, pooh Tile
exception to this rule was tile formulation containing the
alkyd resin, which can satisfactorily replace conventional
wash primers, containing chromates.
6. The self-priming formulation containing tile alkyd resin
showed good results even in the wet adhesion test.

306 Surface Coatings International Part B: Coatings Transactions

Vol.86, B4, 247-328, December 2003
 Effectiveacid pre-treatmentsfor galvanisedsteel
R Romagnoli,V F Vetere and g dd Amo

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Vol.86, B4, 247-328, December 2003