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Surface & Coatings Technology 202 (2007) 479 – 485

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Study of the comportment of fatty acids and mineral oils on the surface of
steel pieces during galvanization
David Balloy ⁎, J.Y. Dauphin, J.C. Tissier
Ecole Centrale de Lille, BP 48, 59651 Villeneuve d'Ascq cedex, France
Received 9 March 2007; accepted in revised form 7 June 2007
Available online 21 June 2007

Abstract

This study shows that vegetable oil like linseed oil can be used as flux in hot-dip galvanization. The natural fatty acids contained in them seem
to be able to play similar role of chloride flux usually used. Moreover, it is also possible to use a mineral oil with an added acid function. “Pure”
mineral oil well protects the steel from corrosion but leads to a very bad result in galvanization. When an acid function is added to this mineral oil,
for example by an addition of hydrochloric acid, the result in galvanization is very good. The coat thickness and the inter-metallic composition
depend not on the nature of the flux.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Galvanization; Flux; Vegetable oils; Mineral oils

1. Introduction The thin coating of dried salt makes a physical barrier

Before the galvanization, the steel pieces are covered by a
flux which is supposed to improve their reaction with the liquid
zinc alloy. Because it is a strategic element in the galvanization
process, the formula of industrial fluxes is generally very
confidential. There are very few publications about this subject,
however, the work of some famous researchers in galvanization
as Bablik [1], Cook [2], Sjoukes [3], Krepski [4,5] and others
[6–11] enables us to understand how the flux works.
After the pickling and rinsing steps, the parts are immersed in
a bath of flux containing aqueous solution of zinc chloride
(ZnCl2) and ammonium chloride (NH4Cl). These two products
are mixed in different ratios but, the more often, the “double
salt” preparation is used (1 mol ZnCl2 for 2 mol NH4Cl). After
emersion from the flux bath, the parts are dried in an oven
around 110 °C, however the molecules stay at hydrated state
(ZnCl2·xH2O, NH4Cl·yH2O). At this step, NH4Cl allows the
drying of the salt because ZnCl2 is very hydroscopic and stays at
the liquid state if used alone.
⁎ Corresponding author. Tel.: +33 3 20 33 53 74; fax: +33 3 20 33 54 99.
E-mail address: david.balloy@ec-lille.fr (D. Balloy).
0257-8972/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.06.021
between the steel and the room atmosphere. The flux also
protects the parts from oxidation during the immersion in the
hot-dip galvanization bath. In liquid zinc at 450 °C, NH4Cl is
rapidly vaporized or decomposes in NH3; ZnCl2 stays in liquid
state and keeps on protecting the steel from the very hot
atmosphere.
The second role of the flux is to produce very active acids –
called “incipient acids” – during its decomposition. The
mechanism of the conventional chloride flux decomposition is
described in the diagrams in Fig. 1.
In a first step, the ammonium chloride (NH4Cl) decompo-
sition leads to hydrochloric acid (HCl). In a second step, this
acid reacts with the zinc (Zn) of the bath to produce hydrogen
(H2) and ZnCl2 (Fig. 1-a). It can also react with the zinc chloride
(ZnCl2) or with the constitution water (H2O) of the hydrated
molecules to produce 2 hydroxy acids (Fig. 1-b and -c). These
hydroxy acids strip the piece surface just before the contact with
the liquid zinc and allow the well reaction between zinc and iron
guaranty of a good coating.
This article will show that fatty acids or mineral oils added
with an acid function can play the same role as the chloride flux.
The use of such organic materials for fluxing steel parts before
galvanization is interesting for several reasons. For example,
480 D. Balloy et al. / Surface & Coatings Technology 202 (2007) 479–485
Fig. 1. Diagrams of the chloride flux decomposition on the zinc bath.
they protect the steel from the oxidation corrosion or they have a
natural acid character [12].
2. Experiments
Linseed oil — a vegetable oil of the trade – and oleic acid —
a pure fatty acid – were used as flux. A cheaper industrial oily
product was also tested. It is a petrochemical origin lubricant, a
paraffinic base oil with a low viscosity at 20 °C. This oil was
provided by the company IGOL under the name “Gavapa”.
2.1. General experimental protocol
Samples of automobile steel plates (0.7 × 30 × 50 mm) were
galvanized with the following conditions of treatment: degreas-
ing (acetone), rinsing (water), pickling (HCl 15% + 2 g/l of
corrosion inhibitor hexamethylene tetramine: HMT), rinsing
(two times in two baths of water), fluxing and drying in
conditions varying according to the flux (10 min in an oven at
110 °C for the chloride flux and in ambient air for the others).
The samples were galvanized for 3 min in a Technigalva® type
bath [13], at 450 °C, with a speed of emergence of 35 cm/min.
All the samples were stocked at room condition for different
time from 3 h to 72 h between the fluxing and the galvanization
operations. The steel sheets composition (Table 1) was analyzed
with a glow discharge light spectrometer Leco (GDL-850).
2.2. “Single bath” process
Some samples were stripped on an acid bath (15% HCl +
2 g/l HMT) covered with a layer of Gavapa oil (Fig. 2). This
process, called “single bath” in the following part, leads to
minimize the number of preparation steps. Pickling and fluxing
treatments are made in one immersion, without rinsing steps.
Table 1
Steel composition
Element C Si Mn
Wt.% 0.003 0.004 0.042%
When the steel sheet is put in the hydrochloric acid through
the oil layer, some of this oil follows the part and limits the
stripping at the beginning. In a few minutes, all the oil is
removed from the surface of the steel. Then the stripping step is
a few minutes longer than with well degreased parts.
When the sheet is removed from this bath, it comes through
the oil layer and is again covered by oil upon withdrawal.
3. Results
3.1. Appearance
Photographs of the samples before and after galvanization
are presented respectively in Figs. 3 and 4.
The first series of steel sheet was uncovered after the
pickling. The parts were not very oxidized even after 72 h of
staying in air (Fig. 3-a), they were just lusterless. Neverthe-
less, there was no adherence of the coating on this sample
(Fig. 4).
Another series of parts was fluxed with a conventional
chloride mixture of ZnCl2 and NH4Cl. An industrial preparation
was used with one part of ZnCl2 for two parts of NH4Cl.
Although the steel was oxidized in some places after a long time
staying exposed to the air (Fig. 3-b), the results after
galvanization were always satisfactory (Fig. 4).
The third series was immerged in Gavapa oil and was well
protected from the oxidization even after 72 h (Fig. 3-c).
However, there was no real coating in these samples (Fig. 4).
The fourth series of steel sheets was immerged in a pure oleic
acid. With this unconventional flux, the results after galvani-
zation were very good. Nevertheless, when the samples stayed
more than 24 h in the open air, some reddish traces appeared on
the uncoated surface and some missing areas in the coating after
48 h and 72 h.
The fifth series of samples was immerged in linseed oil. In
this case the protection against corrosion was very good. After
72 h, the surface was not oxidized and kept at the same
appearance than just after the pickling. The coating obtained by
P
galvanization was just as good as that obtained with the chloride
0.012
flux.
 D. Balloy et al. / Surface & Coatings Technology 202 (2007) 479–485 481

Fig. 2. Diagram of the “single bath” process.

The last series of parts was immerged in the “single bath”, as
described before (Fig. 2). The corrosion protection after
immersion in the single bath was not as good as that obtained
with the other fluxes. The parts were rapidly colored in brown
and small particles were present at the surface. These particles
come from the single bath. They appeared between the layer of
oil and the hydrochloric acid probably from the pickling of the
oxidized steel. The fact that some oil follows the steel sheet
when it is immerged in the single bath was already described in
the process presentation. So when the oxide of the steel is
stripped, it can be pulled at the top of the aqueous acid solution
by the lower density oil hanging to it. Nevertheless, in this case
the results after galvanization were satisfactory, without missing
areas, but the roughness of the coating was a little greater than
that obtained after fluxing in chloride or in fatty oils.
3.2. Thickness
After galvanization, the zinc coating was characterized by
the thickness measurement with a magnetic induction measurer
(Fischer Deltascope MP3C). This measurement was obtained at
10 different points and the average value and the standard
deviation were recorded.
The thickness of the coating obtained by galvanization for
3 min at 450 °C in a Technigalva® bath are presented in Fig. 5.
The measures on the samples galvanized without flux and
with Gavapa flux are not significant (Fig. 4). The thickness of
the other samples is around 50 μm except for the samples
stripped-fluxed in the single bath, which have a thickness
greater than 60 μm. The thickness seems not to be correlated
with the time of waiting before galvanization.
3.3. Micrographs
In all the cases, the section micrographs show that the
coating consists of the typical inter-metallic compounds of a
galvanization in a Technigalva® bath (Fig. 6) [14]. There is no
significant difference in the thickness of inter-metallic com-
pounds in all the samples. The layer of the delta phase is around
10 μm thick and the zeta one is between 30 and 50 μm thick.
The eta layer, formed by the liquid zinc which follows the part
during the emersion of the bath is not really significant because

Fig. 3. Samples before galvanization after 72 h in open air with a) no flux, b) chloride flux, c) Gavapa, d) linseed oil, e) oleic acid and f) single bath.
482 D. Balloy et al. / Surface & Coatings Technology 202 (2007) 479–485

Fig. 4. Samples galvanized 3 min after 3, 6, 24, 48 and 72 h in open air.

the samples are too small. However, in the case of the single When there is no flux or with the non-acid Gavapa oil there is
bath process, this last layer is more important than in the other no reaction between steel and the liquid zinc. In these cases the
samples studied. results in galvanization are very bad and they highlight the
necessity of the ultimate pickling by flux on steel surface in the
4. Discussion zinc bath.
The use of the linseed oil allows a good reaction between the
This study shows that it is possible to obtain a good result in steel and the liquid zinc. The good oxidation protection is not
galvanization using vegetable or mineral oils as flux. only responsible for this good result, because in the case of the
In term of coating, there is no difference in the inter-metallic Gavapa oil, it is neither oxidation nor reaction between Fe and
compounds obtained with all the fluxes tested. Their nature liquid Zn. There are also in the linseed oil some vegetable acids
depends only on the composition of the liquid metal alloys and like oleic, linolenic or linoleic acids (Table 2), which can give to
is typical of those obtained with a Technigalva® bath. this flux an acid function.
The variability of the thickness of the inter-metallic
compounds, like the zeta layer, results more from the
roughness of the steel than from the nature of the flux. As it
is well explained in several works [15,16], the outbursts are
located principally in convex surface – as seen in micrographs
in Fig. 6 – but are independent of the chemistry of the flux,
except if the nature of the flux modifies the roughness of the
steel; that is not the case here. There is no real difference in the
thickness of the coat obtained by the different ways of fluxing.
The coating is thicker and also rougher only in the case of the
single bath process. This can be explained by a high
concentration in iron, at the oxidized state, at the surface of
the sample before galvanization. As described by Krepski [4],
this iron contributes to the formation of very little drosses in the
vicinity of the part surface and leads to a decrease of the
draining of the liquid zinc when the sample is brought out of the
bath.
The more interesting result is about the reactivity between
the steel and the liquid zinc. The behavior is very different for
the fluxes used in this study. Fig. 5. Total thickness for galvanizing 3 min at 450 °C.
 D. Balloy et al. / Surface & Coatings Technology 202 (2007) 479–485 483

Fig. 6. In cut micrographs of galvanized steel plates fluxed in a) chloride mixture, b) oleic acid, c) linseed oil, and d) single bath.

These vegetable acids seem to play the same role as the flux for the galvanization. The acid function – missing in the
incipient hydroxy acids produced by the decomposition of the case of the use of “pure” Gavapa – seems to be present in the
ZnCl2 and the NH4Cl in the classical chloride flux (Fig. 1) and case of the Gavapa in the single bath process. This acid is
lead to the stripping of the steel in the liquid zinc bath as well. probably coming from the pickling bath just below the Gavapa
While these fatty acids are inactive at room temperature, their oil and in contact with it. To satisfy the liquid–liquid
activity for the stripping in the hot liquid zinc would come from equilibrium, the hydrochloric acid diffuses weakly from the
their decomposition. water to the oil. This acid allows the pickling of the steel just
In the case of the pure oleic acid, the protection against before the reaction with the liquid zinc like in the case of the
corrosion seems not to be so satisfactory. It is clearly noted that decomposition of the chlorides. But the hydrochloric acid seems
the oleic acid – very pure – has a greater reactivity with the steel to be a little too strong at room temperature and the parts are
than commercial linseed oil. The first hypothesis expressed to covered by a red–orange film when they stay in open air. This
explain this result is that the oleic acid could be more acidic at film did not prevent the reaction between the steel and the liquid
room temperature than the other acids contained in the linseed zinc. Hence, it is probably not an iron oxide but rather an iron
oil. This explanation is not valid because all of these acids have chloride. The contact with oxygen is not possible through the
a similar acidity, with a neutralization value around 200 mg organic layer but the acid attack of the iron can lead to the
KOH per gram [16–18]. The major difference between these
two products is their composition. Linseed oil is constituted of
only 19% of oleic, 24% of linoleic and 47% of lineic acids, Table 2
against 100% oleic acid for the second. The reactivity of these Composition of the linseed oil [12]
three pure acids has not been evaluated in the work, and it is
Constituent fatty acid g/100 g total fatty acid
possible that the oleic acid is more active in the corrosion of the
Saturated Palmitic 6.3
steel than the linoleic or the lineic acids. However, even with an
Stearic 2.5
oxidized surface, the results in galvanization are very good after Arachidic 0.5
3, 6 and 24 h in open air. After more than 48 h, some uncoated Unsaturated Oleic 19
areas appear, probably due to the excessive oxidization of the parts. Linoleic 24.1
The results obtained with the single bath flux show that the Linolenic 47.4
Behenic 0.2
Gavapa deposited on the steel with this process is as efficient as
484 D. Balloy et al. / Surface & Coatings Technology 202 (2007) 479–485
formation of FeCl2. Vourlias et al. [19] have previously shown
that a layer of FeCl2 is formed at iron wire surface between the
steps of fluxing in a chloride mixture and galvanizing. In this
case the zinc coating obtained is more irregular and not so good
than that obtained in conditions where the FeCl2 layer is limited.
In the present study the coating more irregularly obtained with
the single bath process are in agreement with these
considerations.
5. Interest of the single bath process
In the laboratory conditions: 20n°C and relatively dry
atmosphere, the steel samples covered by the classical chloride
flux are not very oxidized. In the industrial conditions of
galvanization, the atmosphere is more acidic and wetter than in
the laboratory, because there are several baths with hot and/or
acid aqueous solutions which evaporate several tons of water a
week. Also the parts are usually more oxidized between the
fluxing and the galvanizing steps and the time between these
two steps is limited. Moreover, the corrosive atmosphere is
often responsible for the corrosion of the metallic structure of
the plant.
In the single bath process, the hydrochloric acid bath is
covered with a layer of oil which limits its evaporation (Fig. 7)
and so the aggressiveness of the atmosphere. In addition, it is
possible in this condition to heat up the pickling bath without
fear that the amount of acid in the air increases strongly. It is
also possible to increase the efficiency of this step and
compensate the lowering activity due to the presence of oil at
the sample surface. The pickling time is a little longer in the
“single bath” than in the classical process, because when the
parts are immerged in the bath, they have to pass through the oil
layer. The removal of the oil from the surface of the steel, into
the aqueous part takes several minutes. The activity of the
pickling is not optimal during this time.
The main interest of the single bath process is the reduction
of the number of steps in the preparation of the parts before
galvanization. The operations of pickling, rinsing – usually
several times – and fluxing are grouped into only one step. This
can lead to the improvement of the productivity of the plant
because, even without heating the stripping bath, the time saved
by reducing the number of steps is widely greater than the
increase of the pickling time.
An industrial validation of the single bath process was made
on small parts and leads to very good results.
In the future it will be interesting firstly to test a mineral base
oil, the least expensive one, with a viscosity as low as possible,
such as Gavapa, mixed with a well chosen vegetable oily
product to add an acid function, and secondly to control the
acidity of the mineral oil in the case of the single bath process.
Thirdly it is capital to analyze the smokes and the residual
products to verify their non-toxicity. Finally the quality of the
zinc coatings was only appreciated by optical methods and
section micrographic observations. When there was a coating it
was structurally very close to the conventional one but it can't
be excluded that the surface electrochemical properties are
modified. We intend to measure the service life and to
Fig. 7. Lost of weight of a stripping bath with or without a layer of oil at the top.
characterize the electrochemical properties of the zinc coatings
obtained in the different conditions.
6. Conclusion
This study shows firstly that it is possible to replace the
conventional industrial chloride flux used in galvanization by
a vegetable oil like the linseed oil. Moreover it is also
possible to use a mineral oil added with an acid function.
Indeed, it is shown that a mineral oil which well protects the
steel from the corrosion, but without any acid function, leads
to a very bad result in galvanization, with uncoated areas and
poor adherence of the coating. When the acid function is
added to this mineral oil, for example with contact of
hydrochloric acid, the result in galvanization is very good. If
vegetable oils are used as flux, the result is also good. In this
case, the natural fatty acids contained in them are able to play
the role of flux.
Secondly, a process “single bath” is proposed to merge the
steps of pickling and fluxing. So in the same bath, there is in the
bottom the hydrochloride acid to make the pickling of the steel,
and in the top, the mineral oil used as flux. This oil is enriched in
acid by the contact with the acid bath just below it. Firstly, by
limiting the number of the preparation steps, this process could
reduce production costs. Secondly, by covering the hydro-
chloric acid bath with an oil layer, it limits the aggressiveness of
the atmosphere and the corrosion of the plant and of different
steel parts before the galvanization.
Finally, the coat thickness and the inter-metallic composition
depend not on the nature of the flux, but rather on the
composition of the liquid zinc bath and the roughness of the
surface.
Acknowledgement
Thanks to Mr Tran Thien, from the Igol company for his help
and the different oily products he gave to us, and to Mr
Coursimault from the Société Brenonne de Galvanisation
(SBG) for accepting to test the single bath process in his plant.
 D. Balloy et al. / Surface & Coatings Technology 202 (2007) 479–485 485

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