Modelling of the Solidification of the Zinc Coating and of the Resulting Morphology.

Angéline POULON-QUINTIN(1), Marie-Noëlle AVETTAND-FÉNOËL(1), Ali CHIRAZI(2), Guy REUMONT(1), Jacques FOCT(1)* and
Frank GOODWIN(3)
(1)
Laboratoire de Métallurgie Physique et Génie des Matériaux – UMR CNRS 8517
Université de Lille I Bât. C6
59655 VILLENEUVE d’ASCQ Cedex
France
Tel. : +33-3-20-43-49-45, Fax : +33-3-20-43-40-40
e-mail : jacques.foct@univ-lille1.fr
(2)
TOMOMAT Technology Transfer Unit
ICMCB-CNRS
33608 PESSAC Cedex
France
(3)
International Lead Zinc Research Organization, Inc. 2025 Meridian Parkway
Post Office Box 12036
Research Triangle Park NC 27709
U.S.A.
e-mail: fgoodwin@ilzro.org

Key words: hot-dip galvanization, zinc coating, lead, solidification, coating microstructure

INTRODUCTION

Since about one century Zinc based coatings on steel obtained by batch galvanizing, hot dip continuous process or electrogalvanizing play
a major technical role for the good corrosion protection of billions tons of steel parts. Unceasing achievements of R&D as well as inspired
industrial innovations brought a continuous improvement of the corresponding processes. From its uninterrupted character, the progress
may be masked, meanwhile it exists and the industrial demand on cost efficiency, reliability, effectiveness … is pushing further the
frontier. In contrast with a very dramatic research breakthrough on an infinitesimal subject, the present study aims to contribute to a
reasonable improvement concerning a huge amount of material. It concerns spangle formation at the surface of the coating resulting from
the zinc solidification which leads to a surface featuring. In some cases, esthetical feature given by spangles is promoted and furnishes
some sort of “quality label”. More frequently in the continuous process, featureless coating is requested because of its favourable influence
on the following other surface treatments such as painting.
The present study aims to analyse the main phenomena which are responsible for the featuring and to draw a strategy likely to be
transferred to the industrial processing protocol in order to obtain featureless coatings. Through different and complementary
characterization techniques and additional numerical simulations, the chain of the successive operations has been partially or totally
deciphered for sample of similar composition but with different treatments, leading either to enhanced or suppressed feature. The different
mechanisms from which result the best nucleation conditions, appear to be the most critical, therefore a strategy to keep the corresponding
stages of the process under control is discussed.

* Author to whom correspondence has to be addressed.

*
 EXPERIMENTS

Two sets of continuous hot-dip galvanized steel sheets were analyzed: the first one supplied by ILZRO, elaborated at 460°C using a lead
containing zinc bath and referenced as “model” sample; the second one composed of industrial samples produced by CORUS in a Rhesca
simulator (already described in 1) using a zinc bath containing 0.25 wt.% Al and 0.11 wt.% Pb. In the latest case, various conditions of
process parameters were used (table I).

Table I Process parameters used to elaborate CORUS industrial samples.

Sample Pulling out speed Air knives
Bath temperature (°C) Cooling rate
number (mm/s) power
1 465 200 80
2 465 200 100
3 465 500 150 Delay to 380° before fast cooling
4 465 500 80
5 465 50 150
8 465 200 80 Immediate fast cooling
9 480 200 80 Delay to 380° before fast cooling
11 450 200 0 No cooling at all

Many experiments were carried out so as to study these hot dip galvanized coatings. Cross section as well as surface of samples were
characterized thanks to optical microscopy and Scanning Electron Microscopy equipped with Electron Dispersive Spectroscopy
(S.E.M./E.D.S.). Transmission Electron Microscopy equipped with Electron Dispersive Spectroscopy in a dedicated S.T.E.M. system
(allowing probe sizes of the electron beam of few nanometers) was used so as to detect lead in thin foils of hot-dip galvanized coating
obtained by electropolishing with a 95 vol.% acetic acid, 5 vol.% perchloric acid solution at 30V and 0.5A.
Nature of phases in the coating was determined by X-Ray diffractometry thanks to a Philips X’Pert diffractometer with a cobalt K 
radiation (Co=0.178897nm).
Synchrotron micro-tomographic imaging method brought precisions about the nature of the different phases within the galvanized surface
as well as their spatial distributions. Experiments were conducted using the ID19 beam line with a multi-layer monochromator at European
Synchrotron Radiation Facility (ESRF in Grenoble, France).
A computerized contact tridimensional surface profiler KLA TENCON P-10 measured the roughness of the galvanized surface sheet: a
tridimensional topographic image of the surface with a vertical resolution of 0.1µm was namely created thanks to an interpolation of
measures based on the “Mountain software”.
Selective electrochemical dissolution was used in order to evaluate the thickness of the inhibition layer: the method has consisted in
applying a 6mA intensity and recording tension E as a function of time t using an electrochemical system composed of 3 electrodes
(calomel electrode as reference, platinum one for measurement and the sample as work electrode). Electrolyte was NaCl salted water
(50g/L) and the interface of control parameters was a computerized Potentiostat / Galvanostat PG201 manufactured by Radiometer
Copenhagen. Data were collected thanks to the Voltamaster software. If corrosion is supposed to be uniform on a surface of 1cm²,
corrosion speed and thicknesses of coating as well as of inhibition layer can be then evaluated, based on the hypothesis that the coating is
only the -zinc phase. Global aspect of the measured electrochemical potential E as a function of time t is presented on figure1. The
corrosion rate, the thickness of the -Zn coatings and of the Fe2Al5 inhibition layer have been determined.

 area :

Figure 1 Global aspect of the curves of electrochemical potential (E) vs. corrosion time (t) showing four different stages.
 RESULTS

1) The “model” sample: coating morphology study.

First, observations have been made on the “model” sample supplied by ILZRO presenting feature observable to the unaided eye 3: typical
snowflake-like features (or six-fold star pattern) named spangles and obtained during solidification of coating (spangle dimension
distribution centred around 15mm). Thickness of the coating has been estimated to 40µm in average value. Mapping of Al, Fe and Pb
elements (figure 2) allowed visualization of inhibition layer enriched in aluminium and iron, continuous barrier between the steel sheet and
the zinc coating appeared during solidification. An estimation of its thickness is about 3± 1µm, mean value calculated based on 25
measurements along the interface based on SEM-BSE images (~2µm with selective electrochemical dissolution). Moreover indexation of
some peaks on X-ray diffraction patterns confirms the composition of inhibition layer which is Fe 2Al5 phase.

Figure 2 Mapping of Fe, Al and Pb lighting the presence of a continuous inhibition layer at the interface with iron (E.D.S./S.E.M.).

Synchrotron micro-tomographic imaging method leads to a 3D-image of the coating. The nature of the different phases in presence inside
the galvanized coating and their spatial distribution and interconnections can be discussed. Figure 3 represents the morphology of the
inhibition layer of Fe2Al5 (calculated thickness: 2-4µm) that covered entirely the surface of the steel support following the initial roughness
3
. The last remark reveals the non-negligible role played by the steel surface preparation on the final morphology and smoothness of the
final galvanised product.

Figure 3 A portion of protective film of Fe2Al5 covering entirely the surface of steel.

The zinc containing volume (top layer of the coating) can be divided into a nearly pure zinc volume and a volume containing a mixture of
zinc and a small amount of lead (about 2.7wt %). The approximate thickness of the zone containing the zinc and zinc alloys varies from 30
up to 40µm (consistent with previous experimental observations). This 3D-microtomography imaging study shows that the zone which
contained lead is localised at the upper part of the coating.
In order to characterize the morphology of the coating at the nanometer scale, Transmission Electron Microscopy has been utilized. Thin
foils were taken from the galvanized layer nearly parallel to the steel sheet and close to the external sheet surface. TEM views presented
are top views of the galvanized layer. Figure 4 depicts the microstructure of a Zn/Zn grain boundary in the galvanized layer. Electron
diffraction patterns from thin foil at this interface clearly shows -zinc phase and an orientation [0001] normal to the sheet. Comparison
between E.D.S. analyses (figure 5) carried out at the grain boundary and inside the grain shows the apparition of a small peak
corresponding to lead localized at the grain boundaries. The present result agrees with the results of Reumont and al. 5.

-Zn

Figure 4 Bright field T.E.M. image of a grain boundary between two -zinc grains and the corresponding diffraction pattern of the bottom
-zinc grain (zone axis=(001)).

Figure 5 E.D.S. / S.T.E.M. analysis of a zinc grain (Left) and of the interface (Right) showing the presence of lead at the interface.

Rugosimetry of spangles has been also measured. The study 3 of the dendrite arm line showed that their width was quite constant and
inferior to 1µm with a good periodicity when their depth varied from 1µm up to 3µm. Each dendrite grew from the same nucleus as
suggested by their parallelism and single direction of growth. This type of feature due to specific solidification phenomenon always
showed unambiguous periodicity and profile characteristics of dendrite similar from one to another, independently on where they were
localized on the studied sheet.

The use of combined cellular automaton ² and finite difference simulation techniques 3, 4 lead to an imaging of the formation of spangle and
of the lead distribution shown on figures 6 and 7. Figure 6 depicts the rejection of lead within the residual interdendritic liquid phase
forming the boundary zones at the end of solidification. This result was confirmed by EDS/STEM analyses (figures 4 and 5). On figure 7
are presented the results of a simulation of the bottom-up solidification of the liquid zinc film from the inhibition layer surface towards the
air-alloy interface as observed experimentally by studying the direction of dendrites and presence of the eutectic zones (Zn-Pb) on the
surface of the galvanized sheet 3.
 Figure 6 Superficial variation of Pb concentration distribution at the end of the solidification process.

Solid fraction, 65%

Solid fraction, 85%

Figure 7 Evolution of the solid fraction during the solidification of the Zn-Al-Pb system from the plate inhibition layer surface towards the
free surface at the air interface for 65% and 85% solid fraction.

2) The process parameter impact on coating microstructure.

On their surfaces, hot-dip galvanized samples obtained in a Rhesca simulator (supplied by CORUS), generally present spangles whose size
distribution strongly depends on process parameters (tables I and II and figure 8).
The comparison of the surface aspect shows for samples 3 and 5 that a rise of pulling out speed leads to the formation of spangles on the
surface of coating. It is important to note that for both samples, air knives power is the greatest tested value. This suggests that for given
composition and temperature of the bath, it is the combination of the air knives power selected value with the pulling out speed which
controls spangles apparition and development. In fact, air knives power as well as the pulling out speed synergetically control the
temperature gradient during the solidification process.

Various methods such as optical microscopy, S.E.M. and selective electrochemical dissolution have been used so as to determine the
thickness of hot-dip galvanized coating and the last two methods, also to evaluate the thickness of inhibition layer (table II). Estimated
values are at least 3 times lower than those found with the “model” sample (Cf. 1)).
For identical bath temperature and pulling out speed value (samples 1-2, 3-4), an increase of the air knives power leads to a decrease of the
layer thickness (resp. 13-7, 19-12µm, SEM) whereas the effect of a delay before cooling appears to be negligible on the thickness taking
into account standard deviation (samples 1-8, resp. 13-10, SEM) even if the impact on the spangle size is obvious (figure 8).
For the same bath temperature and given air knives power value (samples 3-5, 1-4), an increase of the pulling out speed leads to an
increase of the layer thickness (resp. 8-12, 13-19µm, SEM) in the case of a delay at 380°C before cooling (Table II).
For a given pulling out speed value and a fixed air knives power value (samples 8-9-11), with the hypothesis that cooling rate does not
influence layer thickness as previously noticed, an increase of the bath temperature does not induce any noticeable effect on the estimated
values taking into account standard deviation (resp. 10-11-12µm, SEM).
Concerning the inhibition layer (Table II), the influence of the process parameters is not directly comparable with what concerns the
coating as previously shown even if an effect on its continuity and its waviness have been noticed on cross-section coating BSE/SEM
observations. In this case, bath temperature as well as cooling rate are the key parameters because they directly influence the solidification
process i.e. the microstructure of the coating.

Table II Feature characteristics of hot-dip galvanized samples supplied by CORUS.

Qualitative size of
Spangles Coating thickness (µm) Inhibition layer thickness (µm)
spangles
Sample Selective Selective
Optical Optical
yes no small large S.E.M. electrochemical S.E.M. electrochemical
microscopy microscopy
dissolution dissolution
1 X X 11±3 13±4 12±4 - 0.6±0.2 0.7±0.5
2 X X 5±2 7±3 9±6 - 0.2±0.1 0.6±0.4
3 X X 14±2 12±2 12±3 - 0.4±0.1 1.1±0.9
4 X X 20±4 19±4 19±3 - 0.6±0.3 1.3±0.4
5 X 5±2 8±5 2±1 - 1.1±0.4 0.3±0.2
8 X X X 7±2 10±2 10±3 - 1.0±0.5 1.0±0.7
9 X X 13±3 11±3 11±5 - 0.6±0.3 0.7±0.4
11 X X 14±5 12±3 10±6 - 0.2±0.1 0.5±0.3
Figure 8 Surface aspect of the CORUS samples as a function of the sample number i.e. the process parameters (see Table I) showing their
impact on the morphology (same scale on each micrograph).

For all samples, EDS analyses have been carried out in order to control the presence of the inhibition layer at the interface with the steel
sheet. Estimation of the thickness is based on BSE-SEM pictures. However, electrochemical dissolution results will be considered as the
more pertinent measurements even if it is an average thickness value which is estimated (Table II). Moreover, the “surface” studied with
this technique is larger and therefore more representative of the coating. For a given bath temperature and a fixed pulling out speed value
(samples 1-2, 4-3), an increase of the air knives power does not induce any sensible effect on the thickness of the inhibition layer (resp.
0.7-0.6, 1.3-1.1µm, selective electrochemical dissolution) whereas the effect of a delay before cooling seems to lead to an increase of its
value (samples 1-8, resp. 0.7-1µm, selective electrochemical dissolution).
For a given bath temperature and a fixed air knives power value (samples 3-5, 1-4) as well as with a delay at 380°C before cooling, an
increase of the pulling out speed leads to an increase of the inhibition layer thickness (resp. 1.1-0.3, 0.7-1.3µm, selective electrochemical
dissolution).

At this stage of the study, it should be underlined that between the microscopic phenomena and microstructural (j) data on the one hand
and the different processing parameters Pi (temperature of the bath, composition of the bath, pulling out rate, wipping intensity, …) on the
other hand, the relation is far from being straight forwards.
Therefore two approaches are possible:
 Empirical: based on a statistical research of the optimum result R of the process considered as a function of the different
processing parameters P1, P2 .. Pi .. i.e. R (Pi .. Pi ..)
 And a more comprehensive one, based on the following strategy: determination of R(j) and determination of j(Pi)
The discussion presented below aims to understand how j determine R and how to master j through the control of Pi.

DISCUSSION

The experimental observations and results reported above are consistent with many experiments already detailed in the literature 1, 2, 6.
Taking into account the aim of the study 3 dealing with industrial applications, the present discussion has to keep in mind the analysis of all
the phenomena which are taking place during the processing of galvanizing. Once identified all the parameters controlling the coating
formation at the scale of the reaction zone, the critical processing parameters will be examined.

1) Thermal gradient in the zinc layer.

If x is the rolling direction of the sheet, y the transverse direction and z the normal direction the sign of the component of < T > are

the following .

Meanwhile, with the usual cooling rate and pulling out velocity the variation of temperature at the scale of the reaction zone (10 -3-

10-2 m) is vanishing .

As already pointed out by Strutzenberger and Faderl 1 and more recently by Quiroga et al. 7 the high thermal conductivity of Zn (125 Wm -
K ) and the thickness of the layer (~10 m) make the temperature difference along z extremely small: T>  2.10-2K. Therefore at the
1 -1

scale of the reaction zone the role of thermal gradient is negligible and if the global texture shows any anisotropy between x and y the
origin should result from the texture, the roughness and the composition of the steel substrate. As clearly underlined, although thermal
gradient can be neglected concerning its role on texture of the coating, short range fluctuations of T at the scale of dendrites exist and result
from the release of the latent heat of solidification (7.2 10 8 J m3). This effect combined with the anisotropic growth velocity of solid zinc in
the liquid phase and with the composition fluctuations, is responsible for the spangle formation. All the experimental observations obtained
in the present study as well as numerical simulations, are consistent with the above analysis.

2) Influence of alloying elements in the zinc bath.

Since the prehistory of galvanizing the exacerbating role of lead on featuring has been identified. The present aim i.e. to obtain featureless
coating is therefore contrary to the presence of Pb except if the study of the mechanisms affected by Pb addition helps to understand the
promotion and the inhibition of spangle formation. All the observations achieved in the frame of the present work as well as those quoted
in the literature are consistent with a constitutional segregation of Pb induced by the “late” eutectic solidification at 318°C leading to
nearly pure Pb and pure Zn and a vanishing partitioning coefficient between Zn and liquid zinc. As shown by results obtained by
scanning and transmission electron microscopy, by X-ray diffraction, by microprobe analysis, traces of pure Pb are clearly observed at the
surface of the coating as well as sequestered inside the -zinc. The cellular automata Algorithm which has been proposed to simulate the
role of Pb leads to “virtual” distribution of Pb at the surface of the coating which is similar to the synchrotron observations. Meanwhile the
role of Pb on either the nucleation by a screening effect on possible nucleation sites or by increasing the growth rate of the grains as a
result of a decrease of the interfacial energyL- between the liquid zinc and  could not be decided. This “uncertainly” which has never
been settled once and for all has two main grounds: an uncomplete identification of nucleation sites, the probable low value of L- and the

resulting difficulties to calculate versus XPb the lead fraction.

According to Strutzenberger 1 the traces of Pb at the surface of the coating are responsible to the dull aspect of these zones which could be
related with a decrease of L-.
In contrast with Pb the propitious role of aluminium in the zinc bath has been recognized more than forty years ago. The formation of an
inhibition layer of Fe-Al intermetallics and more precisely Fe 2Al5 has been clearly identified by the here presented results which confirm
many previous studies. Meanwhile the continuous character of the Fe 2Al5 layer was seen for the first time in 3D thanks to synchrotron
microtomography 3. In order to quantify and predict the role of Al during all the steps of the process, a thermocalc assessment of the Zn
corner of the Zn-Fe-Al system already determined by Perrot et al. 8 has been achieved 3. Related calculations also furnish the partition
coefficient between the melting point of Zn (419°C) and the eutectic temperature (382°C) for the liquid containing 5 wt% Al. As discussed
below the inhibition layer which also constitute a diffusion barrier between the steel and the bath appears to be the “Locus” of nucleation.
Independently of the large difference between the eutectic solidification temperature in Zn-Pb and Zn-Al the main difference between Al
and Pb is the large affinity of Al for Fe in contrast with the very low one between Pb and Fe.
For this reason it appeared to us, as well as to many others, interesting to examine the intermediate case offered by tin alloying which will
be published later 9.
3) Driving force for solidification and overcooling.
Because the formation of the coating results from a reaction of the liquid with the steel substrate and from the solidification of the liquid
layer controlled by nucleation and growth of  crystals, the driving force for solidification GL→ includes thermal and chemical
components. If the kinetic of nucleation is too low to accompany the cooling rate, a phenomenon of overcooling should be observed as
well as a recalescence phenomenon. If the growth rate of solid phase is fast enough, the overcooling phenomenon can be totally or partially
overtaken by the release of latent heat of solidification. Following the study devoted to spangle formation by Fasoyinu and Weinberg 6
according to which thermocouple measurements agreed with the presence of a plateau in contrast with Pyrometer determination of the
temperature likely to reveal a recalescence phenomenon, most studies on galvanizing concluded that the overcooling temperature would be
less than 1°C. In the case, the conclusion would be erroneous and would be the consequence of a hidden recalescence effect resulting from
low nucleation rate and high growth rate as well as of the thermal inertia of the system “substrate + Zn”, the mechanisms of solidification
would be different than the one commonly assumed and other strategy of thermochemical processing should be explored. When the
overcooling is confirmed to be small, about 1°C or less, it shows that the nucleation is extremely easy, heterogeneous, and starts just below
TF (g* small; see §2.4.).

4) Growth rate of spangles.

The growth rate of solid phase in liquid zinc is highly anisotropic fast along the <11-20> direction (v b), slow along [0001] (vc) and
intermediate along <10-10> (va). It should be underlined that this order agrees with the decreasing interplanar space for planes (0001),
{10 -10} and {11-20}. As long as one considers grains nucleating from the inhibition layer Fe 2Al5 and reaching the surface, one could
estimate that vb would be between 2 and 3 orders of magnitude larger than v c. Meanwhile this estimation is biased by the large difference
between the dimensions along x or y on the one hand, and along z on the other hand.

The growth rate v is a function of temperature: v = o exp exp - (1)

Where GL is the driving force for solidification (<0) and Hv the activation enthalpy for the attachment of Zn atoms from the liquid to
the interface -L (>0).
As suggested by Quiroga et al. 7, the higher the interface energy the easier their deplacement.
Because GL strongly depends on the local overcooling temperature T when Hv only depends on the growth direction, the value of v
is very difficult to determine and the anisotropy in growth rate may be much lower than expected.

5) Nucleation of the solid phase.

As discussed above, the temperature difference between the gas-liquid surface and the substrate-liquid interface is extremely low: 10 -2 –
10-1°C, therefore in usual industrial conditions, the nucleation of the  solid phase is not starting from the gas-liquid surface. If it would be
the case, the role of the inhibition layer Fe2Al5 in continuous galvanizing or of the composition of the steel (Si, P) in hot dipping
galvanizing would not be so dramatic (Sandelin effect) 10. Moreover, in an other hand, it would be more difficult to understand the presence
of lead at the surface of the coating.

It is now rather well accepted that nucleation takes place either at the liquid-solid interface 1, 2, 3, 6, 7 or at the vicinity 10, that the driving force
for solidification has a strong chemical component and(or) that the nucleation is heterogeneous. In the present study, the solidification can
be qualified as reactive and starts at the liquid-substrate contact with the formation of the Fe 2Al5 layer on which some places will act as
heterogeneous nucleation sites. Each site “i” is characterized by its coordinates (x i, yi, zi), the orientation of the ci axis, and the energy
barrier which has to overcome . As underlined in the above presented results, up to now, all our attempts to obtain direct information
about the “locus” of nucleation failed. The possibility to identify some particular “discontinuities” likely to reveal potential nucleation
through Synchrotron tomography appears at the moment hopeless as long as the definition of tomography is only a bit less than one
micrometer.

The above discussed difficulties to identify directly and precisely the nucleation sites are not surprising, therefore numerical simulations
have been performed on the basis of solidification laws likely to be described by cellular automata 4. In this approach which has also been
explored by Semoroz et al. 2, a random distribution of nuclei on the Fe 2Al5 layer is supposed to be characterized by its superficial density
(), the orientation angle  between the normal and the c-axis with a normalized probability distribution P() and a distribution of
nucleation activation energies gi*. As already underlined, the featuring is also the consequence of the anisotropy of the growth rate v a, vb,
vc depending of the local undercooling T(x,y,z). Despite the very generic character of the hypotheses supporting the simulation, the
agreement between the principal characteristics of featuring, spangle, orientation resulting from the numerical approach agrees rather well
with the experimental observations. As an example, the segregation of lead at the surface predicted by the simulations is similar to the
results presented above as well as with those of the literature 2, 7. An other result obtained by simulation concerning the role of lead seems
to support the conclusion of the “poisoning” effect of Pb 2, 3, 7, when the same density of nucleation sites are distributed at the Fe 2Al5-liquid
interface (only about 20 % of those who operate without Pb are still effective in presence of lead). The mechanism of poisoning is resulting
from the variations of gi*. The higher gi* sites do not become effective because of the very low partitioning coefficient of Pb in the solid
zinc. Lead is rejected by the first crystals and makes the late possible nucleation sites sterile (large gi*). This interpretation contradicts the
frequent hypothesis of simultaneous nucleation which was previously accepted 2, 3.

The statistical distribution of the orientations of the c axes of the nuclei is only partially revealed by the surface texture of the coating
because of the possible interferences between neighbouring grains. This interaction is specially active if the mean distance between active
nuclei -1/2 is less than vb t and(or) if the thickness of the coating is larger than v c t as shown by experiments of unidirectional
solidification 7 (with t the duration of the solidification process).

The present discussion underlines 1) the key role played by the nucleation sites, and therefore 2) the mechanisms which control their
formation : - role of the microstructure of the substrate (composition, orientation, grain size, cold working, rugosity, …) – mechanisms of
formation of the inhibition layer texture, morphology, kinetics of formation, temperature of the bath, alloying elements in the zinc bath.
Facing all the incompletely solved problems concerning the sequences of all the phenomena determining the morphology of the coating,
the interest of carefully achieved observations on samples obtained with a process simulator demands some comments. The above
discussion shows that each of the steps of the process determines the “initial conditions” of the following one therefore the consequence of
each step of the discontinuous thermochemical (some time thermomechanical) process has to be analysed. This explains why among a
population of samples made with a simulator some of them can satisfy the industrial demand, because some set of following parameters
are optimized : temperature of the bath, pulling out rate, air knives pressure, cooling rate, intermediate stay at 380°C …

6) Relief of the surface.

As measured by rugosimetry, the emergence of spangles at the surface of zinc coating is systematically observed, and characterized by
hills formed by trunks and branches of the dendrites surrounded by valleys. The depth of the valleys is about 4 m (± 1 m). This
formation of relief suggests that liquid zinc is welting zinc crystals and therefore that the interfacial energy -L, -G, L-G are such that -G
would be comparable or larger than -L + -G. In the absence of experimental measurements and of ab initio calculation a rigorous
verification is not possible, meanwhile the relation -G  -L + L-G does not seem unrealistic. If  was the average energy of a Zn-Zn bond
a rough estimation of -G ~ 3/at -L ~ /at and L-G 2/at would be possible. If L-G could be increased by suitable alloying element the
relief resulting from spangle formation would be reduced.

CONCLUSIONS

When the first concern of the study is dealing with the industrial application, the following conclusions can be drawn: the characteristics of
the coating depend on all the different treatments which precede the complete solidification and the final cooling. In this aspect, the idea is
to optimize the sequence of the discontinuous thermochemical treatments which can maximize the density of heterogeneous nucleation
sites. The importance of all the pretreatments of the steel sheet preceding the contact with zinc is accessible by the correlation between
these process parameters and the final morphology of the zinc coating obtained in simulator under strictly defined conditions. The
optimization of the zinc bath alloying element content as well as of the temperature of the bath corresponds to the creation of the most
favourable population of nucleation sites. Because each step of the process is partially of totally inherited from the previous ones, the
obtention of a featureless coating results from the mastering of all the intermediate stages and therefore from a good understanding of the
involved phenomena.

From the point of view of fundamentals, up to now many essential data are only accessible indirectly, for example the characteristics of the
population of nucleation sites. A precise determination of growth rate by dedicated experiments as well as ab initio calculation of the
different surface and interfacial energies are beyond the scope of this study, despite they would be necessary for completely predictive
simulations. Meanwhile the conditions of formations of nuclei are becoming penetrable. From the previous discussion one can conclude
that a large dispersion of the nucleation activation energy (gi*) spreading towards low values compared to kT F will lead to vanishing
overcooling T and to a reduction of effective nucleation sites. Therefore a narrow distribution of gi* and if possible an appreciable T
(gi* not too small) is likely to favour the simultaneous growth of many grains of which the interplay is leading to featureless coating.

SUMMARY

Zinc coating showing exacerbated featuring as well as samples obtained in a process simulator likely to master and control the influence of
the industrial parameters have been studied and characterized by different techniques (rugosimetry, electron and optical microscopes
before or after selective electrochemical dissolution, X-Ray diffraction, Synchrotron microtomography).
The discussion of the results and of the role of processing parameters as well as the comparison with numerical simulations obtained from
generic cellular automata algorithms show that the principal lever to utilize in order to make featureless coating is concerning the
nucleation process and therefore the conditions of the reaction bath – steel, composition of the bath and pre-treatment, immersion, wiping,
cooling...

ACKNOWLEDGMENTS

We are very grateful to ILZRO which supports the present study and to B. van-Veldhuizen and M. Huisert from CORUS firm (CA
IJmuiden, the Netherlands), who supplied galvanized samples.

REFERENCES

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