Metallographic Preparation Technique for Hot-Dip

Galvanized and Galvannealed Coatings on Steel

C. E. Jordan, K. M. Goggins, A. O. Benscoter, and A. R. Marder
Lehigh University, Materials Science and Engineering Department, Bethlehem, PA 18015

A new metallographic technique for hot-dip galvanized and galvannealed coatings has been
developed. The new polishing procedure and etchant have shown excellent results on
commercial hot-dip galvanized and galvanneal coatings, as well as on laboratory-simulated
hot-dip galvanneal produced under a variety of thermal processing parameters.

INTRODUCTION of metallographic preparation and etching

Galvanized coatings have been used for
many years, providing sacrificial and anodic
corrosion protection of steel. Zinc can be de-
posited onto steel by a number of different
processes, including hot-dipping, electro-
deposition, and vapor deposition. Galvan-
neal is a galvanized coating that has under-
gone an annealing cycle to transform the
almost all zinc coating to an alloyed iron-
zinc coating. Hot-dip galvanneal has had ex-
panded use in car body parts in the auto-
motive industry because of its improved spot
weldability and perforation corrosion resis-
tance over that of hot-dip galvanized coat-
ings [1]. Because of the increased use of
hot-dip galvanneal by automobile manufac-
turers, there has been new interest in the
research and development of the older and
less costly hot-dip zinc coating process.
Metallographic inspection of these coat-
ings provides a useful tool in the character-
ization of the iron-zinc phase layer growth
that occurs during the galvannealing pro-
cess. Metallography alone cannot determine
the identity of the phases present, but it
can provide useful information w h e n used
in conjunction with other characterization
techniques.
Almost 45 years ago, Rowland [2] made
a significant contribution to the technique
107
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655 Avenue of the Americas, New York, NY 10010
of hot-dip galvanized and galvannealed coat-
ings. In that work he discussed a number
of etchants to be used on coatings depending
upon their immersion time, chemical com-
position, and thermal history. The etchants
developed by Rowland were color etchants,
which could be used to identify phase layers
within the coating based on the color differ-
ence between adjacent phase layers. Row-
land specified the use of different concen-
trations of picric acid, ethyl alcohol, and
water to etch short- and long-time immer-
sion hot-dip galvanized coatings, galvan-
nealed coatings, as well as coatings con-
taining aluminum. He also developed two
alternative solutions for the etching of gal-
vanized coatings containing aluminum.
Rowland's work in color etchants has since
been developed further by Kilpatrick [3].
The coatings discussed in this article are
short-time immersion coatings that are ap-
proximately 10~m in thickness. Metallo-
graphic preparation of thin zinc coatings can
be difficult because the outer edges of the
relatively soft coating can become rounded
during grinding and polishing, thus making
examination difficult. Etching of these coat-
ings can also be a problem because of the
small anode to cathode reaction area ratio,
which causes the zinc coating (anode) to
react rapidly in acidic solutions. Other in-
MATERIALS CHARACTERIZATION 31:107-114 (1993)
1044-5803/93/$6.00
108
vestigators such as Giallourakis et al. [4] have
made an attempt to avoid the difficulties of
metallographic preparation and etching by
developing a cryogenic fracture technique
for the characterization of zinc coatings. This
technique avoids the need for polishing and
etching of the zinc coating altogether.
A new etchant based on Rowland's work
has been developed that is better suited for
today's thinner, short-time immersion, hot-
dip coatings. The etchant was found to work
well for hot-dip galvanized coatings contain-
ing 0.00-0.15 effective wt.% aluminum [5]
that were deposited on a number of differ-
ent steel substrates. The etchant also per-
formed well for coatings that were annealed
under a variety of temperature/time condi-
tions. The preparation technique also uses,
in part, the work of Drewein et al. [6].
Although Drewein's techniques were devel-
oped for electrodeposited coatings, modihca-
tions have been made for improved struc-
tural analysis of hot-dip zinc coatings in the
present investigation.
PROCEDURE
SECTIONING
For standard 31.75mm (1.25in.) mounts, the
sheet samples are cut to 25 x 13ram-size sec-
tions. Sectioning can be performed using
a tabletop hand shear so that the sheet can
be accurately cut to size. The samples are
then placed to form a stack (Fig. 1) with the
25mm-long freshly cut edges parallel to one
EdgesofI n ~ ~ 0 ~ Indicator
vf \ Spacers
pacs* i /
\ * ,=/
%ox; . ' / ,=ta,
M = ~
FIG. 1, Planar view of the mount showing the stack
arrangement of the coated sheet samples.
C. E. Jordan et al.
another. The stack is assembled so that the
long edges are aligned and flush with one
another. The flush orientation of the samples
is important during rough grinding where at
least 2mm of material must be removed from
each sample in the mount, and alignment
ensures this. If one side of each sheet sample
is of particular interest, it is necessary to form
the stack so that the sides of interest are all
facing in the same direction. The reason for
this orientation will be addressed later.
Samples can be separated from one an-
other by placing a small piece of double-stick
tape (spacer) at each short end of the sample,
away from the edge of interest, as shown in
Fig. 2. Any spacer that separates the sheet
samples but keeps their distance apart to
a minimum is suitable. At least six to eight
sheet samples should be used in each stack.
Two additional dummy samples are needed,
one on each side of the stack, to maintain
coating flatness of the end samples. Because
the epoxy resin used for mounting is soft,
stabilizers, such as two cut pieces of steel
welding rod material, should be placed on
either side of the stack to ensure mount flat-
ness during grinding and polishing. As a
point of reference, an indicator (scrap steel
material) can also be included in the mount
(Fig. 1) prior to filling the mould. Epoxy resin
and hardener are then used as the mount-
ing media.
GRINDING
When the mount has cured, excess epoxy
is ground off the surface of the mount until
the metal surfaces of all the samples have
dmm,
samp,s
Sheet ..
sample
" stabilizer
'~ EdgeofInterest
FIG. 2. Individual sheet sample in the process of be-
ing incorporated into the stack arrangement.
Preparation for Hot-Dip Coatings
been completely exposed. The thickness of
the mount is then measured using a mi-
crometer. The mount is rough ground to re-
move at least 2mm of material, so that the
deformation introduced into the coating
during sectioning has been removed. The
amount of material removed can be routinely
checked during grinding if one uses the mi-
crometer to monitor the thickness of the
mount. When a belt grinder is used for
rough grinding, the sheet samples must be
kept parallel to the direction of the belt dur-
ing grinding to prevent edge rounding of
the samples. Edge flatness is critical for ana-
lyzing the zinc coating located at the outer-
most edges of the steel sheet samples.
If the paper used in rough grinding was
120 grit, then grinding should continue on
240-, 320-, 400-, and 600-grit papers, in that
order. The last step in grinding should leave
scratches parallel to the long edges of the
samples to minimize rounding. The mount
should be moved laterally back and forth in
the middle region of the spinning wheel,
off center, with the long edges of the stack
either perpendicular or parallel to the direc-
tion of spin of the wheel [6]. The mount
should then be rotated 90 and held in a sim-
ilar manner while one grinds on a new grade
of grit paper; thus, the new scratches are
perpendicular to those of the previous step.
This method of grinding guarantees that all
of the scratches from the previous step have
been removed. During grinding, the edge
of interest is either the leading edge (first
edge to encounter the motion of the paper)
perpendicular to the spin of the wheel, or
it is parallel to the spin of the wheel, with
the edge of interest closest to the center
of the wheel. The placement of the lead-
ing edges in this manner again minimizes
rounding the edges of interest. After grind-
ing on each paper, the surface is flushed with
alcohol, and the mount is blown dry and
inspected under a light optical microscope
to ensure that (1) all of the scratches are uni-
form in direction in all of the samples in the
mount, and (2) that no scratches remain from
the previous grinding step. The previously
described procedure can be performed on
an automatic grinder (with an applied load
109
of 25psi) by grinding for 60-90 s on each
grade of grit paper.
Immediately after the sample is removed
from the 600-grit paper, the surface is
swabbed with an alcohol saturated cotton
ball, and the mount is flushed with alcohol.
Ethanol (190 or 200 proof) or denatured al-
cohol is suitable for cleaning purposes. The
mount is ultrasonically cleaned for 30-60 s
while standing the mount on edge in a
beaker of alcohol. Precautions should be
taken to be sure that all of the samples in
the mount are submerged in the alcohol dur-
ing ultrasonic cleaning. The mount is blown
dry and inspected. Immediate cleaning of
the mount in alcohol is crucial in maintain-
ing a clean, corrosion-free sample. Ultrafine
grinding continues on an 8- and then 3~m
SiC papers (it is the author's preference to
use 8- and 3~tm papers, but 12- and 5~m
papers are also appropriate for fine grind-
ing), and then the mount is cleaned with al-
cohol (as described earlier) after each paper.
POLISHING
Polishing can begin with a stationary nap-
less cloth similar to the Leco Pan W cloth,
impregnated with 3~tm diamond paste.
Engis diamond extender solution is suitable
as a lubricating media for this and all sub-
sequent polishing steps. A diamond slurry
and extender (pH = 9.6 + 0.2) combination
has also proven to be a successful polishing
media [6]. If a paste is used instead of a
slurry, a d u m m y mount should be used to
work the paste into the new polishing cloth.
Using a d u m m y mount prior to the actual
mount will prevent large scratches from be-
ing introduced into the samples. The mount
should be rotated in a clockwise direction
applying a heavy, even pressure. Polishing
continues for I minute, and then the mount
is cleaned and examined under the light mi-
croscope. The scratches should appear in all
directions, with no parallel scratches remain-
ing from the last grinding step. This proce-
dure is repeated using a new Pan W cloth
impregnated with l~tm diamond paste. Upon
examination after this step, the scratches
present should appear finer.
110
Polishing can then be continued on a sta-
tionary Struers DP NAP cloth charged with
l ~ m paste, or Struers DP spray, HQ. This
polishing cloth need only be charged infre-
quently and can be covered and stored for
future polishing of coatings. A heavy even
pressure must be applied for 30 s, and then
the mount should be cleaned and examined.
The samples should be almost free of
scratches. If large, significant scratches re-
main, polishing should continue for an ad-
ditional 20-30 s, followed by cleaning and
examination. The finish polishing step is per-
formed on a separate Struers DP NAP cloth
charged with 0.25~m diamond paste, or
0.25~m DP-spray, HQ. Heavy pressure for
20 s is required followed by cleaning and
examination. The samples should now be
ready for etching.
ETCHING
The etchant to be used should be prepared
prior to the start of any polishing procedures
so that the sample can be etched at room
temperature immediately after polishing has
been completed. The etchant found to give
the best results was a mixture consisting of
1% picric acid in amyl alcohol and 1% nitric
acid in amyl alcohol. The solution is-pre-
pared by mixing equal parts of 1% picric acid
in amyl alcohol and 1% nitric acid in amyl
alcohol in a beaker. Equal amounts of the
mixed solution are poured into two crucibles.
Into one crucible, 3-4 drops of hydrofluoric
acid (to approximately 50ml of solution) is
added, and a beaker of ethanol is placed near
the two crucibles. It is critical that the etch-
ing solution be prepared with amyl alcohol
and not ethanol. Amyl alcohol-based etch-
ants etch more slowly than ethanol-based
mixtures, thus allowing for more control dur-
ing etching [6].
To etch the samples, the mount is held
with tongs so that the metal surfaces of the
samples face upward. The mount is im-
mersed into the crucible containing no
hydrofluoric acid, and it is slightly agitated
for approximately 20 s. The sample is re-
moved from the crucible and immediately
C. E. Jordan et al.
placed (metal surface side up) into the beaker
containing ethanol. The mount is then re-
moved, the surface flushed with ethanol,
and then immersed into the second crucible
(HF added) and slightly agitated for 10 s.
The surface is flushed again with ethanol,
blown dry, and examined. If the samples are
underetched, the previous procedure is re-
peated using the ratio of 2:1 for the etch-
ing time of the first solution to that of the
second solution.
RESULTS
The etched coatings are shown in Figs. 3, 4,
and 5(a), and are approximately 8-10,m in
thickness. Figure 3 is a hot-dip galvanized
coating, Fig. 4(a-e) shows simulated gal-
vanneal coatings, and Fig. 5(a) is a commer-
cial galvanneal product. All three types of
coatings-hot-dip galvanized, simulated
galvanneal, and commercial galvanneal-
exhibited good relief of structure using the
described preparation technique and etch-
ant. Nomarski differential interference con-
trast in the light microscope allowed the
topographical features of the coatings in
cross section to be viewed.
Figure 6 is an x-ray spectrum of intensity
versus 2 0 values of the hot-dip galvanized
coating shown in Fig. 3. The major peaks
at 36.4, 39.10, and 77.1 correspond to d
spacings of 24.6, 23.0, and 12.4nm that are
FIG. 3. Cross section of a hot-dip galvanized coating
(0.10 effectivewt.% A1-Zn)deposited o n t o a drawing
quality special killed (DQSK) steel.
Preparation for Hot-Dip Coatings
(a)
(c)
FIG. 4. Cross section of a hot-dip galvanized coating
deposited onto a titanium stabilizedinterstitialfree steel
that was annealed for (a) 1 s at 450C; (b) 5 s at 450C;
(c) 10 s at 450C; (d) 20 s at 450C; and (e) 60 s at 450C.
consistent with those for the zinc-rich Fe-Zn
eta phase. Therefore, the x-ray data indicate
that the as-galvanized coating contained es-
sentially all eta phase. Examination of the
coating using wavelength dispersive spec-
troscopy (WDS) analysis confirmed the pres-
ence of blocky crystals of an iron-aluminum-
zinc intermetallic c o m p o u n d located at the
coating/steel interface.
Figure 4(a-e) shows examples of the sim-
ulated galvanneal coatings generated during
thermal processing of an as-galvanized coat-
111
(b)
(d)
(e)
ing (like that s h o w n in Fig. 3) deposited onto
an interstitial free (IF) steel. Because the gal-
vanized coating has u n d e r g o n e a diffusional
transformation u p o n heating, these coatings
have developed a more complex structure
of iron-zinc phases. The x-ray s p e c t r u m
p r e s e n t e d in Fig. 7 was obtained from the
coating s h o w n in Fig. 4(d) and shows that
the largest intensity peaks occur in the 2(9
range of 40-45 . High-intensity peaks for the
Fe-Zn gamma, delta, and zeta phases all
occur at d spacings that c o r r e s p o n d to this
112 C. E. Jordan et al.

(a) (b)
FIG. 5. (a) Cross section of a commercial galvanneal coating. (b) Scanning electron image of the surface structure
of the commercial galvanneal coating shown in (a). (See text for explanation of arrows.)

region. Therefore, it is difficult to identify layer at the coating/steel interface. Also

and quantify the phases present in the gal-
vannealed (alloyed) coating by conventional
x-ray analysis.
For the shorter hold time annealed coat-
ings [Fig. 4(a-c)], an eta phase layer remains
at the outermost part of the coating. Below
this layer there is thought to be a layer of
blocky zeta phase crystals, and a layer of
columnar grains of delta phase. The longer
hold time annealed coatings show no eta
phase remaining in the coating; instead, they
show the presence of a gamma Fe-Zn phase
present in these longer hold time coatings
[Fig. 4(d, e)] are cracks in the delta and
gamma phases, running perpendicular to the
coating/steel interface. Similar metallographic
results were found for coatings deposited
on DQSK (drawing quality special killed),
DQSK preannealed, ultra-low carbon, and
rephosphorized steel substrates. The com-
mercial galvanneal in Fig. 5(a) is very simi-
lar in appearance to the longer hold time
simulation coatings such as shown in Fig.
4(d). In the commercial product, a gamma

2.00
~..62
:i. 28
0,98
0,72
0.50
0.32
0.~.8
0.08
0.02

25.0 30.0 35.0 40.0 45.0 50,0 55.0

1.62l
2.00
i .2B
0.98
0.72
0.50 t
0.32

O~' BI
0.08 FIG. 6. X-ray diffraction spectrum of inten-
0.02 I i i 9., sity (counts) versus 20 values of the as-
55.0 6 55,0 70'.0 75.0 00.0 85.0 galvanized coating in Fig. 3.
0.0
Preparation for Hot-Dip Coatings 113

xiO 3 i
5.00 l
4.05 1
3.20 1
2.45
1.80 !
1.25
O. 80
O. 45
0.20
0.05

25.0 30.0 35.0 40.0 45.0 50.0 55.0

5.00
4.05
3.20 I
2.45
I ,80
'I. 25
0.80

000"45,20
.05 I I I I I I I I I I I I I I I I II I I I I I

55.0 55.0 70.0 75.0 80.0 85.0

50.0

FIG. 7. X-ray diffraction spectrum of intensity (counts) versus 2f) values of the simulated galvannealed coating
in Fig. 4(d).

phase layer is present as well as cracks per-
pendicular to the coating/steel interface.
DISCUSSION
One question that has been raised about the
metallographic procedure is whether the
cracks observed in the microstructure were
created by the technique itself, because of
the brittle nature of the Fe-Zn phases that
form, or are the cracks truly a characteristic
of the coating. Because the gamma phase
is known to be one of the most brittle of the
Fe-Zn phases that develop [7], it has been
proposed that the cracks may have been gen-
erated during polishing. It has been sug-
gested that because of an excess of applied
pressure during polishing and the brittle
nature of the gamma phase, the gamma
phase initially undergoes cracking. The
cracks can then propagate along columnar
delta phase boundaries in the coating to form
cracks that extend the width of the coating.
However, scanning electron microscopy of
the surface of the coating, where no sample
preparation had been performed, revealed
that cracks were present, as shown in Fig.
5(b) (arrows). This hgure is a scanning elec-
tron image of the surface of the coating after
heat treatment but prior to sample prepara-
tion. Thus, the cracks appear to be present
prior to metallographic sample preparation.
It has been found, however, that upon
further polishing of the long hold time sim-
ulation samples [where a signihcant gamma
layer is present, as in Fig. 4(e)], the coating
can become more cracked and difficult to
work with. Care must be taken not to over-
polish the samples.
The most essential part of the metallo-
graphic technique presented here is to keep
the sample surface extremely flat and clean.
During the last steps of grinding and all
throughout polishing, the samples should
be kept free of water, which can cause cor-
114
rosion of the coating. Precautions should
also be taken to maintain edge flatness. The
coatings are approximately 8-10~m in thick-
ness and have a lower hardness than that
of the substrate steel; therefore, to have the
entire cross section of the coating in focus,
the softer outer edge of the coating must be
as fiat as possible relative to the substrate
steel. The stack orientation of the samples
helps to reduce this problem. Nomarski
differential interference contrast also proved
helpful in revealing the topography or tex-
ture of the coatings in cross section.
SUMMARY
A new etchant for hot-dip galvanized coat-
ings has been developed. It has proven
successful for hot-dip galvanized, laboratory-
simulated galvanneal, and commercial gal-
vanneal coatings. The maintenance of coat-
ing sample flatness and cleanliness was
found to be critical in the metallography of
hot-dip galvanized and galvannealed coatings.
The authors thank National Steel, Armco Steel,
LTV Steel, Dofasco, Rouge Steel, Cockerill Sambre,
and Noranda for their sponsorship of this work.
C. E. Jordan et al.
References
1. Y. Hisamatsu, Science and Technology of Zinc and Zinc
Alloyed Coated Steel Sheet, Proc. Galvatech '89, The
Iron and Steel Institute of Japan, Tokyo, Japan, p. 3
(1989).
2. D.H. Rowland, Metallography of hot-dipped gal-
vanized coatings, Trans. ASM 40:983 (1948).
3. J. R. Kilpatrick, A new etching technique for gal-
vanneal and hot-dipped galvanized coatings, Prac-
tical Metallography 28:649 (1991).
4. N. M. Giallourakis, D. K. Matlock, and G. Krauss,
A cryogenic fracture technique for characterizing
zinc-coated steels, Metallography 23:209 (1989).
5. S. Belisle, V. Lezon, and M. Gagne, The Solubility
of Iron in Continuous Hot-Dip Galvanizing Baths, 21st
Meeting of the Galvanizers Association, Monterrey,
Mexico (October 1989).
6. C. A. Drewein, A. O. Benscoter, and A. R. Marder,
Metallographic preparation technique for electro-
deposited iron-zinc alloy coatings on steel, Materi-
als Characterization 26:45 (1991).
7. G. E Bastin, E van Loo, and G. D. Reick, A new
compound in the iron zinc system, Z. Metalkunde
65:656 (1974).
Received November 1992; accepted May 1993.