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Metallurgical analysis of pimples and their influence on the properties of hot

dip galvanized steel sheet

Article  in  Engineering Failure Analysis · December 2012

DOI: 10.1016/j.engfailanal.2012.05.026

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 Engineering Failure Analysis 26 (2012) 81–88

Contents lists available at SciVerse ScienceDirect

Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Metallurgical analysis of pimples and their influence on the properties

of hot dip galvanized steel sheet
A. Azimi a,⇑, F. Ashrafizadeh b, M.R. Toroghinejad b, F. Shahriari c
a
Steel Institute, Isfahan University of Technology, Isfahan 8415683111, Iran
b
Department of Materials Engineering, Isfahan University of Technology, Isfahan 8415683111, Iran
c
Department of Materials Science and Engineering, Shiraz University of Technology, Shiraz 7155713876, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Production of galvanized steel sheets with minimum surface defects has been a major con-
Received 10 October 2011 cern for automotive applications and, therefore, metallurgical assessment of defects and
Accepted 9 May 2012 their effect on the properties of the coated sheet continues to be an important issue. In this
Available online 31 August 2012
paper, pimple defects in hot dip galvanized steel sheets produced in an industrial contin-
uous process have been studied in terms of the microstructure as well as their influence on
Keywords: mechanical properties and corrosion behavior. Surface characteristics and microstructural
Hot dip galvanized sheet
features were examined by scanning electron microscopy and microanalysis. The results
Pimple
Surface defects
indicated that the major cause of pimples was the adherence of metal chips and embedded
Corrosion resistance particles to the sheet surface before the formation of zinc coating. Corrosion resistance of
defect samples was compared with sound galvanized specimens by salt spray and Tafel
polarization tests. The time to red rust was up to 50 h shorter on pimples as compared
to other regions. Evaluation of mechanical properties by tensile testing proved that pimple
defects had no significant influence on strength but they caused a reduction of about 2% in
ductility of the galvanized steel sheet.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction

Hot-dip galvanizing is known as the most common technique for protection of steel sheets and structural sections from
atmospheric corrosion although it can affect the forming characteristics of steel [1]. Due to the competitive manufacturing of
coated sheets, there is an increased interest to produce high quality galvanized steel sheets with minimum defects [2]. Nev-
ertheless, in spite of vast progresses in science and technology of galvanizing process, production of defect free coatings re-
mained a problem, particularly in continuous hot-dip galvanizing. Microstructural defects reduce the formability and
corrosion resistance of steel sheet and macroscopic defects damage the surface quality to such extent that may lead to down
grading the products in applications with high surface quality requirement, e.g. automobile panel [3,4].
One of the common defects, appeared as swelled spots on coated steel sheets, is known as pimple that produces rough
regions on the surface of galvanized coatings [5,6]. The defect is usually produced at the margin of galvanized sheet as a re-
sult of blowing air pattern in air knives [7]. One of the main factors that often lead to pimples is embedded particles in the
coating; such particles are generally composed of dross on top of the galvanizing bath and include some intermetallic com-
pounds [4,8,9]or snout dust containing vaporized zinc particles [2,10]. Outbursts in inhibition layer can be another source of
pimples due to the growth of intermetallic compounds through the coating [5,11]. Pimples have been observed to take place
mainly in zinc coated sheets with thicknesses between 1 and 2 mm; they severely reduce the surface quality of the final

⇑ Corresponding author. Tel.: +98 3113912779; fax: +98 3113912588.

E-mail address: arash.az.ms@gmail.com (A. Azimi).

1350-6307/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.engfailanal.2012.05.026
82 A. Azimi et al. / Engineering Failure Analysis 26 (2012) 81–88

product. Although pimple defects have been mentioned in several papers, their influence on the properties of hot dip zinc
coatings have not been sufficiently reported in published literature. In the present study, the effects of pimples on the met-
allurgical characteristics of continuous galvanized steel sheets are evaluated; the microstructural features of these defects
are presented and the corrosion resistance and mechanical properties of the coated sheet are discussed.

2. Materials and methods

2.1. Sheet material

Samples from JIS G3302 hot-dip galvanized steel sheets produced by a local company were used for this investigation. The
manufacturing conditions including rolling finishing temperature, coiling temperature, cold work percentage and annealing
conditions were the same for all the specimens used in this study [12]. The chemical composition of steel substrate and zinc
coating parameters are shown in Tables 1 and 2, respectively. Table 2 shows that the variations of chemical composition in
the zinc bath for typical samples are negligible. The specimens were selected from a large number of samples to get a coating
thickness in the range of 12 ± 1 lm. The chemical composition of the zinc bath was analyzed by atomic absorption
technique.

2.2. Optical and SEM metallography

Cross sections of the coatings were prepared by conventional metallography method and examined by optical micros-
copy. The specimens were etched in a solution containing 1% nitric acid in amyl alcohol. For the observation of surface mor-
phology, scanning electron microscopy (SEM) was employed and the compositions of defects and coating layers were
determined using energy dispersive spectroscopy (EDS) analysis. In order to remove the coating from the substrate and
examine the origin of defects, hydrochloric acid (HCl) with added inhibitor (hexa methylene tetra amin) was used.

2.3. Corrosion evaluation

Salt spray tests were carried out using a salt spray cabinet according to ASTM B117 standard [13]. The time to 5% red rust
was considered as the criterion for corrosion performance of the specimens. The salt spray tests were carried out in 5% NaCl
solution at 35 °C.
Tafel polarization was performed to further investigate the corrosion behavior. The test was conducted in a 3% NaCl solu-
tion at room temperature using a Parstat model 2273 electrochemical system. A standard corrosion cell kit with a working
electrode, two graphite counter electrodes, and an Ag/AgCl reference electrode were used. Potentiodynamic scanning was
performed by stepping the potential at a scan rate of 1 mV/s from 250 to 350 mV.

2.4. Mechanical testing

Mechanical properties of the galvanized sheets were determined by uniaxial tensile tests. The specimens were punched
according to DIN 10002-1 in the rolling direction of sheets [14] and tested on a Zwick-Roell machine model Z400 equipped
with three extensometers in width, thickness and longitudinal directions. The gauge length and width of the tensile speci-
mens were 80 and 20 mm, respectively. In order to evaluate the influence of defects on formability of the galvanized sheets,
plastic strain ratio (r-value) was calculated from the data obtained by the tensile machine. The plastic strain ratio (r) was
calculated using the following equation [15]:

ew ew ln ðwf =wo Þ
r¼ ¼ ¼ ð1Þ
et ðew þ el Þ ln ðlo wo =lf wf Þ

where w0 and l0 are the initial width and length, and wf and lf are final width and length, respectively; et is the true thickness
strain, ew is the true width strain, and el is the true length strain.

Table 1
Chemical composition of steel sheet substrate (wt%).

Grade C (%) Si (%) Mn (%) P (%) S (%) Al (%) N (ppm) Fe

JIS G3302 0.033 0.009 0.207 0.012 0.008 0.051 0.059 Balance
 A. Azimi et al. / Engineering Failure Analysis 26 (2012) 81–88 83

Table 2
Typical production parameters for specimens.

Specimen Chemical composition of zinc bath (wt.%) Sheet thickness (mm) Bath temperature (°C) Galvanizing line speed (m/min)
Al (%) Fe (%) Pb (%)
1 0.20 0.023 0.030 2 460 ± 1 48
2 0.19 0.022 0.036
3 0.20 0.023 0.030
4 0.20 0.023 0.030

3. Results and discussion

3.1. Structure and analysis of pimples

Fig. 1a shows a typical pimple defect appearing as a swelled area on the surface of galvanized sheet. Such defects have
often been observed near the edge of galvanized sheet, but they may extend to the center of the sheet (Fig. 1b). In the swelled
area, the coating has solidified in a different morphology with no spangle formation. Optical microscopy image from cross
section of the pimpled specimen under etched condition (Fig. 2) showed an embedded particle within the coating.
The results of EDS (Table 3) confirmed that iron was the main constituent of the particle. It can be inferred that the par-
ticle has been adhered to the surface of steel substrate because of the pressing action of rolls in the zinc bath or the subse-
quent rolls.
Surface morphology of the specimens was examined by SEM/EDS to identify the shape, size and the origin of the particles.
A specimen containing two different pimples is shown in Fig. 3 and detailed features of these defects can be observed at
higher magnification in Fig. 4.
Micrograph (Fig. 4a) shows a large size pimple which is covered with a layer of zinc coating and Fig. 4b is the pimple
appearing as a crater on the surface. The results of EDS microanalyses on these pimples are presented in Table 4. The amount
of zinc is high for the crater pimple, probably due to the presence of a coating residue together with Fe at the bottom of the
crater. The chromium and other elements observed in the analysis are related to the chromating treatment of the galvanized
sheet. The chromate solution is generally modified by addition of some elements such as P, Mn and Si to improve the pas-
sivation properties [16]. No iron was detected in the coated pimple whereas in the crater pimple (Fig. 4b), there was some Fe
probably associated with Al due to pick up of intermetallic particles from the bath.
Fig. 5a depicts the appearance of a trapped chip in the zinc coating and Fig. 5b shows the same particle after removal of
the zinc layer by acid solution. Two regions were identified on the chip after detachment from the matrix; the white region is
composed of almost pure zinc, while the dark region is made of iron. According to Table 5, it was confirmed that the particle
was the debris that had been embedded in the zinc coating.
As can be seen in Fig. 6, by stripping the coating, some pimples were removed from the sheet surface. However, complete
coating removal revealed either depression marks remaining on the surface or particles adhered to the steel substrate.
Depressions are generated where adhered chips are pressed onto the sheet surface under the action of rolling pressure.
Fig. 7 shows the particles adhered to the surface of furnace rolls that can stick to steel sheet surface before coating, and lead
to formation of pimples.

Fig. 1. Pimple defect seems as swelled areas on the surface of the galvanized sheet (a) surface of typical pimple and (b) extension of pimples toward the
center of the sheet.
84 A. Azimi et al. / Engineering Failure Analysis 26 (2012) 81–88

Fig. 2. Optical microscopy image from cross section of the galvanized specimen at a pimple defect (etched).

Table 3
The chemical composition of an embedded particle forming a pimple (wt%).

Element Fe Si
Embedded particle 99.52 0.48

Fig. 3. SEM micrograph from two pimples with different features.

Fig. 4. SEM micrograph from (a) surface of a big pimple and (b) pimple with a crater on its surface.
 A. Azimi et al. / Engineering Failure Analysis 26 (2012) 81–88 85

Table 4
Comparison of EDS results from the surface of the big pimple and pimple with crater (Fig. 4) and the sound coating (wt%).

Element Zn Al Cr Fe P O Si Mn
Big pimple 73.01 4.33 8.28 – 8.68 2.54 2.30 0.87
Pimple with crater 90.28 1.21 3.21 1.91 3.39 – – –
Sound coating 81.78 – 9.12 – 6.98 2.11 – –

Fig. 5. (a) The particle appeared after removing the coating on a pimple and (b) SEM micrograph of the particle in (a) after detaching.

Table 5
EDS analysis of the different regions of the particle in Fig. 5b (wt%).

Element Zn Fe
Region 1 100 –
Region 2 – 100

Fig. 6. Depressions remained on the surface of the galvanized sheet in pimple areas after the coating strip.

3.2. Corrosion behavior

Four specimens with pimples were selected to study the role of defects in corrosion resistance. Results of the salt spray
tests in Fig. 8 demonstrate that in specimens 1 and 2 the presence of pimples had a significant effect on corrosion resistance
of the galvanized sheet whereas in specimens 3 and 4 the time to red rust for pimpled specimens was almost equal to that of
the sound specimens. According to experimental data obtained in the present research, the maximum reduction in corrosion
resistance, based on the salt spray tests, was about 23% equivalent to 50 h reduction in the time to red rust.
The severity of damage to corrosion resistance depends on several factors. The first factor is concerned with the fact that
the concentration of chromate solution is usually high near the edges of the sheet and the salt spray specimens are selected
from these regions as pimple defects usually appear in these areas. Second, the concentration of defects is a key factor to
86 A. Azimi et al. / Engineering Failure Analysis 26 (2012) 81–88

Fig. 7. Metallic debris adhered to the surface of furnace rolls in the galvanizing line.

Fig. 8. The effect of the pimple defect on hours to red rust in salt spray test.

reach the red rust faster; the more the amount of pimples, the faster is the time to red rust. Third, the shape of the pimple is
important; pimples with a crater, as in Fig. 4b, are more susceptible to fast red rust. However, the first factor is likely to de-
crease the corrosion resistance more severely since chromium passivation has a strong effect on the corrosion behavior of
galvanized sheets [16].
Fig. 9 illustrates typical results of Tafel polarization tests. The data are in good agreement with the results of salt spray
tests. The pimples caused the Tafel curve to shift towards higher currents compared with the sound specimen. The amount
of icorr in Table 6 for pimpled specimen is 2.5 lA compared to 1.8 lA for the sound specimen. It can be concluded that pimple
defects caused a significant reduction in corrosion resistance of galvanized steel sheet.

3.3. Tensile properties

Figs. 10–12 show the parameters obtained from tension tests for pimpled and sound specimens. These include tensile
strength, elongation percentage and plastic strain ratio (r-value), respectively. It can be observed that, in general, pimples
have a negligible effect on tensile strength of the galvanized sheet, but the elongation is decreased by 2% (from 37% to

Fig. 9. The comparative Tafel curves for the sound and defective specimens.
 A. Azimi et al. / Engineering Failure Analysis 26 (2012) 81–88 87

Table 6
Comparison of Tafel test results for the sound and defective specimens.

icorr (lA) Ecorr (mV)

Sound specimen 1.8 970
Defective specimen 2.5 970

Fig. 10. The comparative results of ultimate tensile strength for the sound and defective specimens.

Fig. 11. The comparative results of elongation for the sound and defective specimens.

Fig. 12. The comparative results of the average plastic strain ratio for the sound and defective specimens.

35%) in some defective specimens. The influence of pimples on average values of plastic strain ratio is even more pro-
nounced; reductions up to 25% were observed in some defective specimens (Fig. 12).
As expected, pimples induce depressions on the surface, leading to local stress concentration during tensile testing. How-
ever, the sheet thickness is too high compared to the pimple depth which is controlled by the coating thickness and, as a
result, these defects play no considerable role in tensile strength of the sheet. On the other hand, tensile elongation is more
sensitive to stress concentration produced around the pimples and, as such, reductions are observed in both elongation and
plastic strain ratio.
88 A. Azimi et al. / Engineering Failure Analysis 26 (2012) 81–88

Few previous published papers on this subject [17] reported that galvanized coatings had little influence on the mechan-
ical properties and the forming limit of steel sheet. On the other hand, it has been stated that mechanical properties may be
improved by change in such coating features as intermetallic phases, coating thickness and interface friction [18]. Formation
and growth of brittle intermetallic phases in hot dip galvanized coatings, particularly gamma layer, can produce a decrease in
formability [1] and is considered detrimental for some press works. The results obtained in the present research on elonga-
tion and average r-values of the defective specimens indicate that the undesirable effect of pimples is considerable, although
it appears less damaging as compared to a continuous layer of brittle intermetallic phase. Thus, apart from the corrosion
resistance, the distribution and concentration of these defects must be taken into account for applications where formability
of steel sheet is a critical factor.

4. Conclusions

In order to evaluate the influence of pimple defects on the properties of hot dip galvanized steel sheet, selected specimens
from a continuous hot dip production line were examined by SEM and evaluated by microanalysis, corrosion and mechanical
tests. The conclusions drawn from the present work are summarized as follows:

1. The main source of pimple defect in continuous galvanized products was iron chips or debris embedded in the coating.
This could be due to the presence of metal chips adhered to the surface of furnace rolls, suspension particles or interme-
tallic phases in the zinc bath. The pressing action of the zinc bath rollers on the adhered particles, then, produced depres-
sions of various sizes and shapes on the coated sheet surface.
2. Based on the results of salt spray tests, pimples reduced corrosion resistance of galvanized sheets equivalent to 23% (50 h)
reduction in time to red rust. Nevertheless, due to rather high concentration of chromate film on the surface of chromated
specimens, some pimpled samples showed the same corrosion behavior as sound specimens. Increase in corrosion cur-
rent density (icorr) in Tafel test was observed for the pimpled specimens as an indication of reduced corrosion resistance.
3. The influence of pimples on tensile strength was negligible but elongation and plastic strain ratio were decreased as a
result of pimple defects in galvanized steel sheet.

Acknowledgement

The authors would like to acknowledge Mobarakeh Steel Company for providing samples of galvanized steel sheets and
laboratory facilities.

References

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