Material & Metalurgi

Hot dip Galvanizing

10/11/2018 Slide - 2
10/11/2018 Slide - 3
 Classification based on composition
• Galvalume: 55% Al, 43.4% Zn and 1.6% Si
• Galfan: 95% Zn and 5% Al

Advantages
• Improved deformation behavior
• Higher corrosion resistance at thermal stress and atmospheric

10/11/2018 Slide - 4
 Applications
Galvanized coatings are applied to iron and steel primarily to provide
protection against corrosion of the base metal. Some major applications of
hot dip galvanized coatings include:
• Structural steel for power generating plants, petrochemical facilities, heat
exchangers, cooling coils
• Bridge structural members, culverts, corrugated steel pipe, and arches
• Reinforcing steel for cooling towers, architectural precast concrete, and bridge decks
exposed to chlorides
• Highway guard rails, high-rise lighting standards, and sign bridge structures
• Marine pilings and rails
• Architectural applications of structural steel, columns, and related building materials
• Galvanized and painted structural steel for aesthetic, color-coded or extended-life
applications, including communication towers, pipe and sign bridges, railings, fencing,
and agricultural equipment

10/11/2018 Slide - 5
 Hot-dip galvanizing process
source: American Galvanizers Association (AGA)
• Surface preparation
• Galvanizing
• Inspections

10/11/2018 Slide - 6
 Hot-dip galvanizing system

Bath method
(Discontinuous (batch) methods (for profiles cut to
length, construction parts, and small parts).
Hot-dip sheet
(Continuous methods for steel strips and wire)

10/11/2018 Slide - 7
 Surface preparation
• The surface preparation step  quality control because zinc will not react
with unclean steel.
• Surface preparation for galvanizing consists of three steps:
• Degreasing - A hot alkali solution, mild acidic bath, or biological cleaning bath
removes organic contaminants such as dirt, paint markings, grease, and oil from the
metal surface. Epoxies, vinyls, asphalt, or welding slag, which cannot be removed by
degreasing, must be removed before galvanizing by grit-blasting, sand-blasting, or
other mechanical means.
• Pickling – A dilute solution of heated sulfuric acid or ambient hydrochloric acid
removes mill scale and iron oxides (rust) from the steel surface. As an alternative to
or in conjunction with pickling, this step can also be accomplished using abrasive
cleaning or air blasting sand, metallic shot, or grit onto the steel.
• Fluxing – The final surface preparation step in the galvanizing process, a zinc
ammonium chloride solution, serves two purposes. It removes any remaining oxides
and deposits a protective layer on the steel to prevent any further oxides from
forming on the surface prior to immersion in the molten zinc.

10/11/2018 Slide - 8
 Galvanizing
• The material is completely immersed in a bath of molten zinc. The
bath chemistry is specified by ASTM B6, and requires at least
98% pure zinc maintained at approximately 840 F (449 C).
• While immersed  the zinc reacts with the iron in the steel to
form a series of zinc/iron intermetallic alloy layers.
• Once the fabricated items coating growth is complete, they are
withdrawn slowly from the galvanizing bath, and the excess zinc is
removed by draining, vibrating, and/or centrifuging.
• The metallurgical reaction will continue after the articles are
withdrawn from the bath, as long as the article remains near
bath temperature. Articles are cooled either by immersion in a
passivation solution or water or by being left in open air.

10/11/2018 Slide - 9
 Microstructure

• Most of the coating is

nearly pure zinc.
• Structure:
• Near to the steel-
coating interface are
prismatic particles of
zeta phase,
• Alpha zinc-iron
intermetallic compound
containing about 6% Fe.

10/11/2018 Slide - 10
 Layer Formation in Hot - dip Batch Galvanizing
Between 435 ° C and 620 ° C
• The basis for layer - formation processes in batch
galvanizing are the reactions between zinc and iron.
Through reciprocal diffusion, intermetallic Fe - Zn phases
are formed

10/11/2018 Slide - 11
 Coating reaction mechanism

Schematic representation of galvanizing reactions with as a

function of dipping time (a) t = 0; (b) t s and © t2 s(t0<t1<t2)
10/11/2018 Slide - 12
 Microstructure of galvanized coating
(h)

(z)

(d)

(G)

10/11/2018 Slide - 13
 Material & Metalurgi

Silicon content in steel killed

 Parameters: The steel type  content
• Apart from the immersion time and, above all, from the
melting temperature, layer growth is also dependent on the
steel type (content of Si and P).
• 0.015 – 0.020% P, its influence is negligible
• < 0.035% Si, which has to be taken into consideration in
explanations of the galvanizing behavior.

Note: The steel is fully deoxidised (killed) before casting by the addition usually of silicon,
manganese and aluminium, but also sometimes vanadium, titanium and zirconium.

10/11/2018 Slide - 15
 Areas with linear growth

10/11/2018 Slide - 16
 The effect of silicon in the steel on galvanizing
The effect of silicon in the steel:
• The effect of silicon in the steel on galvanizing
• In hot - dip galvanizing release the hydrogen absorbed during
pickling.
Classification of Si content
• Low – silicon range ( <0.035% Si)
• Sandelin effect (Range 0.035 – 0.12% Si )
• Sebisty effect (Range 0.12 – 0.28% Si )
• High - silicon Range ( > 0.28% Si )

10/11/2018 Slide - 17
 The effect of silicon in the steel on galvanizing

Hydrogen
Concatenated pore chains
in the zinc coating typical
for absorbed molecular
hydrogen

10/11/2018 Slide - 18
 The correlations described below refer to the
steels

10/11/2018 Slide - 19
 Material & Metalurgi

Influence of Immersion Time

on Layer Thickness
 Influence of Immersion Time on Layer Thickness:
Low range Si (< 0.035%)
• On low - silicon steel with less than
0.035% Si
• Thin zinc coatings below 120 μm are
formed according to a parabolic time
law, except when galvanizing occurs at
500 ° C.
• At a galvanizing temperature of up to
460 ° C, the layer thickness is always
below 100 μ m.
• Noticeable is the strictly linear growth
of the coating at approximately 500 °
C with a growth rate about three
times higher than in the normal
temperature range.
• In the case of a short immersion time
of approximately 1 min the coatings
are always below 80 μ m regardless of
the temperature. This applies to all
the steels examined.

10/11/2018 Slide - 21
 Influence of Immersion Time on Layer Thickness:
Sandelin range (0.035 -0.12% Si)
• The growth behavior of the zinc coatings on
steel in the Sandelin range (0.035 – 0.12% Si).
• The highest growth values occur in the normal
temperature range between 450 ° C and 470 °
C, with about 45 μm/min at 460 ° C (Sandelin
effect). Except for the low and high
temperatures (435 ° C and 550 ° C)layer
growth is linear.
• This means that there are no impediments or
limiting factors disturbing the iron – zinc
reaction.
• At 550 ° C, only coatings with a thickness of
approximately 40 μ m develop on the
otherwise reactive steel, regardless of the
immersion time. This is a phenomenon
generally observed in high – temperature
galvanizing from 530 ° C.

10/11/2018 Slide - 22
 Influence of Immersion Time on Layer Thickness:
Sebisty range (0.12 – 0.28 % Si)
• In the Sebisty range (0.12 – 0.28%
Si), the highest layer thicknesses are
surprisingly observed at the lowest
galvanizing temperatures (435 ° C
and 445 ° C respectively) and the
layer thickness decreases with
increasing melting temperature
(Sebisty effect).
• With strong linear growth behavior,
galvanizing at 500 ° C is again the
exception.
• In the high - temperature range at
550 ° C, the growth rate decreases
rapidly and the coating thickness is
approximately 70 μ m.

10/11/2018 Slide - 23
 Influence of Immersion Time on Layer Thickness:
High-silicon range (>0.28% Si)
• The ratios for steel in the high -
silicon range ( > 0.28% Si) are shown.
The highest growth rate is achieved
at 460 ° C, with a value of 40 μ
m/min,
• which is only slightly lower than in
the Sandelin range.
• The layer growth proceeds according
to a linear time law, except for high -
temperature galvanizing where a
parabolic time law could be observed
for the steels examined.
• This causes the low layer thickness of
approximately 60 μ m above 530 ° C.

10/11/2018 Slide - 24
 Coating thickness as a function of the immersion
time at a melting temperature 500 ° C
• On all four steels the coatings grow
according to a linear time law;
• Sandelin steel significantly shows the
highest growth rate.
• With the hydrogen theory of layer
formation in mind, the reason for this
should be the postulated constant and
heavy hydrogen effusion of the steel in the
Sandelin range.
• In the Figure it appears that the reaction
kinetics at approximately 500 ° C are
similar for all steels examined, that is, the
structural steels are galvanized according
to the same mechanism that triggers the
linear time law.

10/11/2018 Slide - 25
 Material & Metalurgi

Influence of Melting
Temperature on Layer Thickness
 Parameters: Temperature  layer growth
• The reason for this strong temperature dependence of the layer growth is the reaction
of pure α - iron with zinc,
• Between 430 ° C and 490 ° C,
• layer growth on steels (compact alloy layers firmly adhering to the iron are formed) 
followed a decelerated parabolic time law
• Between 490°C - 530oC
• It followed a linear time law. The linear layer growth occurs due to the change of the reaction
type, since a compact δ phase is no longer formed on the steel (Bablik effect).
• They consist of a very thin, difficult to see G phase, an overlaying thicker d phase, and an
adjacent z phase, from which crystals are permanently dissolved out and float off.
• The coating produced at such galvanizing temperatures is completed by the η phase, which
corresponds to the zinc melt
• Over 530 ° C, only the δ phase is stable and compact and thus the reaction type changes
again to parabolic diffusion with controlled growth

10/11/2018 Slide - 27
 Influence of Melting Temperature on Layer
Thickness: Low silicon range
• Apart from the time - dependent depiction,
the depiction of the temperature
• dependence clearly reflects the correlations.
Figures 4.11 a – d show the thickness profile
as a function of the melting temperature. In
Figure 4.11 , the significant increase in
reactivity in the low silicon range at 490 – 510
° C is clearly visible. In the case of very short
galvanizing time (one minute), differences in
layer thickness do not exist. It is also
remarkable that there is hardly any
temperature dependence of the layer
thicknesses in the normal temperature range
between 435 and 460 ° C.

10/11/2018 Slide - 28
 • Figure 4.11 b shows the
temperature dependence of the
layer growth on Sandelin steel.
Prominent are the particularly high
growth rates in the Sandelin peak at
460 ° C. Short immersion minimizes
this effect and a clear Sandelin peak
occurs only at an immersion time of
≥ 5 min. At 550 ° C, equal and low
coating thicknesses occur regardless
of the immersion time examined.

10/11/2018 Slide - 29
 • The characteristic of steel in the Sebisty
range becomes apparent in Figure 4.11
c. At an immersion time of 10 min, the
Sebisty effect is particularly developed
in the normal temperature range, that
is, between 450 ° C and 470 ° C a signifi
cant decrease in the layer thickness sets
in. The temperature range at 500 ° and
the high -temperature range at 550 ° C
must be examined separately, since,
obviously, completely different growth
conditions exist. Here again, all typical
layer thickness effects only develop
visibly at an immersion time of more
than 5 min.

10/11/2018 Slide - 30
 • Regarding the layer thicknesses,
the result of galvanizing in the
high – silicon range (Figure 4.11
d) is similar to the Sandelin
range. The significant differences
in the structural composition and
their reasons will be discussed
later.

10/11/2018 Slide - 31
 Coating thickness as a function of the Si content
in the steel with immersion time of 10 min
• The galvanizing behavior of the steels in
dependence of the Si content proceeds
according to different mechanisms and
these mechanisms are four individual
states that from a strictly mathematical
point of view cannot be depicted as a
continuous curve.
• The fact that it is nevertheless done and
that, for practical purposes, there is
probably no other possibility, simulates
continuity where discrete individual states
should actually be discussed.
• The galvanizing behavior of the four steel
examples described differs only slightly at
500 ° C, and at 550 ° C, that is, in the high -
temperature range, not at all.

10/11/2018 Slide - 32
 Coating thickness as a function of the Si content
in the steel with immersion time of 10 min
Normal temperature
range
• In the normal temperature range,
especially between 435 and 460° C,
all known phenomena of the steels ’
galvanizing behavior are pronounced
• The Sandelin peak, the Sebisty effect,
the temperature independence in
the low - silicon range and the
relatively high layer thicknesses in
the high - silicon range.

10/11/2018 Slide - 33
 Holistic Theory of Layer Formation

Complete overview of the crystalline structure in batch galvanizing for low - phosphorus
construction steels and conventional zinc melt (galvanizing time> 5 min). Note: In real
terms, a transition behavior between the individual structure fields exists.
10/11/2018 Slide - 34
 Influence of Alloying Elements of the Melt on
Layer Formation
• Conventional Zinc Melts
• Alloyed Zinc Melts

10/11/2018 Slide - 35
 Conventional Zinc Melts
• Consists of technically pure zinc to which lead was added
during the initial years of the development of hot - dip
galvanizing.
• This was due to the availability of raw materials and later for
technological reasons. The melt saturates with iron during
operation and contains small quantities of other metal
contaminants like copper
• In the course of the galvanizing industry development, small
quantities of tin and aluminum were added for optical
reasons (brilliance, spangle).

10/11/2018 Slide - 36
 Alloyed Zinc Melts

10/11/2018 Slide - 37
 Common alloy elements
• Pb  precipitates at different spots in the coating, however,
in particular near the surface in the form of small droplets (1
to 5 μ m).
• Sn  accumulates at the external boundary of the palisade
layer ( ζ phase) between the dross crystals.
• If Bi is alloyed, the Sn/Bi/Pb mixture between the palisade -
shaped crystals can penetrate the zinc coating up to the
compact δ 1 layer and loosen the bond in this layer.

10/11/2018 Slide - 38
 Common alloy elements
• Ni, Ti and V,  small amount (Ni amounts to approximately
0.05%)
• Al  The formation of a thin intermetallic phase of FeAl3 or
Fe2Al5 on the steel surface that is stable at least in the initial
galvanizing phase and inhibits the galvanizing process for a
certain time.

10/11/2018 Slide - 39
 Common alloy elements
• Pb, up to approximately 1%
because its high density causes
it to sag to the bottom of the
zinc tank facilitating the removal
of the dross.
• It also protects the tank bottom
from the direct attack of the zinc
melt.
• On the other hand, it reduces the
surface tension of the zinc melt
and results in smooth coatings.

10/11/2018 Slide - 40
 Reduction of coating thickness on Sandelin steel through the
addition of 0.054% Ni to the zinc me(Steel with 0.08% Si, 445 ° C,
5 min) (a) Conventional melt (b) alloyed melt with nickel addition

10/11/2018 Slide - 41
 Inspection
• The inspection of hot-dip galvanized steel is simple and quick.
• The two properties of the hot-dip galvanized coating closely
scrutinized are coating thickness and coating appearance.
• A variety of simple physical and laboratory tests may be
performed to determine thickness, uniformity, adherence, and
appearance.
• Products are galvanized according to long established, accepted,
and approved standards (i.e. ASTM, ISO, CSA etc) and these
standards cover everything from the minimum coating
thicknesses required for various categories of galvanized items to
the composition of the zinc metal used in the process.

10/11/2018 Slide - 42
 Post - treatment
• The purpose of after - treatment of galvanized surfaces is their
protection against white rust.
• The usual treatment, however, rarely applied, is
• chemical passivation,  Chemical passivation by means of chromate -
containing and chromate - free solutions or phosphating principally
requires methods otherwise only used in electroplating
• lubrication with oil, or
• coating with organic or inorganic materials.
• All in all, it has to be stated that the best after - treatment is the
respective proper storage of the galvanized products

10/11/2018 Slide - 43
 References
• Peter Maaß and Peter Peißker, Handbook of Hot-dip
Galvanization, Wiley-Vch Verlag GmbH & Co. KGaA, 2011
• Indra Laksmana, Coating over hot-dip galvanized steel, 10
years of service coating summit 2016, ASCOATINDO
Conference and Exhibition, Bali, 2016
• J.F.H. van Eijnsbergen, Duplex Systems hot-dip Galvanizing
plus Painting, The Hague, The Netherlands, 1994

10/11/2018 Slide - 44
10/11/2018 Slide - 45
10/11/2018 Slide - 46
10/11/2018 Slide - 47
10/11/2018 Slide - 48
10/11/2018 Slide - 49
10/11/2018 Slide - 50
10/11/2018 Slide - 51
10/11/2018 Slide - 52
10/11/2018 Slide - 53
10/11/2018 Slide - 54
10/11/2018 Slide - 55
10/11/2018 Slide - 56
10/11/2018 Slide - 57
10/11/2018 Slide - 58
10/11/2018 Slide - 59
10/11/2018 Slide - 60
10/11/2018 Slide - 61
10/11/2018 Slide - 62
10/11/2018 Slide - 63
10/11/2018 Slide - 64
10/11/2018 Slide - 65
10/11/2018 Slide - 66
10/11/2018 Slide - 67
10/11/2018 Slide - 68
10/11/2018 Slide - 69