1

Practical Applications of Phase Diagrams in Continuous Galvanizing

Nai-Yong Tang
Teck Cominco Metals Ltd.
Product Technology Centre
Mississauga, Ontario, Canada

Practical Applications of Phase Diagrams in Continuous Galvanizing

Nai-Yong Tang
ABSTRACT
Zn-Fe based high order phase diagrams have found a wide range of applications in continuous
galvanizing. With the development of computer software DEAL (Determine Effective
ALuminum), the Zn-rich corner of the Zn-Fe-Al phase diagram is being used daily for scientific
interpretation of bath assays. Computer software PAL (Predict Aluminum Level), also
developed by Teck Cominco Metals Ltd., assesses transient equilibria between the steel substrate
and the liquid galvanizing alloy for the estimation of Fe dissolution and Al consumption in
galvanizing. Aluminum deportment in galvanizing baths has been scientifically described based
on the fact that bath assays corresponding to different locations and depths of a galvanizing bath
formed one tie line in the liquid-Fe2Al5 two-phase field. Zn-Fe based high order phase diagrams,
developed in recent years, afford a better understanding of the mechanisms for a number of
industrial phenomena. These practical applications of the Zn-Fe based phase diagrams will be
detailed in the article.

Practical Applications of Phase Diagrams in Continuous Galvanizing

Nai-Yong Tang
Introduction
Phase diagrams are concise representations of the states of equilibrium available to materials
systems. They clearly illustrate the influence of changes in composition, temperature and
pressure on the equilibrium states. However, their complexity increases exponentially with the
number of components present in a system. If binary phase diagrams are frequently used by
researchers and engineers to understand experimentation and production practices, ternary
diagrams are a luxury only for a privileged few. The mention of ternary phase diagrams in
undergraduate texts is universally brief and limited to the simplest systems. Ternary phase
diagrams available in the open literature are limited in number and are frequently too sketchy for
applications in industrial process control.
The development of high order phase diagrams is mainly driven by practical needs and, to a
lesser degree, by the scientific curiosity of devoted researchers. In recent years, a large number
of ternary and partial quaternary phase diagrams evolved from the binary Zn-Fe system have
been developed.(1-10) These developments are the results of the rapid increase in production
capacity in the galvanizing industry, the increasingly stringent quality requirements from end
users, and the dedication of researchers in the Zn industry who strive to serve the galvanizing
industry better. As a result, the Zn-rich corners of these ternary phase diagrams mostly possess a
high accuracy. The partial quaternary phase diagrams are presented in the form of liquid domain,
a perspective presentation of the Zn corner of the phase diagram. Due to the complexity of the
diagrams, they are largely schematic at present, and a complete isothermal tetrahedron of a
quaternary phase diagram has yet to be developed.
Zn-Fe-Al Ternary System
During the hot-dip galvanizing process, Fe constantly dissolves from the steel being coated and
intermetallic compounds form at the interface between the steel and the coating. The amount of
Fe dissolved from the steel is always more than the amount taken out by the coating, resulting in
Fe saturation of the coating bath and the formation of dross. Experimental results, shown in
Figure 1, indicate that the time period for a continuous galvanizing bath to become Fe-saturated
is only about eight hours.

4
1.2

0.07

0.06

0.05

wt% Fe or Al

0.8
0.04
0.6
0.03
0.4
0.02
0.2

0.01

0
5/28/03 6:00

Fe Dissolution Rate (g/m^2)

5/28/03 12:00

5/28/03 18:00

5/29/03 0:00

0
5/29/03 6:00

Time

Figure 1: Increase in Fe content (pink square) of the bath during the early stage
of production. The pot made of Fe was initially loaded with SHG only and the
bath temperature was kept at 470C. The Fe content in the bath reached 0.02%
before commissioning of the line. The bath was saturated with Fe after less than
about eight hours into the production. Calculations indicate that the Fe
dissolution rate (yellow triangle) decreased with time and saturated at about 0.4
g/m2 for such a low Al bath at 470C. Also shown are Al additions (blue dot) to
the bath.
Continuous galvanizing baths always contain a small amount of Al, frequently less than 0.3%, to
mitigate the reaction between the molten Zn alloy and the coated steel. The Al content of the
bath can be as high as 55% if super corrosion resistance of the coating is required. Consequently,
the continuous galvanizing bath is essentially a Zn-Fe-Al ternary system. The amount of Al
required to process a certain type of product is dictated by the law of economics: to produce a
product with the highest quality at the lowest possible cost, thereby maximizing the financial
return for the producer. After more than a decade of intensive research and development, the
optimum Al content of a coating bath can now be scientifically defined based on the product and
pot specifics: around 0.136% for galvannealed, 0.18% for galvanized for the construction
market, and 0.25% for automotive exposed applications.
The complexity of the problem increases exponentially when one tries to better understand how
an alloying addition to the steel would affect the optimum bath Al level and the coating
properties. It is well known that a small amount of P and/or Si in the steel has a strong bearing
on the galvannealing temperature and the final structure and properties of the coatings.(11-12) To
fully understand the underlying mechanisms, one must possess some knowledge of the relevant
quaternary systems, the Zn-Fe-Al-P and Zn-Fe-Al-Si systems.

5
The situation is similar when one tries to improve the performance of bath hardware. While pot
rolls are frequently made of 316L SS, bearings for these rolls are made of complex engineering
alloys frequently containing Co and other transitional metals. To interpret the performance of
pot rolls, one needs a basic knowledge of the Zn-Fe-Al-Cr quaternary system. Additionally, to
understand the performance of bearings made of Stellite, one needs to know the interplay of Co
with the Zn-Fe-Al ternary system. The following sections will provide detailed explanations on
how high order phase diagrams have been developed to better equip line engineers to meet the
challenges arising from their daily work.
Applications of the Zn-Fe-Al Phase Diagram
The refinement of the phase diagram is initially driven by the need for accurate Fe solubility
curves to determine the effective Al content of a bath based on assays of the total Fe and Al.(13,14)
Although a few groups of researchers participated in the drive,(13-16) only researchers at Teck
Comincos Product Technology Centre fully understood the scientific implication of Fe
solubility, and managed to develop isothermal sections with the highest accuracy. They
repeatedly revised the Zn-Fe-Al phase diagram through a combination of experimentation and
thermodynamic modelling.(6,17,18) To facilitate the practical applications of the phase diagram,
computer software DEAL (Determine Effective ALuminum) was written in C++ (20) using an
event-driven programming technique to ensure its user-friendliness. DEAL has been accepted
by galvanizers with great interest and has become the standard tool for daily management of bath
chemistry. Some galvanizers have incorporated DEAL into their line control systems. On
these galvanizing lines, bath temperature and bath assays are fed directly into DEAL and a
recommendation on bath chemistry adjustment is issued directly by the line controlling system.
In principle, determination of effective Al content of the bath is to determine the Al activity in
the system. It involves the construction of a tie line passing through the point which represents
the bath sample composition in the Gibbs composition triangle. The tie line connects two-phase
compositions in equilibrium. Its intersection with the liquid phase boundary corresponds to the
effective bath Al level. The lever rule is then used to determine the amount of solid intermetallic
particle entrapped in the bath sample. If the bath composition falls into a three-phase region, as
it frequently does in GA production, then determination of the effective Al becomes much easier.
In spite of the fact that bath sample compositions can vary within the full expanse of this triangle,
Gibbs phase rule dictates that the effective Al level remains the same and is a function of
temperature only. Figure 3 illustrates how DEAL is used to calibrate bath assays in GA (a) and
GI (b) productions.

Figure 2: The Zn-rich corner of the Zn-Fe-Al ternary system.

Figure 3a: Bath assay calibration by

DEAL in GA production. The bath
effective Al level is the invariant
composition.

Figure 3b: The tie line passes the assay

point (red dot) and intersects the liquid
phase boundary at the green dot which
indicates the effective bath Al level.

Scientific interpretation of bath assays is only one practical application of the Zn-Fe-Al ternary
phase diagram. The selection of an optimum effective Al level for GA production is an even
more important application of the phase diagram. The greatest contribution of the researcher at
Teck Cominco to the prosperity of the galvanizing industry is the precise determination of the
invariant composition where the liquid, the phase and the -Fe2Al5 phase co-exist, as shown in
Figure 2. This composition is the reference bath chemistry in GA production. The phase
diagram proposed by Tang predicts that the position of this variant is a weak function of
temperature. With an increase in temperature of 1C, the corresponding Al composition of the
invariant point increases by 1 ppm only. Such a prediction has been proven accurate with the use
of Al sensors in galvanizing. If a galvanizing bath maintains an effective bath Al level at the
invariant point, the output of the sensor increases by 10 ppm only when the bath temperature
increases by 10C. On the other hand, if the bath effective Al level is higher than the invariant
composition, the sensor output increases by 70 ppm.
Precise determination of the invariant composition has brought practical solutions to a number of
industrial problems. At the beginning of the last decade, all newly built lines were plagued with

7
excessive bottom dross accumulation in GA production which negatively affected not only line
operating efficiency but also product quality. The lines had to be stopped for bottom dross
removal every week or so. By maintaining the effective Al content of the bath at a level
marginally higher than the invariant composition, intermetallic particles produced in the bath are
all iron aluminide, lighter than the molten metal. As a result, bottom dross accumulation is no
longer a problem. Due to its importance to galvanizing production, the invariant has been
dubbed the knee point by galvanizers.
A clear understanding of the characteristics of galvanizing baths would not be possible without
the Zn-Fe-Al phase diagram. Working with the former Inland Steel, engineers and researchers
from Teck Cominco sampled the bath at 27 locations at three depths and experimentally
determined the distribution of bath composition and temperature. The results were published in
the proceedings of the 1996 Galvanizers Association meeting.(?) It was shown that effective Al
is more or less uniformly distributed in the pot. However, a scientific description of the bath
characteristics emerged only after the present author re-analyzed the results and plotted all assay
data onto the Zn-Fe-Al phase diagram. As shown in Figure 4, points representing bath assays
formed a tie line in the phase diagram,(//) indicating clearly that the bath metal is well mixed due
to the rapid movement of the strip, and that the distribution of bath effective Al in a pot is a
function of bath temperature only.
Figure 4: Bath samples were taken
from 27 locations at three depths of
a pot. When plotted onto the ZnFe-Al phase diagram, these assays
formed a tie line in the liquid- two
phase region. This finding
indicates that the bath is a two- or
three-phase mixture, and that the
bath effective Al is a function of
bath temperature only.

Estimation of transient Fe solubility in the vicinity of steel strip when it is first exposed to the
molten Zn-Al alloy also relies on the phase diagram. Transient Fe solubility is critical for
predicting Al consumption in galvanizing. Iron solubility at the coating/substrate interface is
dictated by the equilibrium between the liquid and the outermost intermetallic compound in the
alloy layer covering the steel surface. This compound is the phase in general galvanizing and
the or the phases in continuous galvanizing. However, when the strip is initially exposed to
the melt, there is no intermetallic compound covering the steel surface, and the bare steel
momentarily co-exists with the liquid. The transient Fe solubility in the immediate vicinity of
the strip surface is, at this time, determined by the metastable equilibrium between the steel and
the molten coating alloy. This transient Fe solubility is much higher than the equilibrium value.
It is more than two orders of magnitude higher than the equilibrium value if the liquid consists of
pure Zn, as shown in Figure 5, and it is about one order of magnitude higher than the equilibrium
Fe solubility when the molten Zn contains a small amount of Al. The amount of Al consumed in
galvanizing the steel strip is mainly determined by the amount of Fe dissolved from the strip
during this transient. In galvanizing production, the dissolved Fe will convert into the phase,

8
either as the interfacial inhibition layer or as top dross particles. In galvannealing, the dissolved
Fe could either be transformed into the phase and/or the phase, depending on the bath
effective Al level. Teck Cominco has developed computer program PAL (Predict Aluminum
Level) to accurately calculate the amount of Fe dissolved from the strip and the feed requirement
in the production.
-32000

6.0

Liquid

G ( J /m o l)

Fe Content in Zn (wt%)

BCC

-34000

-36000

-38000

-40000
0%

5%

10%

15%

20%

Fe (wt%)

5.5

5.0

4.5

4.0
400

450

500

550

Strip Temperature (C)

Figure 5a: The free energies of the

relevant phases in galvanizing. The
liquid is momentarily in equilibrium
with the bcc phase when the strip is
initially exposed to the molten Zn.

Figure 5b: The transient Fe solubility in the

immediate vicinity of the strip submerged in
pure molten Zn as a function of temperature.

The Zn-Fe-Al-Co System

As mentioned earlier, liquid domains have been constructed for several Zn-Fe based quaternary
systems to provide a better understanding of submerged hardware performance in galvanizing
and the interplay of alloying and coating properties. Among these quaternary systems, the liquid
domain of the Zn-Fe-Al-Co system is the most simplistic.
Just a few years ago, sink-roll bearings, including the sleeve and the bushing, were frequently
made of Stellite, the Co-based alloys. These bearings exhibited a unique wear mode. Deep,
almost parallel, grooves developed during service. Galvanizers believed that the grooves were
generated by top dross particles entrapped in the bearings. However, studies indicated that this
wear mode was persistent whether the line was producing galvanized or galvanealed products.
Since GA production was carried out at an effective bath Al content below the knee point
(0.135%Al), the equilibrium compound in the bath was the phase. The particles were totally
incapable of cutting into the bearing surfaces because these particles possess a melting point of
about 670C only and are quite soft at galvanizing temperatures. Close examination of the worn
bearing tested in the laboratory apparatus revealed the existence of CoAl lumps adhered to the
bearing surface, as shown in Figure 6.

Figure 6a: The surface of a Stellite bearing

was totally covered by deep grooves after a
21 day galvanizing campaign.

Figure 6b: Close examination of the worn

surface of bearings revealed the existence of
CoAl lumps.

The knee point in the Zn-Fe-Al ternary system, which is being used as the reference composition
in galvanizing production,(15) has lost its significance in assessing bearing performance. To
better understand the wear mechanism and to seek better materials for bearings, the Zn-rich
corner of the Zn-Fe-Al-Co system, which displays the interplay of various intermetallic
compounds with the liquid (the molten Zn-Al alloy), has been constructed. Such a Zn corner of
the diagram is termed the liquid domain.
At this stage, the liquid domain is still a schematic presentation of the equilibrium states
available at the liquid surface. To construct the domain, one simply forms a tetrahedron using
the isothermal sections of all four sub-ternary systems and then highlights the liquid surface at
the Zn-rich corner which is divided into sections, each of which is in equilibrium with a solid
phase.
The development of the liquid domain of the Zn-Fe-Al-Co system is relatively easy because
isothermal sections for all four sub-ternary systems have been well developed, and the Zn-rich
corner of the system is relatively simple with only four intermetallic phases, the phase, the
phase, the -Fe2Al5 phase and the -CoAl phase co-existing with the liquid at galvanizing
temperatures.
An experimentally determined Zn-rich corner of the Zn-Fe-Co ternary system at 460C is shown
in Figure 7a. It can be seen that the - (FexCo1-x)Zn13 phase exists as a continuous solid
solution, bridging the two binary sides. As a result, the very Zn corner of the ternary system is a
simple sub-binary system of molten Zn in equilibrium with the phase. The ternary phase T,
isomorphic with 1 (Fe5Zn21), exists between two phases. The Zn-rich corner of the Zn-Co-Al
ternary system at 460C is shown in Figure 7b. It can be seen that, due to the strong affinity of
Co for Al, the - CoAl phase forms when the Al content of the molten Zn exceeds 0.015%.
With a detailed knowledge of the equilibrium states available in the Zn-rich corners of the ZnFe-Co, the Zn-Fe-Al, and the Zn-Co-Al systems, the liquid domain of the Zn-Fe-Co-Al
quaternary system can be constructed with reasonable accuracy, as shown in Figure 8. The
liquid is in equilibrium with the phase at low Al levels. Within a rather narrow composition
pipe close to the Zn-Fe-Al ternary side, the liquid is in equilibrium with the Fe phase. The
equilibrium between the liquid and the Co phase is not available in the system. The liquid, when

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saturated with Co, is mainly in equilibrium with the - CoAl phase. This finding is important
for understanding the wear mechanism of bearings made of Co-based alloys in galvanizing.
Figure 8 clearly demonstrates that the steel strip and the submerged hardware made of Co-based
alloys are subjected to different chemical environments. Aluminum in the bath reacts with Fe
dissolved from the strip and forms inhibition compounds at the strip surface. On the other hand,
Al in the vicinity of the submerged hardware readily reacts with Co to form CoAl particles on
the surface of the bearings. These aluminide particles are extremely hard and abrasive in nature.
Studies carried out at Teck Cominco(16) indicate that CoAl particles formed on Co-based alloys
in galvanizing baths and grew to several micrometres in size within about one hour at
temperatures relevant to galvanizing. These hard particles can be readily pressed into the Corich solid solution phase in the alloy when a load is applied, ploughing along and removing
material from the bearing surfaces in the form of chips, much longer than the dimension of the
cutting particles. Aluminum can easily convert wear debris into CoAl particles in the immediate
vicinity of the contacting surfaces of the bearings. Some of the converted wear debris could
attach to the bearing surfaces, forming cobalt aluminide aggregates with an extremely high
hardness, as shown in Figure 9. These aggregates increase in size as the test progresses and act
as blunt micro-cutting tools, creating deep grooves on bearing surfaces. The liquid domain
shown in Figure 8 indicates clearly that the knee point on the Fe solubility curve in the Zn-Fe-Al
sub-system is a reference composition for the galvanizing operation only. To understand the
wear mechanism of submerged hardware made of Co-based alloys, one should focus on the ZnCo-Al side of the diagram where the reference Al composition is 0.015% at 460C. Judging by
the fact that CoAl particles readily formed on a Stellite sample submerged in a galvannealing
bath, the Co solubility at the liquid/Stellite interface is of the order of 100 ppm.
The revelation of this wear mechanism has clarified much of the confusion within the
galvanizing industry. Apparently, sleeve and bushing should not be made of the same Co-based
alloy. By assembling pairs of different materials, such as T-800/Stellite or laser-clad WC on
316L SS/Stellite, the service life and the performance of the bearings have been much improved.
316L SS is being widely used as roll material in continuous galvanizing. Laboratory studies
showed that an inhibition layer could not form on the stainless steel surface until the Al content
of the molten Zn reached approximately 0.17%. When the steel was tested in molten Zn
containing 0.135%Al, a so-called super meniscus formed on the part of the sample which was
exposed to the air.(//) Industrial practices indicated that rolls made of 316L SS suffered from
dross growth in baths with a low Al content. However, these rolls were almost immune to
growth in baths containing Al higher than 0.2%. Recent studies of the corrosion behaviour of
316L SS in a molten Zn-0.13%Al alloy indicated that a full inhibition was in effect when the
bath contained residual Co of about 30 ppm. The inhibition layer formed on the sample surfaces
and grew with time, as shown in Figures 9a and 9b. This phenomenon can also be explained
using the liquid domain of the Zn-Fe-Al-Co system. It shows clearly that the threshold Al level
for the transition from the phase to the phase decreases with an increasing Co content in the
liquid. This suggests that the inhibition layer can form at a lower Al level if the liquid contains
some Co.

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Zn

96
94
92

0.06

0.05

Co Solubility wt%

98

6
8

90

CoZn13

0.04

CoAl

0.03
0.02
0.01

Co

88

Co

0.00
0.00

0.02

0.04
0.06
0.08
Al Content wt%

0.10

0.12

Figure 7a: The Zn-rich corner of the Zn-Fe-Co Figure 7b: The Zn-rich corner of the Znsystem at 450C.
Co-Al system at 460C.

Figure 8: The liquid domain of the Zn-Fe-Al-Co quaternary system.

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Figure 9a: One week.

Figure 9b: Two weeks.

Acknowledgement
Part of the material presented here is taken from the work carried out by Drs. Daniel Liu,
Keith Zhang and Xuebin Yu. The author is grateful to Mr. Artur Filc for drawing some of
the phase diagrams and Mrs. Angeline M. Prskalo for editorial help in the preparation of the
manuscript.

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