Contents

Introduction Theoretical Background. Galvanizing of Steel. Transient Fe Activity at Interface & Nucleation Kinetics. The Structure of the Inhibition Layer. Galvanizing Bath. Why Aluminum. Why Aluminum control. Controlling Factors. Physical processes. Determination of Aluminum Concentration in Zinc Bath. Fuzzy Logic controller. Conclusion.

Theoretical Background
The addition of Aluminum to galvanizing baths for controlling coating microstructure is an integral part of the continuous galvanizing technology. Aluminum can dissolve in all the binary Zn-Fe compounds, thereby creating equilibrium states unavailable to the binary Zn-Fe system. In a continuous galvanizing bath, Fe exists in two forms: it exists in the liquid Zn as solute, or in the solid strip. Al can combine with Fe in the liquid Zn to form (Fe2Al5) particles, which eventually float to the bath surface to form top dross. Al can also react with the steel strip and deposit the phase on its surface as a barrier layer, commonly referred to as the inhibition layer, which prevents the direct contact between the strip and liquid Zn, thereby allowing a free or unalloyed Zn overlay to form. The inhibition layer is desirable for galvanized coatings because it inhibits the formation of Zn-Fe alloys thereby improving the coating adhesion and ductility. However, an inhibition layer should be avoided in galvanizing because a number of coating defects, such as incomplete alloying and sink-roll prints can be attributed to the formation of the inhibition layer, partial or continuous, in the hot-dipping stage of the galvanizing production. In the continuous hot-dip galvanizing of steel strip, sheet in cold-rolled condition undergoes cleaning, recrystallization-annealing, coating with zinc, possibly galvanizing, and skin-pass rolling and chemical treatment in a continuous process. Apart from obtaining the optimal mechanical properties necessary for the specific application, the achievement of a flawless surface is a basic prerequisite for producing a composite material of good quality. A possible defect which is liable to occur during hot-dip coating and impair the optical flawless of zinc coating is the formation of extremely fine pimples caused by ultra fine particles within the zinc coating. These particles are composed of element iron, aluminum and zinc and originate from the precipitation of iron in the zinc bath. They are referred to as dross. Numerous analyses confirm with good agreement that the dross particles, which at room temperature are detected by metallographic techniques either within the coatings or in samples taken from the zinc bath, are intermetallic ternary compounds. Quantitative determinations of the levels of the element iron, aluminum and zinc show that at room temperature the dross particle consists of the phase Fe2Al5Zn. Aluminum is added to the bath in specific amounts to guarantee adequate coating adherence, and there is constant input of iron during the galvanizing process. Source of iron input is the strip being galvanized. Excess iron (above the solubility limit) precipitates as two possible phases. One phase takes the form of an iron-aluminum alloy, which rises, to the surface as of the molten zinc as top dross. The other is an iron-zinc alloy, which settles down as the bottom dross. Aluminum has a greater affinity of Iron than Zinc, resulting in a protective Fe-Al layer coming on the strip in the bath, which retards the development of binary Fe-Zn phase that can cause coating adhesion problems with galvanized steel. This reaction between iron and aluminum also aids in dross control, shifting the resulting dross product from bottom dross to top dross, and so easing removal.

Despite these advantages, it is also necessary to limit the amount of aluminum in the galvanizing bath for several reasons: Adding more than required to minimize the iron-zinc reaction is an unnecessary cost to the process. Excess bath aluminum content can result in coating defects such as sag and ripple. Excess bath aluminum content results in higher coating aluminum content. This is thought to impair the spot weldability and phosphatability of the material. The control of Al is critical in galvanizing process. Ideally, the Al content in a galvanizing bath should be high enough so that the intermetallic particles formed in the bath mostly float to its surface and line stoppages solely for bottom dross removal can be avoided. On the other hand, there should be no inhibition layer, partial or continuous, in the as-galvanized coating, so that the alloying process during post-annealing would not be impeded and a uniform coating with high quality will be assured. Based on the above analysis, the (or 1) to transition point is the optimum composition for galvanizing. At this point, Fe2Al5Znx becomes an equilibrium compound in the bath. Maintaining a bath Al content marginally higher than this level could prevent forming bottom dross. The rate of dissolution from the strip is slow at such a bath Al level because of segregation of Al at the interface. Consequently, the dross formation rate is also slow. On the other hand, the formation of the Fe2Al5 phase at the interface is practically impossible because of severe competitions from the and phases.

Transient Fe Activity at Interface & Nucleation Kinetics

In continuous galvanizing, as well as in general galvanizing, Zn-Fe compounds frequently form in coatings where these compounds are thermodynamically unstable. By varying dipping times and bath Al contents, chemistry of the formation of different alloys/compounds will change accordingly. In essence, a galvanizing bath is a Zn-Fe-Al ternary alloy. The activities of Fe and Al in molten Zn are inter-related through the thermodynamic properties of the intermetallic compounds in equilibrium with the liquid. In a galvanizing bath, Zn is almost pure and its activity is unity. At a given Al content (activity), the Gibbs free energy of the liquid, determined by the sum of the partial free energies of the three components, therefore, is solely dependent on the Fe activity. The lower the Fe activity is, the more negative the free energy of the liquid is. In continuous galvanizing, there are three relevant compounds,, and . Correspondingly, there are three Fe solubility curves, each representing equilibrium between the liquid and the relevant compound.

Fe Dissolution
Ultra-low-carbon steel, the main stream of continuously galvanized strip, is practically pure Fe, and its surface is chemically activated after being thoroughly cleaned. Upon exposure to the molten Zn, Fe quickly dissolves from the strip. The amount of Fe dissolved is always more than that deposited back onto the substrate as intermetallic compounds, and dross is constantly produced in galvanizing. Before a compact alloy layer forms, an equilibrium state cannot be established in front of the substrate/melt interface. Frequently, the transient Fe activity in this region is not only higher than the equilibrium value, but also higher than those sustained by the equilibria between the liquid and metastable compounds in the region. One can conveniently imagine the process of Fe dissolution from the strip as taking place in three steps. First, Fe atoms are separated from the strip surface; then the intruding Fe atoms separate Zn atoms from each other; and finally, the Fe atoms are mixed with the Zn atoms. The enthalpy change associated with the dissolution of Fe is the sum of the enthalpy changes for the three steps. The three steps are sequential, and the number of Fe atoms that can dissolve in the Zn is largely dependent on the probability of a Fe atom escaping from the steel substrate. The energy barrier for the separation of Fe atoms from the strip is approximately equal to the free energy of fusion, given by: Gf =15200-8.20T joule The probability of a Fe atom escaping from the strip, P, can be calculated through the following equation: P=exp (-G/RT) Where R is the universal gas constant, T is the temperature in Kelvin, and G is the energy barrier, which is approximately equal to the Gibbs free energy of fusion for Fe.

Al segregation
In the liquid, the Al and Zn atoms repel each other as indicated by a positive partial molar excess free energy of Al in the binary Zn-Al system. On the other hand, Al has a high affinity

for Fe. Al atoms are expected to segregate to the substrate surface to form complex clusters with the Fe atoms. The enrichment of Al in the interface can be estimated using the following equation: Ci=Cb*exp (E/kT) Where Ci and Cb are the Al concentrations at the interface and in the bath, respectively, and E is the binding energy of the Al atoms to the substrate surface. If one assumes that the binding energy of Fe and Al at the interface is equal to the binding energy of atoms in the inhibition compound, then Al is enriched in the interface by a fraction of 200 at 460oC.

Binary Zn-Fe system

Energy barriers for the formation of Zn-Fe intermetallic compounds are very high and very sensitive to any variation in surface nucleation energy. The expression for Gibbs free energy for the formation of Zn-Fe binary system is given below: 13Zn(1)+Fe ()=Zn13Fe G0=-163408+171T J/mol The nucleation of phase takes place on the substrate surface where the Fe activity is unity. If the phase nucleates at a place where the Fe activity aFe is less than unity, then G0=-163408+171T-RTln(aFe) the formation of phase results in a free energy change of 38065 J/mole at 460oC. The free energy change, assuming the density of the compound as 7.28 g/cm3, with the formation of unit volume of the compound is Gv= -3.06*108 J/m3

Zn-Fe-Al ternary system

The formation of the alloy layer in coatings in baths containing Al level higher than 0.15%, it is a general agreement that a full inhibition effect is expected. Coatings produced in such a bath consist of a Zn overlay with a thin inhibition layer at the coating/substrate interface. The coatings could contain some outbursts if defects are present on the substrate surface or if the immersion time is long enough to cause the breakdown of the inhibition layer. The formation kinetics of inhibition layer on the substrate follows a quasi-linear law in the first second with a rate of typically 0.1m/s. Initially, Al atoms needed for the formation of inhibition layer are readily supplied by the liquid contiguous to the interface. Due to the large difference in the Al contents of the inhibition layer (55%) and the molten CGG alloy (0.18%), the Al required for the growth of the inhibition layer, however, has to be supplied by long range diffusion of Al in the liquid. The nucleation rate of the formation of the compound is exponentially proportional to the energy barrier G = exp (-G/RT) Where is the number of potential nucleation sites. Al segregation to the substrate/Zn surface significantly reduces the Arial density of potential nucleation sites for the and phases.

The Structure of the Inhibition Layer

In the case of galvanizing, a strong inhibition is desired and therefore a high Al of about 0.20% is used. The first reaction during hot dipping in an Al-containing Zn bath is the reaction between Fe and Al, i.e. the formation of inhibition layer. It is earlier reported that the inhibition layer is predominantly composed of an orthorhombic Fe2Al5 phase with a high Zn content. TEM studies on extraction replicas by Guttmann revealed that the layer is formed of two sublayers with an overall thickness of 250nm (Al (bath) = 0.18%). On the basis of data of Al pick-up of the galvanized coatings, produced during an industrial galvanizing campaign, the possible thickness of the inhibition layer was calculated, assuming a homogeneously distributed Fe2Al5 inhibition layer. We generally take the thickness of the inhibition layer in the range of 5nm to 80nm, depending upon strip immersion time.

Galvanizing Bath
The galvanizing bath may be considered as being the place where reaction occurs between zinc and the immersed steel sheet. The galvanizing bath is zinc exchanger- zinc input via the ingot is divided into two outputs and possibly an accumulation. The first output is through the coating of the sheet, which is composed of 2 layers: a very thin layer of interfacial alloy, Fe2Al5 and a thicker layer of zinc. The second output is the dross mix. Zinc accumulation depends mostly on the variations of the bath height. The galvanizing bath is also an aluminum exchanger aluminum from the ingot is also divided into two outputs (the coating and dross) as well as the potential accumulation. The galvanizing bath is an iron exchanger as opposed to zinc and aluminum, iron inputs is essentially due to the sheet surface dissolution especially at the early stages of the galvanizing reaction. This output of iron may also be divided into two outputs (coating and dross) and an accumulation in the bath. The iron, which combines with aluminum to create the interfacial alloy layer, does not pollute the bath.

Working Conditions
The experimental variables and the matrix were chosen as follows: Immersion duration is varied from near zero to 20 s, with emphasis on the short duration. Typical industrial duration is around 2 s. Hydrodynamic conditions are chosen in both the laminar and turbulent range, the industrial bath being considered turbulent. Bath temperature is chosen to be in the range of 460 or 480oC. Immersion temperature was set equal to bath temperature, 20oC higher or lower. Melts were iron saturated, with an Al content of 0.19 wt % to 0.21 wt %. Annealing temperature is set equal to 750oC, the duration is 2 minutes and cooling gas flow rate 20 dm3 per minute.

Effects of hydrodynamics
At one temperature and melt composition but under varying hydrodynamic conditions, the following observations may be made: Relative motion between sample and melt is important, but only to the point that the flow is either laminar or turbulent. In fact, laminar conditions represent the set of results obtained for Reynolds numbers of 0 and 900, as turbulent conditions are for Reynolds numbers of 2000, 3800 and 4500. The inhibiting layer is thinner and more finely grained when hydrodynamic conditions are turbulent. This is true for short as well as long immersion times, when inhibiting layer thickness grows: the system thus possesses a memory of its past history. The differences in morphology are however less visible for 5 s immersions than for 0.1 s immersions. Differences between sets of results are prominent for starting aluminum take-up values. Therefore, one can deduce that nucleation is influenced by hydrodynamics, the latter conditioning Al transports towards the interface. Easy transport means thinner layer more readily completely covering. For longer immersions the behavior is more similar because the curves tend to become parallel. Diffusive transport is then probably the controlling mechanism.

Effects of melt temperature

Experiments have been performed using a dip temperature equal to the melt temperature and under turbulent conditions only.

Rising temperature lead to a considerable augmentation of Al take-up at the interface. Temperature is thus an important parameter.

Effects of melt composition

Higher Aluminum content raises initial Al take-up, when Al concentrations rise from 0.14 to 0.20-wt %. A concentration above 0.20 wt-% does not give any increase in Al take-up, a small reduction is even observed.

Effects of immersion temperature

A dipping temperature slightly above the melt temperature, which is common industrial practice, gives rise to a small increase of interfacial layer thickness. A dipping temperature slightly under the melt temperature gives rise to a small decrease of Al interfacial layer thickness, but to a smaller extent than the above case.

Why Aluminum
Formation of Fe2Al5 > allows deformation Cannot avoid Fe dissolution > Dross The effects of Fe2Al5 inhibiting layer developed on the steel substrate, as well as the interstitial free steel substrate grain size of Fe-Zn reaction kinetics during galvanizing processing, are of great interest to the steel coating industry. Guttmann proposed that the Fe2Al5 inhibition layer, developed on the substrate during galvanizing, forms epitaxially so that Fe2Al5 crystals developed colonies of the same orientation as the underlying substrate steel grain. The colonies from low angle boundaries when contained within an underlying substrate grain interior and, therefore, Fe and Zn diffusion follow normal diffusion rates at these low angle boundaries. For a low Al content bath or a pure Zn bath the entire steel/coating interface reacted with the liquid Zn to form a uniform reaction layer. Three individual Fe-Zn phase layers were observed to form in coated steels: (1) gamma, (2) delta, and (3) zeta phases. But in high Al content bath unlike the pure bath where a uniform Fe-Zn alloy layer formed, the 0.20-wt% Al-Zn coatings showed Fe-Zn alloy layer development which was discontinuous. The presence of Al in the Zn bath causes the formation of a Fe2Al5 inhibition layer.

Inhibition of Fe-Zn reaction

Microstructure Aluminothermic > MnO, SiO2, P2O5 to Al2O3 SIMS analysis shows that the iron oxide, made between 600oC and 460oC, can be partially reduced by the aluminum contained in the bath. This analysis shows that indeed the presence of an important aluminum oxide over the residual iron oxide at the steel/coating interface. That aluminothermic reaction however allows a sufficient iron oxide reduction and the formation of the Fe2Al5 inhibition layer, which lead to a good adhesion.

Improves adherence

Dross modifier
Top (Al > 0.15) / Bottom (Al < 0.12) As the aluminum content increases the precipitation of iron shifts from the phase FeZn7 to the phase Fe2Al5. This means that the occurrence of bottom dross decreases with increasing aluminum content, but the occurrence of top dross increases. The thermodynamic calculations show that at aluminum contents of <0.12% the iron precipitates via the FeZn7 phase, and at contents of >0.14% via the Fe2Al5 phase. At aluminum contents of between 0.12% and 0.14% the transition is variable and both phases are formed. Here FeZn7 mainly forms the bottom dross and Fe2Al5 forms the top dross. So we can say that in our concerning range of Al concentrations we will get only the top dross.

Solubility modifier of Fe in zinc

Al increases Fe solubility decreases

Upon exposure to the molten Zn, Fe quickly dissolves from the strip. The amount of Fe dissolved is always more than that deposited back onto the substrate as intermetallic compounds, and dross is constantly produced in galvanizing. Available experimental results suggest that the Fe supersaturation level in the vicinity of the substrate/Zn interface decreased with an increasing bath Al content. An evaluation of the growth kinetics of the inhibition layer in galvanized coating carried out earlier suggested that the level of Fe supersaturation in front of a growing inhibition layer was about 1.5 times the equilibrium Fe solubility limit. These works suggested the energy barrier for Fe atoms to escape from the substrate increases linearly with the Al content at the interface.

Modification of surface tension of zinc

Al increases strip wettability decreases Improvement in strip wettability, the result could be explained by a better zinc diffusion through the graphite/soot layer and the development of Fe-Zn reactions at the steel coating interface. On adding more Al the thickness of inhibition layer increases, which causes hindrance in zinc diffusion process and hence decreases the strip wettability.

Effect on viscosity
Al increase viscosity decreases

Why Aluminum Control

Affects coated steel properties
Surface appearance Adhesion Ductility Weldability Paintability Corrosion resistance

Controlling factors
The development of the coating is controlled by a number of factors; the most important being the diffusion of iron through the different intermetallic phases during the time the coating is exposed to elevated temperature. The main parameters of process considered during the design of the model are: 1. The Time-temperature path. The temperature path the coating is exposed to will depend primarily on the line speed, furnace temperature and steel gauge, the latter having a major influence on the heat capacity of the system and thereby on the effective heating and cooling rates. The diffusion of iron starts as soon as the steel enters the molten zinc bath; however, iron will only start building up when the zinc solidifies.

2. The coating thickness. 3. The initial iron distribution through the coating; the zinc bath will have iron dissolved. It is assumed that the coating consists of at the onset of the process. 4. The amount of Fe2Al5 at the interface between the coating and the steel base left after the burn off of the flux. It is assumed that thickness of this layer is uniform; as flux will accumulates in grooves and pitches in the steel surface this assumption is questionable. 5. The composition of the steel base. It is, however, assumed that for the low alloy steels studied in this work the steel composition does not have any effect. 6. Surface roughness of the steel base.

Physical processes
The main physical processes taking place are: 1. Diffusion of iron and zinc within each of the phases. The diffusion coefficients D depend strongly on the intermetallic phase and the temperature. The D values must consequently be calculated from the activation energy of the diffusion process and pre-exponential factors for each of the intermetallic phases. The D-values depend to a lesser extent on the compositional variations within each phase. In some cases these variations may be important, as the very short annealing times, typically 4 to 10 seconds, make it likely that some phases will have non-equilibrium compositions during significant portions of the annealing process. In this work it has, however, been assumed that at a given temperature each phase has only one D-value. 2. Grain boundary diffusion opening up fast routes of diffusion. This is assumed to be very subordinate compared to intra-granular diffusion. 3. Nucleation kinetics for the different intermetallic phases. As nucleation takes place sporadically the development of the coating will not be uniform. In this study it is, however, for simplicity assumed that all phases nucleate everywhere without delay. 4. Growth of different phases, e.g. some phases show dendritic growth. 5. Kinetics of the break down of the Fe2Al5 layer at the steel-coating interface. The effect of this layer is to reduce the iron diffusion into the coating. It is assumed that the effect can be simplified as a time dependent factor slowing down diffusion into the adjacent 1 layer.

Determination of Aluminum Concentration in Zinc Bath

The control process of aluminum concentration starts with taking the mass balance of different components of the zinc bath. A mass balance calculation was conducted at the No. 2 CGL of the CRM of TISCO. The objective was to develop an understanding of the effects of processing conditions and zinc alloy ingot additions on aluminum deportment. In the bath aluminum balance, the input comes from zinc alloy ingots. The aluminum output consists of two components: (i) Coating and (ii) Dross. In order to accomplish a material balance, it was necessary to determine the amount of aluminum consumed by the strip and removed by the dross skimming practice.

Quantifying the aluminum of the dross production is a difficult task for a mass balance due to the fact that the dross skimming always contains pure zinc and dross particles. Previous attempts reported in the literature include: (i) calculating the amount of aluminum based on lab scale iron dissolution rate and (ii) estimating the amount of aluminum by difference of aluminum addition and coating aluminum. Direct determination of the amount of aluminum in dross under production line conditions has not been reported. This work describes the process used to calculate the zinc bath material balance at CRM No.2 CGL (TISCO) while producing galvanized products. The dross from the zinc bath was collected, and the full size dross ingots were remelted and analyzed. This process allowed separation of the zinc metal from the dross particles thus providing the actual aluminum content of the dross. Furthermore, multiple regression analysis was used to determine the relationship between coating aluminum content and processing variables. The dross generation rate was also related to the processing variables. The results of the material balance for zinc and aluminum in the zinc bath are presented. The equations for coating aluminum and dross generation rate are also discussed.

Outline of CGL.2
CRM No.2 CGL was installed in 2001 with a design capacity of 285,000 tons of galvanize (GI) annually, producing both automotive and construction products. The zinc bath has a capacity of 160 tons and is powered by two 450 kW inductors. The line is capable of producing coated steel sheet ranging from 0.2 mm to 2.0 mm in thickness and 600 mm to 1524 mm in width. The processing line speed ranges from 60 m/min to 150 m/min and coating weights from 60 g/m2/side to 360 g/m2/side. This wide variation in processing conditions has an important effect on aluminum control in the zinc bath.

Method
A material balance was constructed for both zinc (Zn) and aluminum (Al). The material balance for a finite period of time is given by the following equation. For zinc: Zn (input) - Zn (output) = Zn Zn (input) = charge into bath bath level Zn (output) = Zn (coating) + Zn (dross) level For Aluminum: Al (input) - Al (output) = Al Al (input) = Charge into bath bath level Al (output) = Al (coating) + Al (dross) level Where: Zn: Quantity of Zn unaccounted for. Al: Quantity of Al unaccounted for.

Calculation of components required for mass balance

 Zinc Calculation 1. Zn (input): Calculation of zinc input is based on the number of ingots of two different compositions (zinc alloy (ZA) with 1% Al component and highgrade (HG) pure zinc) charged to the bath. A decrease in bath height, at the end of the trial, a counted as zinc input. 2. Zn (output): Zinc output consists of two components: (i) zinc in coating and (ii) zinc in dross. Zinc in coating is calculated as a function of strip area coated and coating weight. Zinc in dross was measured and formulated as a function of zinc consumption. An increase in bath height is counted as zinc output. 3. Zn: the difference in amount of zinc (input) and zinc (output). Aluminum calculation 1. Al (input): Calculation of aluminum input is based on the number of zinc alloy (1% Al) ingots charged to the bath and the quantity of aluminum due to the bath height decrease. 2. Al (output): Aluminum output consists of two components: (i) aluminum in coating and (ii) aluminum in dross. Aluminum in coating is calculated as a function of various processing parameters. Aluminum in dross was measured and formulated as a function of zinc consumption. The aluminum in any measured bath height increase is considered aluminum output. 3. Al: Difference of the above two parameters.

Information used for mass balance

1.Data
The data used for the mass balance calculation was obtained from No.2 CGL. During this trial, 134 coils were coated and the bath Al ranged from 0.165% to 0.205% while gauge of product ranged from 0.38 mm 1.52 mm. Product mix covered drawing quality, deep drawing quality, lock forming quality and physical quality.

2.Dross Separation
Six jumbo dross ingots were collected from the trial and were remelted. Each dross ingot was cut into smaller blocks for easy handling and remelted in a gas-fired furnace and held at 470oC for 4 hours. The holding period allowed the dross particles to float to the top of the crucible. Dross particles were removed from the melt until the surface appeared clean and shiny. The remaining reusable zinc metal and the skimmed dross particles were separately weighed and recorded. The aluminum and iron contents in the dross particles and the reusable zinc metal were determined by wet chemical analysis.

3.Calculation of Aluminum effective

Aluminum content in the bath is not the amount of Aluminum, which takes part in the reaction or used in coating. The actual amount of aluminum used in coating is the amount of effective aluminum.

In order to determine the active contents from the findings obtained here, a correction chart is developed. It is in principle the solubility curve for iron and aluminum in molten zinc. The formula for calculating the solubility curve is:

Log [(%Fe) 1.72*(%Al) 4.43]=14.18-(12536/T)-4.43*log [8.3424-0.0074*T]1.72*log [19.2692-0.0133*T]

(Contents in [wt %], T in K) in the figure below the solubility calculated at five different temperatures are plotted as downward curves. Below these curves the respective contents are in solution,

0.06 0.05 0.04 0.03 460 0.02 0.01 0 0.17 470 480 490 500 0.18 0.19 0.2 0.21 0.22 0.23

above these curves they are precipitates. Firstly, the aluminum and iron contents determined by analysis of a sample taken from the zinc bath are plotted on the graph. If the analysis value is below the solubility line corresponding to the bath temperature prevailing when the sample is taken, these contents are the active contents. If it is above the line, however, this means that the quantities, which were present in the bath above the solubility, limit as precipitates must be subtracted from the absolute values to determine the active contents. In the case of higher aluminum contents Fe2Al5 bonding takes place, whereby for every two-iron atoms five aluminum atoms are bonded. From this the slope of the correction straight line for higher aluminum contents of Fe/Al = 2*56/5*27 = 0.83 is arithmetically derived for the weight ratio. This means that each percent of iron bonds with 1/0.83 =1.21 percent of aluminum. Starting from the result of a zinc-bath analysis, the active iron and aluminum contents can be read off via a correction line of slope 0.83. If the analysis value is above the solubility curve of the corresponding bath temperature the contents must be reduces along the correction curves until the solubility line is crossed. Here, the solubility curve of the temperature at which the zinc-bath sample was taken of for which the active contents are to be determined should be used. For the point of intersection of the correction curve and the selected solubility line the active aluminum and iron contents can then be read off at the axes. We know the initial concentration of the Fe and Al in the bath and also the bath temperature. Corresponding to that value we can get the value of the coefficient of the correction curve passing through that point of (%Al, %Fe) co-ordinates. C= Fe% - 0.83*Al% Now putting this value of C in the figure given below we can find out the Aleff % for that condition. -0.09 0.17 -0.1 -0.11 -0.12 -0.13 -0.14 -0.15 -0.16 -0.17 -0.18 From here we can easily find out the Al effective in the bath corresponding to that temperature and contents of the bath. 460 470 480 490 500

0.18

0.19

0.2

0.21

0.22

0.23

Here in the graph we find that in the desired range the value of Const. varies linearly with respect to the value of Aluminum in the bath. So we can get a linear relation of const. depending on the value of Aluminum in the bath. On doing regression analysis we find relations for different temperature levels. Those are For 450oC: Const = -0.9048*Aleff + 0.0208 R2 = 0.9999 o For 455 C: Const = -0.9212*Aleff + 0.0253 R2 = 0.9999 o For 460 C: Const = -0.941*Aleff + 0.0308 R2 = 0.9999 o For 465 C: Const = -0.9649*Aleff + 0.0374 R2 = 0.9998 o For 470 C: Const = -0.9937*Aleff + 0.0454 R2 = 0.9997 For 475oC: Const = -1.0283*Aleff + 0.055 R2 = 0.9997 For 480oC: Const = -1.0698*Aleff + 0.0666 R2 = 0.9995 For 485oC: Const = -1.1197*Aleff + 0.0804 R2 = 0.9994 For 490oC: Const = -1.1794*Aleff + 0.097 R2 = 0.9992 For 495oC: Const = -1.2508*Aleff + 0.1168 R2 = 0.9989 o For 500 C: Const = -1.3362*Aleff + 0.1405 R2 = 0.9987 From the above relations we find that the slope and the constant of the straight line equation is changing with the change in temperature of the bath so we will have to find out the dependence of these variables on temperature finally we get relations for the slope and the constant with respect to the temperature. Slope(m) = -0.0083* temp + 2.8877 R2 = 0.9408 Constant(c) = 0.0023* temp - 1.032 R2 = 0.9407 On doing regression analysis we find a relation of Al effective depending on the bath temperature, Fe% of the bath, and Al% of the bath. The relation is Aleff = (C+ 1.032 0.0023* T)/(2.8877 0.0083 * T) Here T is in degree centigrade and the value of C we can find from the above given relation. On comparing the exact value of Aleff and the value we find out by the above equation is given in a plot below:

-0.09 0.17 -0.1 -0.11 -0.12 -0.13 -0.14 -0.15 -0.16 -0.17 -0.18 0.4 0.2 0 -0.2440 -0.4 -0.6 -0.8 -1 -1.2 -1.4 -1.6

0.18

0.19

0.2

0.21

0.22

0.23

460 470 480 490 500 460(cal) 470(cal) 480(cal) 490(cal) 500(cal)

y = 0.0023x - 1.032 2 R = 0.9408 460 480 500 520 slope(m) constant(c) Linear (slope(m)) Linear (constant(c)) y = -0.0083x + 2.8877 2 R = 0.9409

From the above plot we find that the exact and measured value are quite close to each other so we can take the equation derived as a relation to find out the Aleff for the Zinc bath at that condition.

4.Bath height measurement

Operation conditions and ingot addition practice can change the bath height and result in a possible accumulation (increase in the bath height) or depletion (decrease in the bath height) in the zinc bath. The bath height change was measured using a custom-made set up during the trial. The amount of zinc due to changes in the bath height was determined based on the bath dimension and liquid zinc density at 460OC ( =6.58 g/cm3).

5.Mass balance

The figure given above shows the schematic mass balance for a zinc bath. Spreadsheets were prepared (i) from operational data that characterized the strip being processed and the types and weights of materials added and removed, and (ii) from analytical data that characterized the bath, dross and coating chemistries.

Results and Discussion

1. Coating aluminum content and processing variables:
As coating Al is not routinely measured, it is necessary to estimate the amount of Al in the coating for the mass balance. Regression analysis was performed to determine the effects of the processing parameters on coating aluminum content. The following parameters were determined to have a significant effect on coating aluminum content (significant at a 99% confidence level). CtgWt: Coating weight (g/m2/side) EffAl: effective aluminum (%) Imm time: immersion time (sec) Trd: strip turn down temperature (oC) Pot: pot temperature (oC) The relationship between these five parameters and coating aluminum is given by the following regression equation. Coating Al (g/m2/side) = -3.89+0.0022*CtgWt+5.29*Aleff+0.029*Imm time+0.0014*Trd+0.0053*Pot r =0.84, N=108 This relationship indicates that coating aluminum content can be controlled by these five parameters. This relationship is in agreement with published information that coating aluminum

content increases with increasing coating weight, effective bath aluminum content, immersion time, pot temperature and strip turn down temperature.

2. Mass balance
The weights of ingot additions and all material outputs are expressed in kilograms. The mass balances are the result of 3185 minutes of operation where all input and output materials have been measured: Weight of ingots (ZA and HG). Weight and analysis of the coating. Weight and chemical analysis of the dross mixture. During this trial, the bath height decreased by 4.9 cm (bath height start- bath height finish). This indicates that the amount of zinc in the bath has been depleted. Therefore, the total amount of zinc/aluminum input should be expressed as follows: Zn (input) = Zn (ingot) + Zn (Decrease in bath heights) Al (input) = Al (ingot) + Al (Decrease in bath heights) 3. Process Model

Strip

Zinc Pot

(Zn, Fe & Al)

Zinc bath contains mainly three components: 1. Zinc 2. Aluminum 3. Iron Assumptions made for our model: 1. The iron atom what is going out, as dross is the loss of iron from the bath, i.e., the iron diffusion from the steel surface is taken as negligible in amount so basically the iron amount in dross is taken as the loss in the iron composition in the bath. 2. Dross generation is taken as constant for whole process and also its composition. 3. Al concentration is taken as uniformly distributed in the bath. 4. Bath temperature is taken to be same for every point and bath is taken as homogeneous. 5. Because the line speed variation is small so the line speed is take as a constant.

6. The coating is taken as a uniform layer of - phase and the zinc, i.e., formation of other phases are discarded. 7. Zinc bath is taken to be as a mixture of Al, Zn & Fe only because the contribution of other elements is very low. Algorithm for our model: 1. The model is working as an expert system which checks the aluminum concentration available in the bath is sufficient for the next processing mother coil. So, all the calculation and prediction are done for the next mother coil based on the current position of the zinc bath. 2. Mother coil dimensions are taken as input and we know the composition of the bath before getting into the process. 3. Now the next step is to calculate the Aleff in the bath, which is a function of Fe%, Al% and the bath temperature at the starting. 4. The next step is the calculation of Al amount coming out of the bath as coating, which we find as a function of strip temperature, bath temperature, Aleff, speed and coating weight. 5. The next step is the calculation of Zndross, Aldross & Fedross from the given rate of generation of dross. 6. Now we know the Alcoating, and we know the coating weight from these two values we can get the zinc amount coming out in the coating. Here Zncoating = Coating Weight - Alcoating. 7. So we can tell the final bath composition because we know the Zn consumption and the Al consumption and we can also tell the Fe% in the bath because we know the value of Fe coming out as dross. So finally we can predict the bath composition, which is transferred as an input for the next coil.

Start

Initial Bath Condition

0.19 % < Al < 0.21 % Effective Aluminum

Add Al & Zn Ingots according to requirement

Mother coil Dimensions, Coating Weight, Speed, Strip entry temperature

Dross weight calculation

Coating Aluminum

Zinc in coating

Zn, Al & Fe in dross

Calculation of final bath composition

Initial Bath Condition

Bath temp .

Al%

Fe%

C=Fe%-0.83*Al% Aleff = (C+ 1.22515 0.002711* T)/(3.581074 0.00976 * T)

Effective Aluminum Initial Bath Condition

Bath temp .

Al%

Fe%

Mother coil Dimensions, Coating Weight, Speed, Strip entry temperature

Coating Al (g/m2/side) = -3.89+0.0022*CtgWt+5.29*EffAl+ 0.029*Imm time+0.0014*Trd+0.0053*Pot

Coating Aluminum

CtgWt = Coating Zinc + Coating Aluminum

Zinc in coating Zinc in coating Coating Aluminum Dross Components

Final bath composition

Conclusions
1. The aluminum and zinc accounted for in the mass balance was 92.1% and 90.1% respectively. 2. Breakdown of the zinc consumption is: 91.2% of the zinc input is consumed by the coating layer. 8.8% of the zinc input goes into the removed dross. 3. Breakdown of the aluminum consumption is: 74.6% of aluminum input is consumed by the coating layer. 25.4% of aluminum input goes into the removed dross mix. 4. A strong relationship was found between zinc consumption rate, rate of dross generation and rate of reusable zinc metal generation (significant at a 99% confidence level). Regression analysis showed coating weight, effective aluminum, immersion time, strip entry temperature and bath temperature have a significant effect on coating aluminum content (significant at 99% of confidence level).