Surface treatments

Continuous and hot dip galvanization

M.P. Delplancke – Ogletree

 Introduction
Principle: production of a zinc layer on steel by dipping the steel substrate in a
molten zinc bath

Objective: to increase the corrosion resistance (sacrificial anode)

Life-time of the protection : proportional to the zinc layer thickness (10 to 120 µm).

Two types of industrial activities (processes, products, markets)

–  Continuous galvanizing for steel sheets or wires, life time of the order of 5
years
–  Hot dip (batch) galvanizing for steel parts (masts, buckets…), life time of the
order of 20 years (higher thickness)

Competition: electro-galvanizing
–  Better quality for electrolysis layers (better visual finishing)
–  BUT higher productivity and thickness and lower costs for dipping
=> tendency: increasing market share for dipping
 Introduction
Similar processes are used for other metal layers:
–  Zinc alloys : i.e. Zn-Al
–  Aluminum
–  Tin
Economical aspects (source IZA)
Production in % of total continuous galvanized sheets
Product Market Layer Key attributes Applications
part (%) composit
ion
Galvanized 75% Pure zinc formability, durability, range of Steel framing, heating,
thickness, paintability, cost ventilation, roof and floor
effective, strength and speed of decking, pre-painted building
installation panels…
Electro- 15% Pure zinc Surface finish, weldability, Autobody outer panels,
galvanized electromagnetic shielding computer cases
Galvanneal 5% Fe-Zn formability, weldability, paintability Autobody outer panels, pre-
alloy painted appliances wrappers
Galvalume 4% Zn-55%Al Corrosion performance for bare Bare and painted roofing and
alloy coating, paintability, low formability siding
Galfan 1% Zn-5%Al Compromise between corrosion Pre-painted architectural
alloy resistance and formability, panels, automotive equipment
paintability
 Introduction
Galvanizing: major zinc market
 Introduction

Market share by first-use and end-use

source Nyrstar Annual report 2010

 Galvanizing : Thermodynamics
Fe-Zn phase diagram

•  Possible reactions between

the two metals

•  Succession of inter-metallic
phases : Γ, δ1, ζ, η

•  Low solubility of Zn in Fe

•  Usual process temperature

440 – 520°C
 Galvanizing : Thermodynamics
Properties of the different phases

Phase compound Fe(wt%) Crystal Density Hardness

η Zn <0.03 Hexagonal 7.14 37

ζ FeZn13 5-6 monoclinic 7.18 270

δ1 FeZn7 7-12 Hexagonal 7.25 450-470

Γ FeZn3 21-28 Cubic 7.36 510-550

FeZn10 (steel 7.85) (steel 150)
FeZn21

•  The existence of intermetallics is favorable to adhesion

•  The phases rich in iron Γ and δ1 have higher hardness than the substrate =>
favorable for shock resistance of the layer but negative for formability
 Galvanizing : Thermodynamics
Layer and interface aspects

Dipping 10 min at 450°C

 Galvanizing : Thermodynamics
Dross formation

Origin : During the process intermetallics are formed in the zinc bath. Having a
higher density than zinc, they accumulate at the bottom of the galvanizing
bath

Action: mechanical extraction with liquid zinc

Composition: 50 wt% Fe-Zn crystals - 50 wt.% Zn

=> importance of recycling the drosses

Quantity of drosses (D):

–  6 -15 kg dross per ton of treated steel
–  Increases with increasing Tbath or Tsteel or line velocity
–  Decreases with increasing layer thickness
 Galvanizing : Thermodynamics
Fe-Al phase diagram

•  No liquid phase in the

temperature range of
galvanizing

•  Presence of FeAl3, Fe2Al5,

FeAl2

•  Very negative free energy

of formation for the
intermetallics

•  Kinetic of formation is also

high
 Galvanizing : Thermodynamics
Al-Zn phase diagram

•  Large solubility of Al in
zinc

•  Alloys are possible

(Galfan, Galvalume)

•  Small Al additions (<

1wt.%) in classical
galvanizing

Role of Al:
•  To form a protective layer
•  To decrease the dross formation (2-3 kg/T)
•  To obtain floating dross in place of sinking dross
 Galvanizing : Thermodynamics
Fe-Al-Zn phase diagram
At 450°C
Al

Fe
 Galvanizing : Thermodynamics
•  For Al < 0,11 wt.%, the usual Fe-Zn phases are stable (ζ and δ1)

•  For intermediate Al content:

–  First common stability zone with Fe2Al5 and δ1
–  For higher Al content only Fe2Al5 is stable
–  Only top drosses are formed

•  The quantity of Al addition to

stabilize Fe2Al5 increases when
the iron content of the zinc bath
increases

•  The minimum Al content also

varies with T

•  Al addition decreases the iron

solubility
 Galvanizing : Thermodynamics

Structural effect of Al additions

•  A very thin layer of Fe2Al5 is

produced at the interface with
steel : « inhibition layer »

•  If this layer is dense and has

a good adhesion, the
corrosion of steel is stopped

•  The zinc layer is free of Fe-Zn

compounds
 Galvanizing : kinetics
Effect of the following parameters on the Al up-take at the interface:

–  Bath and steel sheet temperatures

–  Bath composition
–  Hydrodynamic condition : Re number in laminar and turbulent flow due to
the dipping velocity

Turbulent Conditions
Aluminum at interface (mg/

Measures
m2 )

Measures
curve

Time of immersion (s)

The inhibition layer is formed during the first seconds of immersion.

 Continuous galvanizing : industrial process
The galvanizing cell:
–  Contains ~ 200T of zinc heated by induction
–  The steel sheet enters the bath obliquely without contact with air and exits
vertically
–  Before solidification the zinc thickness is adjusted by a gas jet.

120m/min steel sheet

width 1.5 m Control of immersion’s temperature
thickness 0.3 mm

Control of deposit’s
thickness by jets of gas
(knives of air)

Zinc tank
Depth 2m, length 4m
Width 3.5 m
 Continuous galvanizing : industrial process
A full production line:
 Continuous galvanizing : industrial process
Process parameters:
1. Annealing
–  Essential to optimize steel structure after cold rolling
–  Temperature profile: (i) linear ramp to the annealing temperature Ta, (ii) level
at this temperature, (iii) cooling to intermediate aging temperature Tag, (iv)
cooling to exit temperature (temperature for entering the galvanizing cell)
–  Annealing under a reducing gas atmosphere (N2 – 5%H2)
–  Control of the ratio = r= pH2O/pH2. At T= 800°C, r = 0,39 (prevention of iron
oxidation)

2. Immersion
–  Without contact with air
–  Temperature of steel sheet close to bath temperature (maximum difference
20°C), necessary for the thermal balance of the cell.

3. Galvanizing cell
–  Induction heating: generally 450 – 470°C
–  Addition of Zn-Al ingots (batch addition)
–  Regular control of bath chemistry (Pb, Cu, Ca, Al, Cr, Ni)
–  Line velocity: ~ 120 m/min, immersion time = a few seconds
 Continuous galvanizing : industrial process
Outlet:
–  Dynamic equilibrium between zinc fluxes up and down => good verticality
–  Zinc thickness higher for higher line velocity
–  After 0.5 s, the « air knife » limit the thickness
–  Zinc layer totally solidified at the top of the vertical line

Characteristic numbers:
–  Steel coil: 20T
–  Steel thickness: 0.25 – 1.5 mm
–  Steel width; 825 – 1650 mm
–  Maximum line velocity: 180m/min
–  Typical quantity of zinc for a steel sheet coated on both sides: 100 g/m2

For Galvannealed:
–  After thickness control, in-line annealing at ~ 500°C: diffusion of iron in the
zinc layer and formation of intermetallics without free zinc => weldability,
paintability and ductility of the coating.
 Hot-Dip batch galvanizing
Principle: immersion of individual parts in the molten bath
–  Batch process
–  Applied on final products, no further processing before end-use
–  Zinc thickness higher than in continuous galvanizing (no real possibility of
controlling) => longer life time
–  Use of dedicated cells adapted to part dimensions (screws, bolts, masts…)

Flow sheet
1. Part preparation
–  Alkaline degreasing: solution of Na2CO3 +NaOH+ detergents+surfactants at
60 – 80°C
–  Rinsing
–  Pickling: HCl at 120-210g/l at room temperature or sand blasting
–  Rinsing
2. Fluxing
–  Dissolution of oxide layer formed during rinsing and protection against
corrosion
–  Composition: ZnCl2.2(NH4Cl) or ZnCl2.3(NH4Cl) at 180°C – 230°C
 Hot-Dip batch galvanizing
–  Mechanism:
ZnCl2 .2 ( NH 4Cl ) → ZnCl2 ( NH 3 ) + NH 3 ( g) + 2HCl ( g)
FeO ( or ZnO ) + 2HCl + NH 3 → FeCl2 ( NH 3 ) or ZnCl2 ( NH 3 ) + H 2O ( g)

–  Flux has low viscosity and density and is aggressive towards steel
–  Formation of matte:
FeCl2 + Zn (l ) → Fe + ZnCl2 → matte

3.  Galvanizing: two options

–  Dry galvanizing: fluxing is made in a separate reactor and followed by
drying => steel is protected during intermediate storing and immersion in the
zinc bath is softer
–  Wet galvanizing: immediate immersion after wet fluxing => huge
turbulences
–  Uncontrolled hydrodynamics (thermal gradients, flux reaction)
Hot-Dip batch galvanizing