0. Work of: M. Monnoyer, B. Corlu, T. Machado Amorim, L. Dosdat, C. Dieu
Interest of new generation ZnAl3.7Mg3.0 (Magnelis ® ) coatings for the Energy and Construction Market
Ir D. Parein
Work of: M. Monnoyer, B. Corlu, T. Machado Amorim, L. Dosdat, C. Dieu

1. ArcelorMittal in a nutshell
What is ZnAlMg coating: Magnelis ?
Exceptional Properties
Corrosion resistance – specific behaviour
Self healing effect
Abrasion resistance
Applications

2. Leader in North America Leader in Latin America*
ArcelorMittal Worldwide
85 Mt of Steel
ArcelorMittal is the world's leading steel and mining company
209,000 employees in more than 60 countries.
An industrial presence in 19 countries
Value geographical breadth/ product diversity/ raw materials security
Leader in all major global steel markets
Automotive
Construction
Household appliances
Packaging
Energy
Wordclass R&D and technology
Leader in North America
Leader in Latin America*
No 1 in Europe
Major producer
in the CIS
Leader in
Africa
ArcelorMittal
Others
Information on the graph updated by Adina Sinea (March 2013) 2

3. ArcelorMittal for Energy
from steel to solutions...

4. ~ 4 mmt participation to energy markets …
Plate for oil and refined products rail car transport
Plate for oil tankers
Steel products for coal, gas power stations, nuclear, electricity transmission ...
Slabs for plate production for LSAW pipe
HRC for spiral welded pipe
Plate for LSAW pipe
Spiral welded pipe
Seamless pipe
Tube and plate for oil refining
Plate for CTL/GTL
Plate for storage tanks
Plate for gas treatment
Plate and krybar for LNG
Blooms for compressed natural gas
Clad plate for subsea flowlines and risers
Wire products for flexible risers
Plate for slurry pipes (oil sands)
Blocks for pumps and blow-out preventers
Slabs
Plate
Tubular products
Sections and Beams
Wire rod
Slabs for HRC for welded tubes
HRC for welded tubes
Welded tubes
Seamless Tubes
… strategic choice to further develop

5. broad energy product portfolio …
Seamless OCTG
API 5CT, EN, NF, DIN, CSN,UNI
Hunting premium
 23/8” – 16”
up to Q125
Seamless Pipe
API 5L, ASTM, ASME, EN
 0.5” – 20”
up to X70
Spiral Line Pipe
EN, API, DIN, CSN, GOST
 123/4” – 56”
up to X70
Longitudinal Welded Pipe
API 5L, ASTM, DIN, EN
 4,5” – 56”
up to X65
Coating Services
Varnish, lacquer, enamel, poly- ethylene, cement- plastic, bitumen, cement mortar, epoxy
tubular
product family
Structural Steels
non-alloy
fine grain
offshore
proprietary HISTAR Fritenar + offshore
Wire
including flat wire for flexible pipe
Rebar
including Krybar for cryogenic applications
long carbon
product family
Construction plate
Plate for Offshore and Line Pipe
Pre-qualified
2Y 60 up to 3”
Shipbuilding plate
Specialty plate
Stainless & clad steels
Cryogenic steels
Pressure vessel steels
Special formats
Jack-up rig leg components
Blocks for blow-out preventers
plate
product family
HRC for
Line Pipe
HRC for OCTG
Special flat carbon products
Magnelis: corrosion resistance
fire resistant steels
light flat carbon
product family
… covering all steel needs
for energy-related projects

6. unmatched global reach …
employees
presence in
60 countries
5 continents
2013 steel shipments
84 million tons
AM Projects Oil&Gas]
flat carbon steel mill
plate mill
beams & sections
pipe & tube
R&D centre
project centre
sales office
… we feel comfortable serving you
any place in the world

7. MAGNELIS®| Exceptional Corrosion resistance

8. Heavy gauges applications in Oil & Gas and Construction Market│
Major Corrosion issue
Structural parts often submitted to high level of corrosion stress due to direct exposure to:
Aggressive atmosphere chemistry (salt, offshore, industrial or animal pollution…)
Exposure to sand abrasion
Soil burying
Water immersion or dripping
Concrete immersion …
Thick gauge (2 to 6 mm) = increased risk of cut edge corrosion
Thinner gauge ( < 2mm ) (use of High Strenght Steels) = increased risk of parts perforation
 Need for high performance or additional corrosion protection means
M. Monnoyer, B. Corlu, T. Machado Amorim, L. Dosdat, C. Dieu – Galvatech 2015 8

9. Heavy gauges applications in Oil & Gas and Construction Market│
How to improve life time ?
High performance or additional corrosion protection means
Thick standard Zn-based coatings 600gr/m² or more
Alternative Al-based coatings (Aluzinc, Aluminized type 2…)
Batch galvanizing
Drawbacks: high cost, impact on in-use properties (profiling, welding)
Alternative substitution:
thin, high corrosion resistant
ZnMgAl (Magnelis) coating?
Zn – 3.7Al – 3.0Mg 9

10. Corrosion Protection Mechanism: Lower Oxygen Reduction
At the initial stages of corrosion process, metallic coating consumption is governed by oxygen reduction rate
Erest ZnMgAl
Erest GI
Coating dissolution
ZnMgAl GI
Polarisation curves (5%NaCl – pH=7)
Oxygen reduction
Jcorr (µA/cm2) GI
~20
ZnMgAl
~10
ZnAlMg allows decreasing oxygen reduction rate by a factor 2 compared to standard HDG-Zn 10

11. Corrosion Protection Mechanism: Inhibiting Corrosion Products
When the coating corrodes, corrosion resistance is closely linked to the inhibiting properties of corrosion products that precipitate both on steel and coating surfaces
Initial state
Coating
Steel
Environment O2
OH-
Mn+ e-
Advanced state
Coating
Steel
Environment
Corrosion products O2
OH-
Mn+
Mn+ (Zn2+/Mg2+/Al3+) +
CO32- / Cl- / OH- / SO42-
More compact and stable the corrosion product layer is, more important is the hindering effect on oxygen reduction
June 2nd, 2015 11

12. LDH ≥ ZHC = ZHS > HZ > ZC > ZnO
Corrosion Protection Mechanism:
Compact corrosion products
Main Zn and ZnMgAl corrosion products formed in cyclic corrosion tests and in field exposure
Zinc oxide: ZnO
Zinc carbonate (ZC): ZnCO3
Hydrozincite (HZ): Zn5(CO3)2(OH)6)
Simonkolleite (ZHC): Zn5(OH)8Cl2 / Zinc Hydroxide sulphate (ZHS) Zn4SO4(OH)6
Layered Double Hydroxide (LDH): Zn0.61Al0.39(OH)2(CO3)0,195.xH2O
ZHS
ZHC HZ ZC
ZnO
Corrosion inhibition
LDH ≥ ZHC = ZHS > HZ > ZC > ZnO
High compactness  zinc basic salts
Low compactness  ZnCO3 and ZnO
Inhibition power of corrosion products is in direct relation with their compactness
June 2nd, 2015
3% Mg is minimal needed cfr study at Tsukuba University /Japan- March 2010 12

13. Corrosion Protection Mechanism:
Corrosion Products of Magnelis (ZnAlMg)
Alloying elements present in ZnAlMg coating will contribute to the precipitation of compact and stable corrosion products
Samples analyzed after 2 years of exposure in Brest (Marine environment)
Zn-Al LDH
ZHS
ZHC HZ
ZnO
ZnAlMg + ++ -
HDG-Zn
+++
On standard HDG-Zn, poor protective corrosion products are detected in high amount
Important quantity of ZnO and HZ, presence of ZHS and ZHC
On ZnAlMg, major presence of protective corrosion products
ZHC/ZHS and LDH, low amount of HZ, no ZnO 13

14. Corrosion Protection Mechanism:
Corrosion Products in real corrosion simulation
Compact Simonkolleite is observed on ZM surface after 10 VDA cycles
Porous Mg carbonate
EDS: Mg>>Zn , C, O
Compact Simonkolleite
EDS: Zn>>Mg, Cl, O
Simonkolleite is the protective corrosion product
Mg carbonate forms but is not protective

15. Corrosion Protection Mechanism: Role of Al and Mg
4/28/2017
4/28/2017
Corrosion Protection Mechanism:
Role of Al and Mg
The role of Mg2+ ions is to stabilize the protective Zn-corrosion products (ZHC, ZHS), avoiding their transformation into ZnO
The role of Al is the formation of protective and stable LDH corrosion product
The strong barrier effect of corrosion products formed on ZnMgAl is clearly shown from electrochemical trials in controlled potential conditions 15 15

16. Magnelis outperforms standard pre and post galvanized materials
Exceptional Corrosion Resistance
In a Salt Spray Test
Magnelis (20µ) compared with pre galvanized (20µ)
Magnelis (20µ) compared with post galvanized (85µ)
Galvanised
Magnelis
Salt Spray test
Z after 6 weeks Magnelis after 34 weeks
Magnelis outperforms standard pre and post galvanized materials

17. Exceptional Corrosion Resistance: In a Marine environment
Sea
Test results of the French institute of corrosion
Samples
Brest
Test Area: Brest (FR), C5M environment (marine, 2 meters from the sea)
Similar test done in Florida (US) (C4/C5 environment) with same results
Also in Marine environments Galvanized steel corrodes
3 times faster than Magnelis®
Confidential

18. Improved Cut Edge protection: Mechanism
Al3+
Environment
Mg2+
Zn2+
Current Density (J)
Oxygen reduction
-1.05
Coating dissolution
Hydrogen reduction
E (V/SCE)
Steel dissolution
OH- O2 e-
Steel
Coating
On cut edges, coating dissolves preferentially to protect steel
Corrosion products precipitation on cut edges  self-healing mechanism 18

19. Self healing effect observed in outdoor exposure after 9 months
Improved Cut Edge protection:
Assesment in Field exposure
Red rust evolution observed on ZnAl3.7Mg3 coated samples with varying thicknesses during 9 months outdoor exposure on marine site (French Corrosion Institute in Brest, Marine environment)
Evaluation by computer assisted image analysis
Steel thickness=4mm
Steel thickness=5mm
Steel thickness=5,5mm
1month
3months
6months
9months
Coating thickness: 25µm
Self healing effect observed in outdoor exposure after 9 months 19

20. Coating thickness: 20µm, steel thickness: 2mm
Improved Cut Edge protection:
Life time extension of perforated steels
Red rust evolution observed on ZnAl3.7Mg3 coated perforated samples compared to standard HDG-Zn and HDG-AlZn during 5 years outdoor exposure on marine site (French Corrosion Institute in Brest, Marine environment) - Evaluation by computer assisted image analysis
Coating thickness: 20µm, steel thickness: 2mm
Es after 5 yeatrs
Self-healing Comparison
Magnelis (ZnAl3.7Mg3 ) >4 years
HDG-Zn  1 year
HDG-AlZn  no self healing effect
Results after 5 years: 20

21. MAGNELIS®| Sand abrasion resistance

22. Coating hardness has a direct impact on the abrasive wear resistance
Abrasion resistance:
Microhardness as reference for abrasion resistance
Coating hardness has a direct impact on the abrasive wear resistance
Material HV
Galva 64
Galfan 69
Aluzinc
129
Magnelis®
141
Batch galva:
Outer Zn layer of batch
Intermetallic layers 70
More than 179
Magnelis® hardness is much higher compared to standard zinc coatings and Zn layers of batch galva

23. Abrasion & Corrosion resistance: Real outdoor exposure
First desert field : Dubai, collaboration with the French Corrosion Institute (Worldcoat project) 23

24. Abrasion & Corrosion resistance:
First results of real exposure in Dubai
First set-up (Magnelis & HDG) exposed since 2 years
Second set-up (Magnelis & batch galva) exposed since 1 year 24

25. Magnelis: Broad usage
Applications:
Magnelis: Broad usage
Outstanding corrosion resistance
Self healing effect assuring protection of the edges
Cost effective alternative for aluminium, stainless and batch galva
Thickness available from 0.45 mm until 6 mm
Very good corrosion protection in soil
Structures for solar structures
Storage tanks – Silo’s
Decks for parking lots,
Sound isolation wall panels
Civil engineering & Public Works …
Profiles, Tubes
Structural material, Cladding,
Cable trays,
Expanded metal, Concrete moulds,
Building & Construction

26. Conclusions: Magnelis offers…
Improved corrosion resistance (3% of Magnesium)
Edges protection thanks to the Self healing effect
Very good abrasion resistance
Excellent resistance in soil and concrete
Excellent adhesion for post painted
Excellent formability
Environmental friendly coating
A breakthrough material for tubes