Al Seminar

Intermetallics
and
Aluminium for (Beverage) Cans
Dr. Havovy Cama
Alcan International Limited,

Banbury Laboratory,
Southam Road,
Banbury OX16 2SP.
Email: havovy.cama@alcan.com
Alcan International Limited © Alcan International Limited
Topics
• A brief Introduction of Alcan Inc.
• Definition of intermetallics and can stock
• Production and processing of can stock alloys

" Effect on intermetallic particles
" Techniques to characterise intermetallic particles
• Ways of enhancing can stock performance

Recent History
• Merger of
" Alcan Aluminium Limited
" Algroup
" 17th October, 2000.
" New Company Alcan Inc. (name adopted since March 2001)
• Global Provider of Aluminium, Packaging and

Solutions
Aluminium
Aluminium
Primary Fabrication
Fabrication Packaging
Metal Americas &
Europe
Asia
Research and Technology - Alcan Inc.
R&D Budget - 2000

Alcan Inc.
Number of Employees = 53000
By Sector Geographical
Repartition
Packaging Primary Other Europe
17,000 17,000 9,000 23,000
Fabrication Fabrication North

Europe Americas & America
12,000 Asia 21,000
7,000

Aluminium Processing
HOMOGENISATION
CASTING
ROLLING

Typical processing route for Canstock Alloys
DC Cast Ingot
Approx. 660mm x 1850mm x 8600mm Scalping
AA3104 (CBS), AA5182 (CES) Rolling face (+ side faces)
Preheat / Homogenisation
Hot Roll
Break Down Mill to ~ 35mm
475- 630 °C
Hot Tandem Mill to 2-3mm
Target exit temp 300-350 °C
Cold Roll
Finishing Operations
Final gauge < 250 µm
Post Lub application /
Lacquering
To customer specification
DC Casting of Sheet
Ingots

Continuous Casting of Sheet Ingots

Homogenisation

Pusher Furnace

Breakdown Mill

Cropping & Tandem Mill Rolling

Cold Rolling

Products

Products

New Product Applications after the Merger

World Beverage Can Market for Al
China
Middle East
South East Asia
South Africa
South America
Central America
Japan
US&Canada
Europe
1995 (total 202 billion cans) 2000 estimate (total 233 billion cans)
15% increase
Banbury Laboratory
Banbury
Located 26 miles north of Oxford

- 2 miles off jn. 11 on M40

Projects at Banbury Laboratories
Raw Materials
Metallurgy
Surface Sciences
Process and Product

Modelling
Technical Customer
Support

Importance of Intermetallic Type
for
Aluminium Canstock Performance

Importance of Improving Can Stock Performance
(The Canning Market)
• Probably the single largest use of aluminium.

" 12% of total global Al output used to make beverage
cans
• Market is still evolving

" Cost reduction.
" Weight reduction (down gauging).
" Pressure from non-aluminium materials.
" Need for product innovation.

Aluminium Beverage Can
Can End (5XXX Alloy - Mg rich)
Can Body (3XXX Alloy - Mn rich)

Drawn and Ironed (DI) Cans
The DI cans are cleaned, decorated and lacquered at the

customer plant prior to filling them with beverage.

Drawing and Ironing (D&I) Process
Cup on Punch
Ironing Dies
Ironed
untrimmed can
Redraw Die
Cooling Ports
Dome tooling

Schematic Diagram
AA Compositions of Canning Materials
wt.% Mn
2.0
Can Body Stock

1.5 AA3004 <0.3Si
<0.7Fe
<0.25Cu
1.0
AA3104 AA5017 <0.2Si <0.2Si
<0.35Fe <0.35Fe
<0.6Si <0.15Cu <0.15Cu
<0.8Fe <0.1Cr <0.1Cr
0.5 0.02-0.25Cu
<0.25Si Tab Stock
<0.4Fe
AA5042 AA5182
Can End Stock
<0.1Cu AA5052
0.0 0.15-0.35Cr
0 1 2 3 4 5
wt.% Mg

Can End Manufacture

Cans in the 21st Century
Thinner, stronger and different shapes

Technical Improvements
•Down gauging,
•Light weighting (reduced 25 - 30 % in last 20 yrs)
0.016 .406
Gauge Gauge
(inches) (mm)
0.014 .356
0.012 .305
0.010 .254
0.008 .203
1980 1985 1990 1995 2000 2005

Ingot: 0.66 m x 1.850 m x 8.6 m
What are Intermetallic Particles ?
These are large particles (10-100 μm) formed in the matrix

during solidification of the melt.
50 μm

Constituent Particle Formation
During Solidification
Major Alloying
Elements Trace Chemistry
As-cast Particle
Population
•Phase type
•Size Distribution
•Spatial Distribution
•Morphology
Solidification
Grain Refiner Conditions

Feature Detection and Classification (FDC)
Technique
• The apparent concentration of Fe+Mn vs. Si of each point is plotted
• Reference to the literature and experimental data on standard samples have

led to boundaries between the phases being determined
• Great care should be taken to 25

6 or 3
allow for α
" particle size app wt% Fe
" solute effects β
" neighbouring phases

" partial transformation 0 5.0 app wt% Si

Feature Detection and Classification
(FDC) Technique
FDC on single field @ x860
25
20
15
Fe+Mn
10
Al6(Fe,Mn)
5 Alpha
Assigned duplex on IBAS
0
0 0.5 1 1.5 2
Si
Al6Fe α
Note: Duplex particles fall in both classifications, depending upon the
position of the probe analysis point.
Intermetallic Extraction & Analysis
Al + butanol Al-butoxide + H2
• The technique was developed at Sintef during the 1980s, enabling

sufficient quantities of dry butanol to be distilled for the reliable extraction
and collection in the absence of H2O, of sufficient particulate for
subsequent analysis.
• Extracted Particles are ground and analysed using X-ray diffraction and
resultant traces are compared with those from known intermetallic types

X-Ray Diffraction of Intermetallics
evaporation grinding
Ultrasonic + methanol Sample (+ petroleum jelly)
Zero reflection Si disc
X-ray detector
Co X-ray tube θ
nλ = 2d ⋅ sinθ

XRD Traces
Peaks used in calibration curve are marked using */+

XRD
• Comparison of peak positions and relative
peak intensity with standard spectra give

calibration curve
phase identification
Log Peak ratio IA/IB

X
R∝
• Comparison of peak intensity ratios with 1− X
standard calibration curves gives estimate
of relative concentration of phases

0 1
• For multiple phase mixtures spectra are X=Fraction phase A
complex and interpretation difficult

Bridgman Furnace
furnace
alumina crucible
solid-liquid interface
thermal shield
water bath
rolling 'O' ring

seal water cooled
jacket
stepper motor
controlled drive rod

Effect of Casting Speed and Alloy Composition
on Intermetallic Phase Selection
120
100 Al3(Fe,Mn)
Speed
mm/min 80 Al6(Fe,Mn)
α-Al(Fe,Mn)Si
60
40
20
A B C
Al-1.25%Fe-0.25%Mn Al-0.5%Fe-1.0%Mn Al-0.5%Fe-1.0%Mn

-0.2%Si-1.2%Mg-0.2%Cu -0.2%Si-1.2%Mg-0.2%Cu -0.4%Si-1.2%Mg-0.2%Cu
Increase Fe/Mn Base Alloy Increase Si
Effect of Alloy Composition and
Casting Conditions on Intermetallics
• Their composition and crystallographic structure

depends upon the alloy composition and casting velocity
of the ingot and cooling rate of the melt.
" The type of intermetallics can change during processing
• Their size depends on casting velocity

" Increasing the casting velocity decreases particle size.
" Size of particles affects final product performance
(recrystallisation, can scoring).

Equilibrium Phase Diagrams
Al6(Fe,Mn)
αc=Al(Fe,Mn)Si
αc
Mg2Si
• Results only as good as database used
• Metastable phases formed during casting. Depending on

homogenisation time and temperature, they transform totally or
partially to equilibrium phases.
Homogenisation
T(oC)
2 stage heating
HTR
Time (Hours)
Depending on type of furnace, homogenisation times can vary from a few

hours to up to a day.
Effect of Time on Amount of Alpha Phase in AA3104
After Isothermal Exposure at 550 oC
100
After isothermal (rapid heating rate) exposure of
%Al6(Fe,Mn) transformed to alpha

90
AA3104 at 550°C
80
70
60
50
40
30
20
10
time (hours)
0
0 2 4 6 8 10 12 14 16 18 20
In the temperature range 550-630 °C, the amount of Al6(Fe,Mn)

transformed to α-Al(Fe,Mn)Si increases with increasing exposure time
until it reaches a maximum (equilibrium) concentration determined by
the alloy composition and homogenisation temperature. The
transformation rate is initially rapid and then slows down.
The Effect of Si Content on the Type of Intermetallic
Present after Homogenization
After isothermal Exposure of
Al-0.5%Fe-1%Mn-1.2%Mg-0.2%Cu-x%Si alloy at 550°C
120
%Al6(Fe,Mn) transformed to
100
80
alpha
0.2%Si
60
0.4%Si
40
20
0
0 50 100 150
exposure time (minutes)
Increasing the Si content in the alloy increases the rate of the Al6(Fe,Mn)
to α-Al(Fe,Mn)Si transformation.
Homogenisation of 3xxx Alloys
AA3104: Al-0.4%Fe-0.9%Mn-1.2%Mg-0.2%Cu- 0.2%Si
Al6(Fe,Mn) Mg2Si
Si α
α
Si
Temperature

AA3104: Al-0.4%Fe-0.9%Mn-1.2%Mg-0.2%Cu-0.2%Si
After Isothermal Heat Treatment at 600 °C for 15 mins

Cell Edges
αc-Al(Fe,Mn)Si
Al6(Fe,Mn)
20 µm

AA3104: Al-0.4%Fe-0.9%Mn-1.2%Mg-0.2%Cu- 0.2%Si
After Ramped Heat Treatment

TEM images of AA3104 ramped to 300°C then isothermally treated.
100nm 100nm 100nm
400 °C / 12m 450°C / 5m 450 °C /15m

Particle Break-up During Rolling (CBS)
Breakdown mill rolling produces slab

Hot rolling produces reroll
Cold rolling produces final gauge sheet
Improved Can Body Stock
• Thinner
" Downgauge further
• Good strength
" Solid solution strengthening, strain hardening
" Controlled by alloying and thermomechanical processing
" Strength limited by customer tooling performance
• Galling control
" Need for continuous die cleaning for good can surface
" Believed to be controlled by correct size and amount of alpha phase
• Earing control
" To minimise metal wastage after D&I process
• Cost
" Controlled by cost of alloying additions and final gauge
Wall Ironing Process (CBS Manufacture)
Galling
Ironing Die
Entry
Exit
Punch Travel Direction
Score lines
Improved Canstock
(With respect to Galling resistance)
• Need enough alpha particles of optimum size

• Can be obtained by increasing the Si concentration
• Decreasing homogenisation temperature

Improved Can Body Stock
• Thinner
" Downgauge further
• Good strength
" Strength limited by customer tooling performance
• Galling control
" Need for continuous die cleaning for good can surface
" Believed to be controlled by correct size and amount of alpha phase
• Earing control
" To minimise metal wastage after D&I process
" Controlled by alloying and thermocmechanical processing
• Cost
CBS Performance
20
15
volume%
Low Fe+Mn
10 Medium Fe+Mn
High Fe+Mn
5
0
cube Goss Brass Cu S

Can End Stock - AA5182
Al-0.04%Si-0.16%Fe-0.040%Cu-0.48%Mn-4.60%Mg
Mg5Al8
Al6(Fe,Mn)
Tau - AlCuMg
Mg2Si

Improved Can End Stock
• Good strength
• Good Formability
" Reduce number of coarse particles
• Earing control
" To minimise metal wastage during seaming
• Cost

CES Performance
Number density of Fe phases Number density (total)
6000 10000
5000
Number density
Number density
8000
Ingot Ingot
4000
Slab 6000 Slab
3000
Re-roll 4000 Re-roll
2000
Final Final
1000 2000
0 0
0.1%Si 0.2%Si 0.3%Si 0.1%Si 0.2%Si 0.3%Si
Number density of Mg2Si Kahn Test UPE
7000 50
6000
Number density
40
UPE (kJ/m^2)
5000 Ingot
4000 Slab 30 L-T
3000 Re-roll 20 T-L
2000 Final
10
1000
0 0
0.1%Si 0.2%Si 0.3%Si 0.1%Si 0.2%Si 0.3%Si

Always let the upstream end of
your business know what the
downstream end is doing.

(Prepared By R. A. Ricks - Alcan International Ltd.)

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Intermetallics

Dr. Havovy Cama

Alcan International Limited,

• A brief Introduction of Alcan Inc.

• Definition of intermetallics and can stock

• Production and processing of can stock alloys

• Ways of enhancing can stock performance

Alcan International Limited © Alcan International Limited

• Global Provider of Aluminium, Packaging and

Alcan International Limited © Alcan International Limited

Fabrication Fabrication North

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Located 26 miles north of Oxford

Alcan International Limited © Alcan International Limited

Process and Product

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

• Probably the single largest use of aluminium.

• Market is still evolving

Alcan International Limited © Alcan International Limited

Can End (5XXX Alloy - Mg rich)

Can Body (3XXX Alloy - Mn rich)

Alcan International Limited © Alcan International Limited

The DI cans are cleaned, decorated and lacquered at the

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Can Body Stock

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

Thinner, stronger and different shapes

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

These are large particles (10-100 μm) formed in the matrix

Alcan International Limited © Alcan International Limited

Alcan International Limited © Alcan International Limited

• The apparent concentration of Fe+Mn vs. Si of each point is plotted

• Reference to the literature and experimental data on standard samples have

• Great care should be taken to 25

" solute effects β

" neighbouring phases

Alcan International Limited © Alcan International Limited

• The technique was developed at Sintef during the 1980s, enabling

Alcan International Limited © Alcan International Limited

Zero reflection Si disc

Alcan International Limited © Alcan International Limited

Peaks used in calibration curve are marked using */+

• Comparison of peak positions and relative

peak intensity with standard spectra give

Log Peak ratio IA/IB

standard calibration curves gives estimate

of relative concentration of phases