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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

Alcan International Limited © Alcan International Limited


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
Alcan International Limited © Alcan International Limited
Research and Technology - Alcan Inc.
R&D Budget - 2000

Alcan International Limited © Alcan International Limited


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

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Aluminium Processing
HOMOGENISATION
CASTING

ROLLING

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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
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DC Casting of Sheet
Ingots

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Continuous Casting of Sheet Ingots

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Homogenisation

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Pusher Furnace

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Breakdown Mill

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Cropping & Tandem Mill Rolling

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Cold Rolling

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Products

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Products

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New Product Applications after the Merger

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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
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Banbury Laboratory

Banbury

Located 26 miles north of Oxford


- 2 miles off jn. 11 on M40

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Projects at Banbury Laboratories

Raw Materials

Metallurgy

Surface Sciences

Process and Product


Modelling

Technical Customer
Support

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Importance of Intermetallic Type
for
Aluminium Canstock Performance

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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.

Alcan International Limited © Alcan International Limited


Aluminium Beverage Can

Can End (5XXX Alloy - Mg rich)

Can Body (3XXX Alloy - Mn rich)

Alcan International Limited © Alcan International Limited


Drawn and Ironed (DI) Cans

The DI cans are cleaned, decorated and lacquered at the


customer plant prior to filling them with beverage.

Alcan International Limited © Alcan International Limited


Drawing and Ironing (D&I) Process
Cup on Punch

Ironing Dies
Ironed
untrimmed can
Redraw Die

Cooling Ports

Dome tooling

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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

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Can End Manufacture

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Cans in the 21st Century

Thinner, stronger and different shapes

Alcan International Limited © Alcan International Limited


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

Alcan International Limited © Alcan International Limited


Ingot: 0.66 m x 1.850 m x 8.6 m
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What are Intermetallic Particles ?

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


during solidification of the melt.

50 μm

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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

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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

Alcan International Limited © Alcan International Limited


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.
Alcan International Limited © Alcan International Limited
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

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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

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XRD Traces

Peaks used in calibration curve are marked using */+


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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


Alcan International Limited © Alcan International Limited
Bridgman Furnace

furnace
alumina crucible

solid-liquid interface
thermal shield
water bath

rolling 'O' ring


seal water cooled
jacket

stepper motor
controlled drive rod

Alcan International Limited © Alcan International Limited


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
Alcan International Limited © Alcan International Limited
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).

Alcan International Limited © Alcan International Limited


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.
Alcan International Limited © Alcan International Limited
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.
Alcan International Limited © Alcan International Limited
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.
Alcan International Limited © Alcan International Limited
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.
Alcan International Limited © Alcan International Limited
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

Alcan International Limited © Alcan International Limited


Homogenisation of 3xxx Alloys
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

Alcan International Limited © Alcan International Limited


Homogenisation of 3xxx Alloys
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

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Particle Break-up During Rolling (CBS)

Breakdown mill rolling produces slab


 Hot rolling produces reroll
Cold rolling produces final gauge sheet
Alcan International Limited © Alcan International Limited
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
" Controlled by alloying and thermomechanical processing
• Cost
" Controlled by cost of alloying additions and final gauge
Alcan International Limited © Alcan International Limited
Wall Ironing Process (CBS Manufacture)

Galling

Ironing Die
Entry
Exit

Punch Travel Direction

Score lines
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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

Alcan International Limited © Alcan International Limited


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
" Controlled by alloying and thermocmechanical processing
• Cost
" Controlled by cost of alloying additions and final gauge
Alcan International Limited © Alcan International Limited
Alcan International Limited © Alcan International Limited
CBS Performance
20

15
volume%

Low Fe+Mn
10 Medium Fe+Mn
High Fe+Mn
5

0
cube Goss Brass Cu S

Alcan International Limited © Alcan International Limited


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

Alcan International Limited © Alcan International Limited


Improved Can End Stock
• Good strength
" Solid solution strengthening, strain hardening
" Controlled by alloying and thermomechanical processing

• Good Formability
" Reduce number of coarse particles

• Earing control
" To minimise metal wastage during seaming
" Controlled by alloying and thermomechanical processing

• Cost
" Controlled by cost of alloying additions and final gauge

Alcan International Limited © Alcan International Limited


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

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

Alcan International Limited © Alcan International Limited


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