Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium

AMG TITANIUM ALLOYS & COATINGS
GfE Metalle und Materialien GmbH
Multinary Masteralloys for Highly Alloyed
Ti Alloys and Titanium Aluminides
Volker Guether, Matthias Achtermann (GfE Metalle und Materialien GmbH)
Anke Poetzsch (GfE Fremat GmbH)
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Outline
1. AMG Titanium Alloys & Coatings (GfE)
2. Production of master alloys
3. Motivation for multinary master alloys
 processing capability
 productivity and costs
 microstructure and properties
3. Production and properties of AlSnZrMo master alloy
for Ti-6246
4. Summary and outlook
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
AMG Titanium Alloys & Coatings (GfE)
AMG Advanced Metallurgical Group N.V.
(Netherlands)
AMG Graphite
& Silicon


Silicon metal
Natural
graphite
AMG Antimony

AMG
Mineracao
Antimony ore  Tantalum ore
and -trioxide  Niobium ore

3,275 employees

15 countries

4 markets
AMG Titanium
AMG
Alloys &
Vanadium
Coatings
 Master alloys
 Ferrovanadium
for Titanium Ferronickeland Superalloys
molybdenum
 Ti Aluminides
 Coating materials
 Vanadium
Chemicals and Oxides
 Metals-based
powders
AMG
Superalloys

Tantalum- and
Niobium oxide
 Chromium
metal
 Ferrotitanium
 Metals-based
powders
(energy, aerospace, infrastructure, specialty metals & chemicals)

AMG Engineering
AMG Processing
AMG Mining
3 business segments
Volker Guether
AMG
Aluminium

Aluminium
master alloys
 Additives

Revenue 1,216 $m
in 2012

Gross Profit 197 $m
in 2012

EBITDA 85 $m in
2012
AMG ALD
Vacuum
Technologies
 Vacuum
furnace
systems
 Own &
Operate heat
treatment
facilities
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Production of master alloys (1)
Basic production route of master alloys via ATR
•
•
raw materials metal oxides and aluminum as well as auxiliary
materials are being mixed/homogenized
mixture is ignited and reacts exothermally (aluminothermic /
thermite smelting process) within a refractory-lined or
copper vessel
V2O5 + Al
VAl + Al2O3 +
heat
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Production of master alloys (2)
2nd step: VIM alloying / refining
1st step: ATR
V-Oxide
VIM-Process
Al
Vacuum
Induction
Melting
AluminoThermic Reduction
Process
Slag
Metal
VAl 50:50
VAl 65:35
Al
Crushing
Inspection:
- Magnetic separation
- Visual inspection
- Blacklight inspection
- X-ray inspection
- Automatic sampling
- Chemical analysis
- Release by QM
Crushing
Sizing
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Motivation (1)
 processing capability
•
Highly alloyed Ti alloys and -TiAl alloys contain substantial amounts of master alloys
Ti-Al6-Sn2-Zr4-Mo6
-TNM® Ti-43,5Al -4Nb -1Mo -0,1B (at.-%)
-TNB Ti -45Al -8Nb -2Cr -0,2C (at.-%)



18 wt.-%
20 wt.-%
34 wt.-%
•
The mechanical stability of compacted electrodes (particularly for -TiAl alloys) is being
limited due to substantial powder volumes.
•
The processing of granules instead of powders would be preferred but requires the
suppression of high melting phases which may be more likely to achieve in a
multinary master alloy system.
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Motivation (2)
 productivity and costs
•
addition of one master alloy into a compact instead of
partitioning the master alloys into three or even more powders
•
cost savings with regard to raw materials
 e.g. ZrO2
Zr
•
save grinding costs and increase materials yields (granules vs. powders)
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Motivation (3)
 microstructure and properties
•
binary master alloys of high melting elements with Aluminum
such as Nb, Mo or Ta contain high dense / high melting phases in
equilibrium conditions
 the processing of such master alloys as powders is mandatory in order to
assure the dissolution / alloying in the final Ti alloy
•
such high melting phases can be avoided / suppressed by further alloying
with third or fourth elements
 master alloys can be processed as granules
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Motivation (4)
Formation of extended high melting phases under equilibrium conditions
ATR NbAl 70/30
NbAl3
Nb2Al
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Motivation (5)
advantage of multinary systems: improve control on phase formation
disadvantage: limited number of ternary phase diagrams are available but
no quaternary or higher phase diagrams
subject to experimental work
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
AlSnZrMo master alloy for Ti-6246 (1)
Experimental
• aluminothermic co-reduction and alloying of



MoO3
ZrO2
Sn
• addition of heat in order to boost the reaction
• conditioning of slag system
(shift thermodynamic equilibrium conditions)
MoO3 + ZrO2 + Sn + KClO4 + slag conditioner + Al  Al28 –Sn12 –Zr24 –Mo36 (wt.-%) + slag + heat
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
AlSnZrMo master alloy for Ti-6246 (2)
chemical analysis in wt.-%
Al
Sn
Zr
Mo
O
N
C
ATR alloy
29,15
11,90
22,20
35,65
0,16
0,001
0,043
Volker Guether
specification
27 - 30
10 - 13
22 -25
34 -37
< 0,2
< 0,01
< 0,02
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
AlSnZrMo master alloy for Ti-6246 (3)
Metallographic investigations: alloy consists of 4 different phases
slag – alloy interface
Volker Guether
center
alloy-bottom interface
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
AlSnZrMo master alloy for Ti-6246 (4)
BSE EDX semi-quantitative phase analysis
Al3Mo(Zr)
ZrSn
Al2(ZrSn(Mo))3
(MoZr)3Al
sporadical
with small
sizes
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
AlSnZrMo master alloy for Ti-6246 (5)
element mapping
center
Zr
Al
Al3(Mo,Zr)
Al2(ZrSn(Mo))3
Volker Guether
SnZr
Sn
Mo
SnZr
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Summary
• multinary alloying provides the opportunity to suppress or even prevent
the formation of extended high melting phases in master alloys
• this is an important pre-condition to process granules instead of powders
in order to improve the VAR consumable electrode stability
particularly for highly alloyed Ti alloys and Titanium Aluminides
• GfE has developed and successfully introduced multinary master alloys
for the production of Ti-17, Ti-6246, TiAl TNM, TiAl 48-2-2 and others
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy
Thank you for your attention!
GfE‘s team during the 100 year anniversary in 2011
Volker Guether
Multinary Masteralloys for Highly Alloyed Ti Alloys and Titanium Aluminides
May 19-21, 2014 • Hilton Sorrento Palace, Sorrento, Italy

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