Mat Sci Lbeck 10a

FACH
HOCHSCHULE
LÜBECK
Materials Sciences
Metals
Dr.-Ing. Norbert Hort

norbert.hort@gkss.de
Magnesium Innovations Center (MagIC)

GKSS Forschungszentrum Geesthacht GmbH
FACH
HOCHSCHULE Metals
LÜBECK
Applications and Processing
• How are metal alloys classified and how are they used?
• What are some of the common fabrication techniques?
• How do properties vary throughout a piece of material
that has been quenched, for example?
• How can properties be modified by post heat treatment?
Page 2
FACH
HOCHSCHULE Taxonomy of Metals
LÜBECK
Metal Alloys
Ferrous Nonferrous
Steels
Steels Cast Irons
Cast Irons Cu Al Mg Ti
<1.4 wt% C
<1.4wt%C 3-4.5 wt%C
3-4.5 wt% C
T(°C) microstructure:
1600 ferrite, graphite
δ
cementite
1400 L
γ+L
1200 γ 1148°C L+Fe3C
austenite Eutectic:
1000 4.30
γ+Fe3C
α+
α800 727°C Fe3C

γ
ferrite Eutectoid: cementite

600 0.76 α+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)
Co , wt% C
Page 3
1
FACH
HOCHSCHULE Steels
LÜBECK
Low Alloy High Alloy

low carbon Med carbon high carbon
<0.25 wt% C 0.25-0.6 wt% C 0.6-1.4 wt% C
heat austenitic
Name plain HSLA plain plain tool
treatable stainless
Cr,V Cr, Ni Cr, V,
Additions none none none Cr, Ni, Mo
Ni, Mo Mo Mo, W
Example 1010 4310 1040 4340 1095 4190 304
Hardenability 0 + + ++ ++ +++ 0
TS - 0 + ++ + ++ 0
EL + + 0 - - -- ++
Uses auto bridges crank pistons wear drills high T
struc. towers shafts gears applic. saws applic.
sheet press. bolts wear dies turbines
vessels hammers applic. furnaces
blades V. corros.
resistant
increasing strength, cost, decreasing ductility
Page 4
FACH
HOCHSCHULE Low Alloyed Steels
LÜBECK
a) Amount of Carbon (wt.-%/100)

b) Signs for alloying elements (PSE)
c) Amount of alloying elements (based on a multiplication factor)
E.g: 15 Cr 3, 25 CrMo 56, 22 S 20
Factor Alloying elements
4 Wo Sieht Man CroCodil? Am Nil.

10 Al, Pb, Cu, Mo, Nb, Ti, V, Zr, ...
100 P, S, N, C
1000 B
Page 5
FACH
HOCHSCHULE Refinement of Steel from Ore
LÜBECK
Coke
Iron Ore Limestone
BLAST FURNACE
heat generation
gas C+O2 →CO2
refractory
vessel reduction of iron ore to metal
layers of coke CO2 + C→ 2CO
and iron ore 3CO + Fe2O3 →2Fe+3CO2
air purification
slag
Molten iron CaCO3 → CaO+CO2
CaO + SiO2 + Al2O3 → slag
Page 6
2
FACH
HOCHSCHULE Ferrous Alloys
LÜBECK
Iron containing – Steels - cast irons
Nomenclature AISI & SAE

10xx Plain Carbon Steels
11xx Plain Carbon Steels (resulfurized for machinability)
15xx Mn (10 ~ 20%)
40xx Mo (0.20 ~ 0.30%)
43xx Ni (1.65 - 2.00%), Cr (0.4 - 0.90%), Mo (0.2 - 0.3%)
44xx Mo (0.5%)
where xx is wt% C x 100

example: 1060 steel – plain carbon steel with 0.60 wt% C
Stainless Steel -- >11% Cr
Page 7
FACH
HOCHSCHULE Cast Iron
LÜBECK
Ferrous alloys with > 2.1 wt% C

more commonly 3 - 4.5 wt%C
low melting (also brittle) so easiest to cast
Cementite decomposes to ferrite + graphite

Fe3C Æ 3 Fe (α) + C (graphite)
generally a slow process
Page 8
FACH
HOCHSCHULE Fe-C True Equilibrium Diagram
LÜBECK
T(°C)
1600
Graphite formation
1400 L Liquid +
promoted by
γ +L Graphite
• Si > 1 wt% 1200 γ 1153°C
Austenite 4.2 wt% C
• slow cooling
1000
α+γ γ + Graphite
800
740°C
0.65
600
α + Graphite
400
0 1 2 3 4 90 100
(Fe) Co , wt% C
Page 9
3
FACH
HOCHSCHULE Types of Cast Iron
LÜBECK
Gray iron
graphite flakes
weak & brittle under tension
stronger under compression
excellent vibrational dampening
wear resistant
Ductile iron
add Mg or Ce
graphite in nodules not flakes
matrix often pearlite - better ductility
Page 10
FACH
HOCHSCHULE Types of Cast Iron
LÜBECK
White iron
<1wt% Si so harder but brittle
more cementite
Malleable iron
heat treat at 800-900ºC
graphite in rosettes
more ductile
Page 11
FACH
HOCHSCHULE Production of Cast Iron
LÜBECK
Page 12
4
FACH
HOCHSCHULE Lattice transformations in iron
LÜBECK
1536 °C
δ
1390 °C
δ-iron
body centered-cubic (bcc)
911 °C
γ-iron
face centered-cubic (fcc)
lattice constant a=0,364 nm
(at 911°C)
α-iron
face centered-cubic (fcc)
lattice constant a=286 nm
(at roomtemperatur)
Page 13
FACH
HOCHSCHULE Metastable Fe-C-Diagram
LÜBECK
Page 14
FACH
HOCHSCHULE Fe-Fe3C-diagram
LÜBECK
Reaction C-content wt%
Austenite: γ-Fe (fcc) max. 2,06 at 1147°C
Ferrite: α-Fe (bcc) max. 0,8 at 723°C
Cementite: Fe3C 6,67
Secondary cementite:foms because of the decreasing

6,67
C-solubility in the γ-mixed crystal
Tertiary cementite: foms because of the decreasing C-

6,67
solubility in the α -mixed crystal
Page 15
5
FACH
HOCHSCHULE Microstructures of C-steels
LÜBECK
Page 16
FACH
HOCHSCHULE Armco-Iron
LÜBECK
α-Iron
Page 17
FACH
HOCHSCHULE C15 N (normalised)
LÜBECK
α-solid solution (bright) + pearlite (dark)

Page 18
6
FACH
LÜBECK

Page 19
FACH
LÜBECK

Page 20
FACH
HOCHSCHULE Influence of the cooling rate
LÜBECK
Page 21
7
FACH
HOCHSCHULE Isothermal TTT-diagram for Ck45
LÜBECK
Page 22
FACH
HOCHSCHULE Continuous TTT-diagram
LÜBECK
Page 23
FACH
HOCHSCHULE Martensite Formation
LÜBECK
Diffusionless transformation
Allotropic modifications
Fe: fcc – bcc
Critical quenching rate
Page 24
8
FACH
HOCHSCHULE Influence of the alloyelements on
LÜBECK
the martensite temperature
MS = 550 - 350% C - 40% Mn - 35% V

- 20% Cr - 17% Ni - 10% Mo - 10% Cu
- 5% W + 30% Al + 15% Co
All elements in percent by weight
Page 25
FACH
HOCHSCHULE Pearlite
LÜBECK
Page 26
FACH
HOCHSCHULE 15 CrNi 6 (annealed)
LÜBECK
annealed microstructure with spherical Cementite

Page 27
9
FACH
HOCHSCHULE
LÜBECK
15 CrNi 6 (hardened)
hardened microstructure (Martensite, Bainite)

Page 28
FACH
HOCHSCHULE Influence of the alloying elements on the
LÜBECK
microstructure
According to their effect on the microstructure you distinguish between:

- elements that can be found elemental (e.g. Pb, Cu)
- ferrite forming elements (Cr, Al, Ti, Ta, Si, Mo, V, W)
- austenite forming elements (Ni, C, Co, Mn, N)
- Elements, which have the tendency to form intermediate compounds
carbide forming elements: Mn, Cr, Mo, W, Ta, V, Nb, Ti
nitride forming elements: Al, Cr, Zr, Nb, Ti, V
Page 29
FACH
HOCHSCHULE Influence of the alloying elements I
LÜBECK
Al: fine grain, forms nitrides

C: increases the hardness potential (max. achievable hardness)
Co: increases high temperature strength
Cr: increases the effective hardening depth, forms carbides, high corrosion
resistance Cr ≥ 13%
Mg: enables the formation of spherical graphite in cast iron
Mn: increases the hardening depth, binds sulphur
Mo: decreases the sensitivity to pitting, forms carbides, increases high
temperature strength
Page 30
10
FACH
HOCHSCHULE Influence of the alloying elements II
LÜBECK
Ni: increases toughness, stabilises austenite

Si: increases strength and wear resistance, increases the elastic
limit, promotes the formation of graphite (cast iron)
Ti: stabiliser in corrosion resistant steels
V: forms carbides, increases the elastic limit in spring steels
W: increases high temperature strength and wear resistance (forms
carbides), used in high-speed steels and hot-work steel
Page 31
FACH
HOCHSCHULE Influence of impurities
LÜBECK
N: embrittlement by precipitations (nitrides), sensitive to ageing

P: temper embrittlement (phosphor accumulates at the grain
boundaries between 350 and 600°C)
S: Fe-S leads to so-called. “red shortness“ (Fe-S at the grain
boundaries decreases plasticity during deformation at 800 to 900°C)
H: hydrogen-embrittlement (moisture during welding)
Page 32
FACH
HOCHSCHULE Influence of the alloyelements
LÜBECK
Page 33
11
FACH
HOCHSCHULE Jominy Quenching Test
LÜBECK
zunehmende
Abkühlge-
schwindigkeit
Page 34
FACH
HOCHSCHULE Hardenability of steel
LÜBECK
Hardeness potential: maximal achievable hardness (dependent

on the C-contend)
Hardening depth: achievable hardness depth (dependent on
additional alloying elements, particularly Cr)
hardness alloyelements
high-alloyed steel
low-alloyed steel
unalloyed steel
distance from the surface
Page 35
FACH
HOCHSCHULE Hardenability of Steel
LÜBECK
Hardened in
• Water 60
c) x40Cr13
hardness in HRC
50
• Oil
40
• Air
30 b) 40Cr4
20
a) C45
10
0 10 20 30 40 50 60 70 80
distance from the front surface
Page 36
12
FACH
HOCHSCHULE Hardening Depth
LÜBECK
The critical cooling rate decreases with increasing content of

alloyelements. A quenchant with a lower severity of quenching is
sufficient to form martensite.
a) unalloyed steel,
quenched in water
b) low-alloyed steel,
quenched in oil
c) high-alloyed steel,
quenched in air
Page 37
FACH
HOCHSCHULE Limitations of Ferrous Alloys
LÜBECK
1) Relatively high density

2) Relatively low conductivity
3) Poor corrosion resistance
Page 38
FACH
HOCHSCHULE Nonferrous Alloys
LÜBECK
• Cu Alloys • Al Alloys
Brass: Zn is subst. impurity -lower ρ: 2.7g/cm3
(costume jewelry, coins, -Cu, Mg, Si, Mn, Zn additions
corrosion resistant) -solid sol. or precip.
Bronze : Sn, Al, Si, Ni are strengthened (struct.
subst. impurity aircraft parts
(bushings, landing & packaging)
gear) NonFerrous • Mg Alloys
Cu-Be : -very low ρ: 1.7g/cm3
precip. hardened Alloys -ignites easily
for strength -aircraft, missiles
• Ti Alloys
-lower ρ: 4.5g/cm3 • Refractory metals
-high melting T
vs 7.9 for steel • Noble metals -Nb, Mo, W, Ta
-reactive at high T -Ag, Au, Pt
-space applic. -oxid./corr. resistant
Page 39
13
FACH
HOCHSCHULE Aluminium
LÜBECK
• Discovery: 1808 durch Sir Humphry Davy

• Melting point: 660,37°C
• Density: 2,702 g/cm3
• Crystal lattice: fcc
• el. conductivity: 237 MS/m
• heat conductivity: 237 W/mK
• el. Potential: -1,662 V
Page 40
FACH
HOCHSCHULE Aluminium Alloys
LÜBECK
miscellaneous
Transport 25 %
26 %
Electricity
9%
Construction
20 %
Packing
20 %
Page 41
FACH
LÜBECK
Applications wrought alloys

further processing by rolling, extrusion, pulling into semi-finished parts
shipbuilding: superstructures: AlMgMn

self-supporting spherical tanks: AlMg4,5Mn plates up to 75 mm thick
boatbuilding: mast for sailboats (replaced wood totally)
Automotive: sheets - extrusions:

AlMgMn – aged, AlMgSi – non aged, AlMg, AlCuMg
Page 42
14
FACH
LÜBECK
Applications automotive body shell
Audi A8 from 1994 to 2002
delta-transverse
control arm
6110A-T6
2,4kg
Page 43
FACH
LÜBECK
Applications aircraft construction Boeing 777
Page 44
FACH
LÜBECK
Applications aircraft construction A340 (65% Al-alloys)
fuselage: 2025-T3
plated Al/not weldable
Stringer in the body:
7150-T6
body structure:
AlMgSiCu
AlMgLi
AlMgSc
weldable
Page 45
15
FACH
LÜBECK
Applications aircraft construction A340

half of an aircraft wheel
2214-T6
60kg
window frame
7175-T74
1,1kg
Page 46
FACH
LÜBECK
Applications extruded profiles
Capalex extrudes a lot of Otto Fuchs extruded profiles for

different extrusion alloys building industry and engineering
e.g:1050, 2014, 2024,
3003, 5083, 6005, 6060, 6061,
6063,
6082,
6463,
7075
Page 47
FACH
LÜBECK
Applications train construction

ICE trailer made by extruded profiles
AlZn4,5Mg1 and AlMgSi0,7 (profiles)
AlMg4,5Mn and AlMgMn0,8 (sheets)
Page 48
16
FACH
LÜBECK
Applications structural material in the building industry

sheets and belts AlMn1Mg0,5 not age-hadenable
windows and profiles AlMgSi0,5 age-hardenable
Page 49
FACH
LÜBECK
Applications packing industry
maximum performance by minimum material

usage (foils 6 ... 200 µm)
Page 50
FACH
LÜBECK
further applications
Aluminothermy: welding of rails,

reduction of chrome and vanadium
4 Al + 3 O2 2 Al2O3 ΔHR = 3352 kJ/mol
powder metallurgical production of aluminium high performance materials

• Oxide Dispersion Strengthened ODS
milling of Aluminium and Graphite in ball mills, production of Al2O3 und Al4C3,
the material has a better high temperature performance, application: e.g. pistons
• spray forming
the aluminium melt is sprayed by an nitrogen yet under vacuum, fast cooling, low
grain size, high over saturation and new alloying-systems possible,
application: e.g. cylinder liner
Page 51
17
FACH
LÜBECK
Primary processing - Bauxite

• named after the French town Les Baux, Provence
• product of the weathering of aluminium silicate stones,
• composition has a wide range:

- Al2O3 - Hydrargilit, Böhmit, Diaspor, Corund 46 - 66%
- silicic acid 1 - 7%
- iron oxide – red colour 2 - 25%
- titanium oxide 2 - 3%
• 90 % of the Bauxite is found in the tropes
• open pit mining, because of the low strength it can be mined without explosions
• further processing mostly in the industrialised countries because of the low

transportation costs, as the aluminium consumption
Page 52
FACH
LÜBECK
Primary extraction Bauxite [Al(OH)3, Al2O3, AlOOH]
Main processing steps: H2O

• refining of the Bauxite cracking, milling
• reduction to Alumina
• electrolysis dissolve
NaOH [NaAl(OH)4]
removal of solids red mud
precipitation
Al[OH]3
exhaust gas
energy, carbon calcination
(H2O)
[Al2O3]
energy, carbon electrolysis
[Al]
Page 53
FACH
LÜBECK
Primary processing – refining of the bauxite

decomposition Bauxite caustic soda
in an autoclave
or in a autoclave
pipe reactor
mixer
thickener
red mud
roaster
Filter
stirrer aluminium oxide
Page 54
18
FACH
HOCHSCHULE
LÜBECK

• Bayer Process: dissolve, removal of red mud, precipitation
• dissolve the bauxite in hot caustic soda with the addition of lime
n[Na2O]
K= ≈ 1,35
NaOH + Al(OH)3 → Na + Al(OH) + − n[ Al3O3 ]
4
Caustic behaviour
behaviour of concomitant elements during

leaching:
Fe precipitation red mud
SiO2 precipitation red mud
TiO2 precipitation red mud
Ga accumulation circulation, extraction
V accumulation circulation, extraction
Page 55
FACH
LÜBECK

• moving of the balance by caustic to prevent decomposition of Al2O3
• removal of the red mud - 40% water, rest: insoluble components, dumping
1-2 t wet mud / t processed alumina
n[Na2O]
K= ≈ 1,7
autoclave
n[Al3O3 ]
red mud
thickener
Page 56
FACH
LÜBECK
Primary processing – refining of the Bauxite

•Solution is changed to supersaturated by cooling to 55-75°C, Al(OH)4- solved as
Al(OH)3* x H2O
Aluminiumhydroxide and 10-16% water in the crystal is precipitated
•Al(OH)3 is added to the supersaturated solution – reused material
• causticity is increased by removal of Al2O3 process is uneconomic from 3,3 - 3,6
NaOH+ Al(OH)3 ← Na+ + Al(OH)−4

From thickener Caustic soda
Filter To calcination
Mixer
Page 57
19
FACH
LÜBECK
Primary processing – reduction to Alumina

• calcination in a rotary furnace or in a fluidised bed furnace
• Temperature 1200-1300°C
• Usage for processing to Aluminium or as fireproof material
- melting temperature: 2053°C
2 Al(OH)3 + xH2O + Energy→ Al2O3 + (3 + x)H2O3
Al(OH)3 + xH2O
Al2O3
electrolysis
Page 58
FACH
LÜBECK
Primary processing - electrolysis

• Anodes and clipping made from carbon, conductor from iron
• processing temperature 950-970°C
• Electrolyte: Cryolite - Na3AlF6
• 0,5kg coal / 1kg Al
• 4kg Bauxite / 2kg Alumina / 1kg Al
• 15 kWh / kg Al – overall process
Page 59
FACH
LÜBECK
Further processing
• continuous casting
• Nearly no diffusion in the solid, therefore high
concentration gradients and segregations
Page 60
20
FACH
LÜBECK
Further processing
• tempering of the ingots: reduction of the stresses and the segregations
• hot forming: - rolling:
hot rolling to starting thickness, then hot rolling to the
finished dimensions hot rolling at 400-540°C, during
cooling and reheating normally recrystallisation
- extrusion moulding: 520-540°C
• cooling: slow - fast
• solution annealing: for age hardenable alloys 450°C-540°C, following
cooling with 0,3-500 K/s
• cold forming: rolling etc.
• age hardening: - natural aging: RT, a few days
- artificial aging: up to 200°C, up to approx. 20h
Page 61
FACH
LÜBECK
In general you distinguish between
Cast alloys: • good filling of the mould and good castability required
• relative high alloy element contents 10-12%
• applications: cast engine parts, rims, door handles, Pans,
etc.
Wrought alloys: • deformation capability important
• relative low alloy element contends 1-2%, up to 6-8%,,
• applications: plates, cans, foils, extruded profiles, etc.
Age hardenable: Final strength is reached by precipitations

(highest increase in strength)
Non age hardenable: Final strength is reached by cold forming, decreases

deformation capability
Some casting alloys are also age hardenable, but the denotation is normally for
Wrought alloys.
Page 62
FACH
LÜBECK
Al Fe Si
Fe
Al Mg
Al Si Non age
Si
harden-
Si Al Si Al Mn able
Al Mg Mn Al Mg Mn
Mg Al Si Cu Al Zn
Al Mg
Al Al Si Mg Al Mg Si
Zn Al Mg Si Zn Al Cu (Si, Mn)
Al Cu Mg Age-
Al Cu
Cu Al Zn Mg harden-
Cu Al Zn Mg able
Al Zn Mg Cu
wrought
Li
Casting alloys Al Cu (Mg) Li
alloys
Page 63
21
FACH
LÜBECK
international used nomenclature

Introduced by the Aluminium Association USA
denotation main alloying element
1XXX unalloyed
2XXX Cu
3XXX Mn
4XXX Si
5XXX Mg
6XXX Mg und Si
7XXX Zn
8XXX other, e.g. Li
9XXX unusual
Page 64
FACH
LÜBECK
The technical Aluminium alloys are designated in the following way

1xxx: pure aluminium (99% Al)
Age hardenable, high strength
2xxx: Al + Cu + Mg
Aircraft industry
Non age hardenable, corrosion resistant
3xxx: Al + Mn
Railway industry
Non age hardenable, low thermal expansion
4xxx: Al + Si
coefficient
Non age hardenable, corrosion resistant, weldable
5xxx: Al + 4% Mg Automotive industry, ship building, household
Age hardenable, medium strength
6xxx: Al + Mg + Cu + Si
Furniture industry, ladders
Age hardenable, very high strength
7xxx: Al + Zn + Mg + Cu
Laboratory alloys, aircraft industry
Age hardenable, light weight, relative brittle
8xxx: Al + Li + Mg + Cu
Aircraft industry
Dispersion hardened, high strength
9xxx: powder metallurgy
Aircraft industry
Page 65
FACH
LÜBECK
Age hardenable and non age hardenable alloys
• increase in strength in Al-alloys is possible in five different mechanisms:

- Strengthening by deformation
- Solid solution strengthening
- Age hardening
- Grain refinement
- Dispersion hardening or particle hardening
• requirements for age hardening:

- significant solubility during homogenisation for the component that should be
precipitated
- decreasing solubility with decreasing temperature - sufficient driving force
- and sufficient diffusion speed
• non age hardenable:

- no precipitations possible
- In general lower strength compared to age hardenable alloys
Page 66
22
FACH
LÜBECK
Strengthening of an alloy by coherent an semi coherent particles
1 - solution annealing: if
possible, complete solution in
the solid solution of the
component which should be
precipitated Θ
2 - quenching: creation of an
unbalanced condition to create
a driving force Cu
3 - age hardening: particles of
a meta stabile phase
precipitates
a) Phase diagram
b) Temperature-time-curve
c) Strength over time
Page 67
FACH
LÜBECK
Age hardening: phases and interfaces
interface Coherent semi coherent incoherent
Every crystal plane A few crystal planes No continuous

Miss fitting
is continued are continued planes
Lattice structure, Different lattice Different lattice

reason Lattice parameters parameters structure or
Same orientation orientation
Page 68
FACH
LÜBECK
hardening:
dislocations and particles
• incoherent particles
- Interface can’t be passed -
only by-passing Dislocation
• coherent and semicoherent

Dislocation-
particles, as in hardening by ring
precipitation,
cutting and by-passing
• by-passing
„Orowan-Mechanism “
• cutting
„Kelly-Fine-Mechanism“
Page 69
23
FACH
HOCHSCHULE Copper
LÜBECK
Discovery: in use since at least 6000 B.C.

probably the oldest used Metal,
Melting point: 1083°C

Density: 8,9 g/cm3
Thermal conductivity: 393 W/mK only Ag is better
Electrical conductivity: 58 MS/m only Ag is better
el. Potential: positive noble metal
Page 70
FACH
HOCHSCHULE Copper Alloys
LÜBECK
miscellaneous
transportation 7%
8%
building industry
39%
electrical industry
37%
mechanical engineering
9%
Page 71
FACH
LÜBECK
other applications
chemical industry: approx. 2 %
• production of fertiliser,
small amounts of copper sulphate are lethal for algae, bacteria etc.
Fungicide for seeds and pest control in winegrowing
• galvanic copperplating
• production of blue pigments
• blue colour in fireworks
Page 72
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FACH
LÜBECK
Ore mining:
• in open pit as in underground mining
• mainly in Chile and USA
Raw material:
• Chalcopyrite - CuFeS2
• the ore contains only approx 0.5-1% Copper
• with Flotation concentrated to 30%
• the concentrate consists of equal fractions of
copper, iron and sulphur
Processing:
• oxide ore: hydrometallurgical, world wide: approx. 15-20%
• sulphide ore: pyro metallurgical
Page 73
FACH
LÜBECK
Pyro-metallurgy
concentrate (25-35% Cu)
drying
exhaust gas (SO2)
flux slag
air (O2) melting slag cleaning
(0,5-1% Cu)
copper matte (60-70% Cu)
scrap converter exhaust gas (SO2)

blister copper (98-99% Cu)
scrap pyro. refinement exhaust gas (SO2)
anodic copper (99-99,8% Cu)
electrolysis Au, Ag, Pt etc.
cathodic copper (>99,99% Cu)

Page 74
FACH
LÜBECK
Melting: CuFeS 2 + O 2
→ ( xCu − Fe − S ) + FeO + ySO 2
• Oxidation/removal of a part
of the Fe and S
concentrate (25-35% Cu),
• mostly in a hot gas and flux
flash smelting furnace
• reaction heavily exothermal
exhaust gas (SO2)
• SO2 to produce H2SO4
1800°C
• slag with up to 5 % Cu
cleaned in ELBO
slag cleaning
copper matte (60-70% Cu) slag (0,5-1% Cu)
Page 75
25
FACH
LÜBECK
Converter - 1.step: 2FeS+ 3O2 ⇔ 2FeO+ 2SO2
• copper matte - CuS2+FeS 2FeO+ SiO2 ⇔ Fe2SiO4

is mixed with air
• purpose: longest distance between

S and Fe copper matte (60-70% Cu)
• 1. step: removal of the iron exhaust
gas (SO2)
- reaction is heavily exothermal
– scrap for cooling slag
- slag from the 2. converter step (15% Cu) air
- SO2 for production of H2SO4
Blister Kupfer (98-99% Cu)
Page 76
FACH
LÜBECK
Converter - 2.step:
2Cu 2 O + Cu 2 S ⇔ 6 Cu + SO 2
• purpose: removal of S 2Cu 2 S + 3 O 2 ⇔ 2Cu 2 O + 2SO 2
• metallic phase for the first time
copper matte (60-70% Cu)
• separates from the copper matte
because of the higher density exhaust
gas (SO2)
• copper slags strongly
slag
slag has a Cu-content of 15%,
air
back to 1. step
• remaining content of S and O

Blister copper (98-99% Cu)
are below the solubility,
blisters during solidification – Blister copper
Page 77
FACH
LÜBECK
Peirce-Smith-Converter
Page 78
26
FACH
LÜBECK
pyrometallurgical refinement – anodic oven

blister copper (98-99% Cu)
• O2-content raised to 0.8-1% by blowing air into
exhaust gas (SO2)
• Oxidation of ignoble metals – e.g. Fe, Zn, Pb possibly S
natural gas
• removal of the oxides with the slag made from SiO2
• O2-contant has do be reduced for electrolysis,
blowing reducing gases into the melt e.g. natural gas
O2 reacts to CO or H2O
casting wheel
Anodes
Page 79
FACH
LÜBECK
Reactions in the anodic oven

1. period 2. period
O2 ⇔ 2OCu C3H8 ⇔ 3C + 8HCu
2Cu + OCu ⇔ Cu2O 2HCu + OCu ⇔ H2O
OCu + (Pb, Fe, Zn)Cu ⇔ [(Pb, Fe, Zn)O]slag C + OCu ⇔ CO
2OCu + SCu ⇔ SO2 CO+ OCu ⇔ CO2
Cu2OCu + (Pb, Fe, Zn)Cu ⇔ 2Cu + [(Pb, Fe, Zn)O]slag
Blister copper (98-99% Cu)

exhaust gas (SO2)
scrap pyro. refinement
Page 80
FACH
LÜBECK
refinement electrolysis:
• purity changed from >99% to 99,99%

for el. applications
• removal of Bi, Co, Ni, Pb, S, Sb, Sn, Se, Te
• Electrolyte: CuSO4-H2SO4-H2O + X
• ignoble elements: accumulation in the electrolyte
- difficult to remove - and anodic mud
• extraction of Ag, Au, Pt from the anodic mud,
approx. 0,25 Mio €/t
electrolysis Au, Ag, Pt etc.
cathodic copper (>99,99% Cu)

Page 81
27
FACH
LÜBECK
Refinement electrolysis: Cu 2+
+ 2 e − ⇔ Cu kathode
0
2+
0
Cu anode ⇔ Cu + 2e −
voltage 2V
direct current 10.000 A
Page 82
FACH
LÜBECK
further processing methods
miscellaneous
art casting 10%
2% Sand casting
38%
continuous casting centrifugal casting

47% 3%
Page 83
FACH
LÜBECK
Copper – corrosion resistance
• usage in roof building

also as a status symbol
• even oxide layer protects

against corrosion
• green patina develops after a few years
4 Cu + O2 2 Cu2O (copper(I)-oxide) – dark red
2 Cu + O2 2 CuO (copper(II)-oxide) - black
2 Cu + CO2 + H2O + O2 CuCO3. Cu(OH)2 – blue-green
Page 84
28
FACH
LÜBECK
Example: pressure vessel made from SF-Cu – oxygen free and reduced
with phosphor – on both sides WIG-welded
Page 85
FACH
HOCHSCHULE
LÜBECK
Copper alloys overview
• CuZn - brass
• Cu Al - Aluminium bronze
• CuSn – tin bronze
• Cu-Ni - Cupronickel
the most copper alloys are not age hardenable, no decreasing solubility
with appropriate diffusion speed
strengthening by
deformation hardening or
solid solution hardening
exception: Cr, Co, Be

age hardenable with Be (1,6-2,1 weight.%) strength about 1400 N/mm2
used for paramagnetic parts or spark-free tools
Page 86
FACH
LÜBECK
Copper-zinc-alloys (brass)
• technical most important group of the copper materials
• 5 to 50% Zn, min. 50% Cu,

up to 30% Zn also „Tombak“ from Malay „Tambaga“ for copper
• strength increases with increasing zinc content,

max. 600 MPa for approx. 45 weight.% Zn
• Application: armatures in ship building and plumbing trade
• Nickel silver is a formerly often used alloy with 45-67 % Cu, 10-29 % Ni,
rest Zn, today mostly replaced by stainless steels
Page 87
29
FACH
LÜBECK
Copper-zinc-alloys
α fcc, up to 35% Zn,

little stressed parts
α+β 37,5-46 weight% Zn,

β-phase: intermetallic fcc,
strength increases with
β-content
β 46-50 weight% Zn
technical not relevant,
γ embrittles and is therefore

avoided
Page 88
FACH
LÜBECK
Copper-zinc-alloys – alloying elements
• distinction between chip brass - with Pb - and special brasses -

with Al, Mn, Fe, Sn, Si Ni
• Pb insoluble in Cu Zn-alloys, improves the brittleness of the swarf, often

used in alloys for machining: CuZn36Pb3 classical material for automatic
lathe
• Al, Fe, Sn: improves the strength
• Al, Ni: improves the corrosion behaviour
• Mn, Fe: with Al, Si for improving the wear and gliding properties
• Al, Sn: moves the α/ α +β phase border to higher Cu-contents
Page 89
FACH
LÜBECK
Examples: Decorative parts made from α-Messing

or Nickel Silver by cold deformation
Page 90
30
FACH
LÜBECK
Copper-tin-alloys
(bronze or tin bronze)
• alloys often with 8,5-12 % Sn,

up to 20 % bell-founding
• slow diffusion: transformation

α+δ α+ε only after long
annealing treatment
• cold deformation requires

homogenisation to get rid of the
segregations
• δ-phase is hard and brittle, used to

influence the probabilities
Page 91
FACH
LÜBECK
Copper-tin-alloys
• high corrosion resistance, many alloys are resistant

to seawater, distinguish between wrought and
casting alloys
• wrought alloys: up do 8.5% tin, good el. conductivity

- not as good as copper,
used for: plug connector, stamping part, electronic
parts, slide bearing and springs
• casting alloys: 9-13% tin, protective effect increases

with Sn-content, bronze for bells: 20%,
used for: slide bearings, valve housings, impellers,
fittings and piston rod
Page 92
FACH
LÜBECK
Copper-tin-alloys – alloying elements

Pb: in solid state nearly no solubility,
decreases machinability and hot-deformability,
improves gliding properties – material for bearings
Zn: Reduction of the melt,

moves the α-phase boundaries to lower tin-contents,
narrows the solidification interval
P: Reduction of the melt,

improves the castability,
enlarges the solidification interval
Ni: increases the melting point

moves the α-phase boundary to lower tin-contents,
improves strength and corrosion properties
Page 93
31
FACH
LÜBECK
Copper-aluminium-alloys (aluminium bronze)

• 9.4% max. solubility for Al,
only reachable by slow cooling
and a homogenisation,
7.4-7.8 % for sand and chill casting
• β α+γ2 by slow cooling

α+γ2 decreases the strain,
fast cooling in practice,
fast emptying of the mould in
sand casting
• Fe- and Ni-containing alloys
age hardenable, annealing in the
β-region, quenching, aging
Page 94
FACH
LÜBECK
Copper-aluminium-alloys
Example:
Propeller made of
aluminium bronze
Page 95
FACH
LÜBECK
Copper-beryllium casting alloy

• hardenable if more than 0.2% Be
casting alloys up to approx. 3%
• for chemical industry,

polymer press moulds
and spark free tools
e.g. in mining,
• toxic Be-vapours during casting

cause ague and
other poisoning symptoms,
Beryllose
gas offtake and breathing protection
Page 96
32
FACH
LÜBECK
Copper-nickel-alloys
• alloys with 10-30 % Ni
• complete solubility of Cu and

Ni in the solid and melt
• application of binary alloys

mostly as material for
coins
• alloys are partly ferromagnetic,

Curie temperature nearly linear
dependent on the Ni-content
Page 97
FACH
LÜBECK
Copper-Nickel-alloys
• alloys with up to 40-50% Ni
very high el. resistivity of CuNi44, application for
electrical resistors
• high thermal electromotive force, used for thermocouples
• 1, 2, 5 EURO-Cent: with Cu roll-plated steel

10, 20, 50 EURO-Cent: Nordic Gold - CuAl5Zn5Sn
1 EURO-coin: ring: Nickel-brass,
core: CuNi25 / Ni / CuNi25
1 EURO-coin: ring: copper-nickel,
core: CuZn20Ni5 / Ni / CuZn20Ni5
Page 98
FACH
LÜBECK
Copper-nickel-alloys – corrosion resistance
example:
Sea water cooling system
on a „Off-Shore“-platform
made of the sea water
resistant
CuNi10Fe1Mn
Page 99
33
FACH
LÜBECK
Page 100
FACH
LÜBECK
Page 101
FACH
HOCHSCHULE Magnesium Alloys
LÜBECK
Materials Week 1927
Page 102
34
FACH
LÜBECK
Mg-cast parts, VW 1500
source: Automotive Light Metals
Page 103
FACH
LÜBECK
Properties of Magnesium
Advantages: Disadvantages:
• high specific strength • limited corrosion
(density: ∼1.8g/cm3) properties
• good castability • low high-temperature
properties
• good workability
• low deformability
• nearly unlimited available
(hexagonal
• recyclable crystallstructure)
Page 104
FACH
LÜBECK
Page 105
35
FACH
LÜBECK
• Casting
- High pressure casting (AZ, AS, AE, AM)
- Gravity casting (AZ, K, ZK, ZE, EZ, QE, WE)
- Squeeze casting (AZ, AS, AE, AM, K, ZK, ZE, EZ, QE)
- Thixo casting (AZ, AS, AE, AM)
• Extrusion (AZ31, AZ61, AZ80, WE54, WE43)
• Rolling (AZ31, HK31, HM21, ZK60)
• Forging (AZ31, AZ60, AZ80, ZK)
• Joining
Page 106
FACH
LÜBECK
Slip systems of magnesium
(0002) Basal planes, (10-11) Pyramidal planes

normal temperature slip (first order), high temperature
slip
(10-12) Pyramidal planes (10-10) prismatic planes

(second order), principal twin planes high temperature slip
Page 107
FACH
LÜBECK
High Pressure Die Casting (HPDC) of Mg-alloys

hydraulic closing
unit
hot chamber die casting
die
casting piston
intake
casting cylinder
melt
Page 108
36
FACH
LÜBECK
High Pressure Die Casting (HPDC) of Mg-alloys
hydraulic closing unit

cold chamber die casting
die
casting piston
casting cylinder
Page 109
FACH
LÜBECK
Typical Physical Properties
Property Unit Temp. AZ91 AM60 AM50 AM20 AS41 AS21 AE42
Density g/cm3 20 1.81 1.80 1.77 1.75 1.77 1.76 1.79
Liquids temp. ´C 598 615 620 638 617 632 625
Incipient melting t. ´C 420-435 (420-435) (590)
Lin. thermal. exp.c.µm/(m·K) 20-100 26.0 26.0 26.0 26.0 26.1 26.1 26.1
Sp. heat of fusion kJ/kg 370 370 370 370 370 370 370
Specific heat kJ/kgK 20 1.02 1.02 1.02 1.02 1.02 1.02 1,02
Thermal conduct. W/K m 20 51 61 65 94 68 84 84
Electrical cond. MS/m 20 6.6 nm 9.1 13.1 nm 10.8 11.7
nm: not measured Expected values (not proved) in brackets
Page 110
FACH
LÜBECK
Magnesium – extruded material

Influence of the alloy
•alloy development
Properties of the material
•Thermomechanical induced
changes in the microstructure
•correlation between microstructure
and mechanical properties
•influence of the process parameters
Production of structural parts
Quality management
© Otto Fuchs Metallwerke

Page 111
37
FACH
LÜBECK
extruded profiles: inhomogeneous microstructure
10µm 10µm
cross section
longitudinal direction
10µm
Page 112
FACH
LÜBECK
Microstructural development during extrusion
indirect extruded
AZ31 AZ61 AZ80
hydrostatic extruded
J. Swiostek (Sp), J. Bohlen, D. Letzig, K.U. Kainer, In: K.U. Kainer (Ed.) „Magnesium Alloys and Their
Applications IV”, Wiley-VCH, Weinheim 2003, ISBN 3527-30975-6
Page 113
FACH
LÜBECK
Mechanical Properties of Commercial Magnesium Alloys
Page 114
38
FACH
LÜBECK
Corrosion Prevention Strategies - Decrease of Impurities

10 Corrosion rates (ASTM B117)
Corrosion rate [mm/y]
0
AZ91 AM60 AM50 AM20 AA 4250 AZ91
HP HP HP HP conv.
Corrosion rates of various Mg high purity alloys measured in 240 h salt spray test
(ASTM B117) compared with aluminium alloy AA 4250 and conventional AZ91.
Hydro Magnesium 2000
Page 115
FACH
LÜBECK
Automotive parts
Page 116
FACH
LÜBECK
Inner door frame (Mercedes-Benz SL)
source: Hydro Magnesium

Page 117
39
FACH
LÜBECK
Air intake manifold (BMW V12-engine)
source: Hydro Magnesium

Page 118
FACH
LÜBECK
Steering wheel of the S-Type JaguarZ
source: Automotive Sourcing

Page 119
FACH
LÜBECK
Mg cylinder block with Al cylinder bushings
source: BMW AG
Page 120
40
FACH
LÜBECK
Page 121
FACH
LÜBECK
Page 122
FACH
LÜBECK
Page 123
41
FACH
LÜBECK
Page 124
FACH
LÜBECK
Page 125
FACH
HOCHSCHULE Nickel
LÜBECK
• Density: 8,91 g/cm3, heavy metal

• Structure: fcc
• Melting point: 1455°C
• Magnetism: ferromagnetic
• El. potential: -0,25 V, ignoble
Page 126
42
FACH
HOCHSCHULE Nickel Alloys
LÜBECK
miscellaneous,
incl. chemical
5% non iron alloys 12 %
alloying of
steels
10 %
electro plating alloying of

8% stainless steal
65 %
Page 127
FACH
LÜBECK
Miscellaneous:
• fine distributed Ni can absorb 17 time his on volume of hydrogen,
used as a catalyst for the hydration of oil
• production of NiCd- and NiMH batteries
• deposit: - at 21. place of the elements in the earth’s crust, 0.015%,

- more often as Zn and Cu,
- the core of the earth consists of Fe, Si, O, S und 5% Ni
• over 50mg of nickel and nickel compounds are toxic,

chronic damages, can be lethal,
demonstrably cancer producing
in contact Nickel allergy possible
Page 128
FACH
LÜBECK
Ore mining
• mostly in Canada, Zimbabwe, Russia
and Australia
• open pit and underground mining
Raw materials
• sulphured: at the time the main raw material silver swan nickel mine, HWE, Australia
mixture of Fe-, Cu- and Ni-ores
Pyrrhotit (Fe7S8), Pentlandit [(Ni,Fe)S8], and Chalcopyrite (CuFeS2)
• oxide: mostly Peridotit and Serpentin
• Ni content: 0,8-3 % in the ore
further processing
• production of a concentrate
• sulphured ores: pyro metallurgical, extraction of Cu, Co, Fe, Au
• oxide ores: hydro-, o. pyro metallurgical – depends on the Ni-content
Page 129
43
FACH
LÜBECK
Production of the sulphured concentrate
• combined conditioning by magnetic separation

and or flotation
• several possibilities depending on the metal
content and the further metallurgical processing:
- Pentlandite (Ni), Chalcopyrite (Cu) u.
Pyrrhotit (Fe) each separate
- Pentlandite together with Pyrrhotit
- Pentlandite together with Chalcopyrite
• often used procedure:
- separation of the Pyrrhotite, if enough Fe
- separation of Pentlandit and Chalcopyrite
and separated further processing
• further processing can differ a lot
Page 130
FACH
LÜBECK
Pyro-metallurgy of the sulphured Ni-ores

conzentrate (5-15 % Ni)
air Roasting SO2 separation of the Fe bonded S
SiO2 Melting SO2 separation of gangue - stone - and Fe

matte (ca. 10 % Ni)
Convert SO2 remaining is Fe oxidised and removed with

the slag
converter stone (15-45 % Ni)
separation of nickel sulphide und
separation
copper sulphide
ca. 75 % Ni
Electrolysis Mond-Process
99,5 % Ni 99,9 % Ni
Page 131
FACH
LÜBECK
Electrolysis
Ni3S2 3Ni + 2S
• sulphur remains as anodic mud
Mond- or Carbonyl process

• formation of Carbonyl from Ni, Fe, Co etc. at 40-80°C in contact with CO
Ni + 4CO Ni(CO)4
• reaction to Nickel and CO at 200°C

Ni(CO)4 Ni+4CO
• separation of the other carbonyls by control of the catalysts
Page 132
44
FACH
LÜBECK
Ni-wrought alloys
• very low alloying element contents < 1 %
• corrosion resistance is the most important issue
Ni-wrought alloys wit Mo,Cr and Co

• 40-60% Ni
• used as corrosion resistant bars, tubes and sheets
Ni-Mn-alloys
• alloying element content up to 1 – 5.5 % Mn
• NiMn3Al as negative part of the thermocouple
• NiMn1 for electroacoustical parts
Page 133
FACH
LÜBECK
Ni-Cu-alloys
• 25-35 % Cu
• very good corrosion resistance
resistance to heat is good, but
not as good as for pure Ni
and NiFe
• applications: ship technology,
turbine construction,
chemical industry, valves,
pumps, heat exchangers
• „Monel“: 65% Ni, 33% Cu, 2% Fe,
very corrosion resistant in many
acids and bases
• „Constantan“: 55% Cu, 45 % Ni, nearly constant el. resistivity over T
Page 134
FACH
LÜBECK
Superalloys
• developed for: - temperatures above 600°C to 1150°C
- simultaneously high stress
- high corrosion and oxidation resistance
• application: turbine blades, furnace chamber wall, furnace parts,
high temperature-processing plants, heat shieldings
• processing: forging, casting
or powder metallurgy
• basis metals: Fe, Co u. Ni
• trade names: Hastelloy®, Incoloy®,
Inconel®, Nimonic®,
Monel®, René®,
Patents often expired,
name replaced by „Alloy“
Page 135
45
FACH
LÜBECK
Ni-Base superalloys
• superalloys, which achieved most success
• service temperature ~900-1150°C

with 0,85 highest homologous temperature
of all materials with simultaneously mechanical
and corrosive loading
• over 650° higher strength as high

temperature steels
• fcc solid solution with 12-30% Cr, γ-Phase
• solid solution strengthening in γ-phase by Cr, Co, Fe, Mo, Wo, Ta
• corrosion resistant because of Cr2O3

Page 136
FACH
LÜBECK
Ni-Base superalloys
+ continuous fcc crystal structure up to the melting point,
lower diffusion rates as in the bcc lattice
+ sufficiently high Al- and Cr-contents for the
corrosion protection are possible
+ high volume contents of a second phase for
particle hardening possible up to 70%
+ approx. 210 GPa about the same high Young’s modulus as Co u. Fe
- low melting point of all basis metals, high homologous temperatures

limit the long term service to temperatures below 1150°C
- low thermal conductivity and high thermal elongation,
high sensitivity to thermal fatigue
Page 137
FACH
LÜBECK
Strength of the Ni-superalloys because of γ´-phase, Ni3Al
• γ´- and γ-phase are both fcc, coherent, but the γ´-unit cell is twice as big as the
γ-unit cell, so you need at least two dislocations to deform, temperature resistant
• produces elastic distortion of the lattice
• γ´-volume content: up to 70 % in casting alloys
γ´-unit cell
Ni
γ´-phase
γ -phase
Al
Page 138
46
FACH
LÜBECK
• Annual production: ca. 8 Mio t lower than Fe, Al, Cu, Pb

• El. potential: -0,76 V ignoble than iron
• Density: 7,14 g/cm 3
• Structure: hexagonal
• Melting point: 420°C
• Boiling point: 906°C volatile
• Brinell-hardness: ~370 HB hard
• Ultimate strength (rolled): 120-140 N/mm2 middle
• Ultimate strength (cast): 30-40 N/mm2 low
• Price LME: approx. 1.300 $/t (2005)
Page 139
FACH
HOCHSCHULE Zinc Alloys
LÜBECK
chemicals
8% miscellaneous
5% Zn-alloys
brass
18% 13%
zincing
50%
semi finished parts
6%
Page 140
FACH
LÜBECK
Miscellaneous:
• casting fever: ZnO-vapour during melting or welding, abnormal fatigue,
increased body temperature, shivering,
fades away after a few hours, no permanent damage
• Zincoxide - ZnO, white powder - in salves and powders because of

dehydrating and antiseptic – germ-killing - effect
• ZnO and TiO2 as mineral filter in sun lotions - covering -

in contrast to chemical filters
• usage of ZnO during the vulcanisation of caoutchouc
• at the end of the 19. century ZnO replaced white lead as colour pigment,
today ZnO is replaced by TiO2
Page 141
47
FACH
LÜBECK
Ore mining:
• predominant in Canada, China, Peru and USA
Raw material
• mineral: mostly - 90% - Zinc blende - ZnS
• ore: developed by weathering, galmei
• Zinc content between 5 and 20%
• Zinc ores often in combination with lead ores
• after concentration - flotation:
45-60% Zinc, up to 10% Pb and Fe, 25-30% S
furthermore Cadmium and mercury
further processing
• 90% in a hydrometallurgical way
Page 142
FACH
LÜBECK
Flotation – enrichment of the ore
• separation of ore and gangue with the use of bubbles
• the ore particle attach to the bubbles and can be

collected on the surface
• „frothers“ stabilise the bubbles
• „collectors“ change the ore to hydrophobic or the

gangue to hydrophilic
air
• Flotation is used to concentrate 90 % of all
Cu, Zn, and Pb ores
ore
concentrate
Page 143
FACH
LÜBECK
Hydrometallurgical processing
concentrate (45-60% Cu) roll oxides (62-70% Zn)
air roasting washing

exhaust
waste water
gas(SO2)
H2SO4 leaching
Zn-Fe-Pb residua
Zn-solution (~140g/l Zn)
Zn-dust
CuSO4 1. cleaning
As2O3 Cu-As, Ni, Co etc.
Zn-dust
CuSO4 2. cleaning
Cd, Cu
electrolysis melting
cathodic zinc (>99,99% Zn)

Page 144
48
FACH
LÜBECK
Roasting in a fluidised-bed furnace

• conversion from ZnS in easy to dissolve (in H2SO4) ZnO
• roasting at approx. 900-1000°C, O2 partial pressure 10-1 - 10-2 bar
• reaction is exothermal,
burning of sulphur
• performance can be increased by calcinate
adding O2 exhaust
gas
• reaction temperature can be
controlled by cooling coils concentrate
in the fluidised bed
calcinate
• the time the material remains
in the furnace can be controlled
air
by the amount of air
Page 145
FACH
LÜBECK
Reactions during roasting
Zinc oxide 2ZnS + 3O2 = 2ZnO + 2SO2
bas. Zinc sulphates ZnS + 11O2 = 2ZnO•2ZnSO2 + 2SO2
Zinc sulphate ZnS + 2O2 = 2ZnSO4
Hematite 4FeS + 7O2 = 2Fe2O3 + 4SO2
Magnetite 3FeS + 5O2 = Fe3O4 + 3SO2 desired
Zinc ferrite ZnO + Fe2O3= ZnFe2O4 undesired,

because its non
Zinc silicate 2ZnO + SiO2 = Zn2OSiO4 dissolvable
Page 146
FACH
LÜBECK
Production of the rotate oxides – rotating process

• rotating process: concentration of Zn containing scrap, dust etc. in a
rotary furnace
• residuals and coal together in the rotary furnace at 1200°C, no

further firing required
• Zinc vaporises at TS=906°C and oxidises Zn containing

in the furnace atmosphere residuals and
coal
• approx. 95% of the Zn are extracted
• elution of the chlorides and fluorides,

otherwise the electrolysis is disturbed
• similar products from the rotating pipe

Cu and Pb-production rotate oxides
Page 147
49
FACH
LÜBECK
Production of the rotate oxides – rotating process

• solid bed
ZnOsolid + Csolid = Zngas + COgas
CdOsolid + Csolid = Cd + CO
PbSO4solid + 4Csolid = PbS + 4COgas
• Gas atmosphere
Zngas + COgas + O2gas = ZnOsolid + CO2gas
Cdgas + COgas + O2gas = CdOsolid + C02gas
PbSgas + 4CO + 4O2 = PbSO4solid + 4CO2gas

Page 148
FACH
LÜBECK
Leaching of the roasted material and the rotate oxides
• leaching under stirring at 55-95°C
ZnO + H2SO4 aqua = ZnSO4 + H2O
• starting at pH = 1.5, neutralisation with the

roasted material and the rotate oxides
to pH =5.2
solution and
solids
• remaining material precipitates with
the thickener, further processing thickener
with a barrel or disk filter
• solution: Zn, Cu, Cd, Ni, Co, Mg, Mn, Ge filter

solid: Fe, noble metals, As, Sb, Al2O3
Page 149
FACH
LÜBECK
hot-cold leach cleaning
• Fe, Cu, Ni, Cd, Co and H are more ignoble than zinc, so they
disturb the electrolysis
• hydrogen overvoltage, separation of the metals – leach cleaning
• 1. cleaning - hot (80-95°C) : precipitation of Cu, Co and Ni,

addition of Zn dust (2-3 g/l) and As2O3 as a activator, filtration
(Cu2+ , Co2+ , Ni2+ ) + Zn = (Cu,Co,Ni) + Zn2+
• 2. cleaning - cold (75-80°C): precipitation of cadmium,

addition of Zn dust (2 g/l) and CuSO4 as a activator, filtration
(Cu2+ , Cd2+ ) + Zn = (Cu,Cd) + Zn2+

Page 150
50
FACH
LÜBECK
Alternative – hot-cold leach cleaning

cooling tower
filter filter
Zn-dust
Zn-dust
As2O3 to
ZnSO4 electrolysis
1. cleaning 2. cleaning Co-filter cake
Cd-melting furnace
Cd-
electrolysis
Cu-filter cake
Page 151
FACH
LÜBECK
leaching step with thickener

Budel-Zink, Netherlands
thickener
leach cleaning
Budel-Zink, Netherlands
Page 152
FACH
LÜBECK
Extraction electrolysis
• differences to refinement electrolysis:

- Anode is not dissolved
- O2-precipitation at the inert anode
• neutral leach from the leach cleaning is thinned

with cell leach - H2SO4 -, from 155 to 60 g/l
• cathodic reaction: Zn2+ + 2e- = Zn

anodic reaction: H2O = H+ + OH- = 1/2O2 + 2H+ + 2e-
overall reaction: Zn2+ + SO42- + H2O = 1/2O2+ + 2H+ + SO42- + Zn
• cathodic sheet are made from lead, anodic sheets from aluminium
Page 153
51
FACH
LÜBECK
Extraction electrolysis – process sequence

• 40-80 anodes and cathodes per cell, approx. 100 cells per electrolysis
• series connection
• 3400 kWh/tZn cooling tower cooling tower
leach from to leaching

leach cleaning
distributor distributor
electrolysis electrolysis to casting

1. sequence 2. sequence
circuit reservoir circuit reservoir Stripping machine
Page 154
FACH
LÜBECK
Extraction electrolysis – hydrogen overvoltage

• H-precipitation starts before the Zn-precipitation according to the potentials
cathode Zn2+ + 2e- = Zn E0=-0,76V

anode H2O = H+ + OH- = 1/2O2 + 2H+ + 2e- E0=-1,23V
total Zn2+ + SO42- + H2O = 1/2O2 + 2H+ + SO42- + Zn E0=-1,99V
• Kinetics inhibit the H precipitation, the real decomposition voltage is

higher, as calculated from the potentials
• Electrolyte gets 8-10°C warmer
• Inhibition of the H precipitation deceases with increasing temperature,

because of the movability of the ions.
cooling of the electrolyte – cooling towers
Page 155
FACH
LÜBECK
Primary zinc - composition

• DIN-EN 1179:
former
“refined zinc”
former
“commercial
zinc”
• Fe, Pb, Sn, Cd and Ni lead to intercrystalline corrosion in Zn-Al-alloys,

so some limits may not be exceeded
the high purity of the “Feinzink” - 99,99% - enabled the wide usage of Zn
Page 156
52
FACH
LÜBECK
Secondary zinc - recycling

• scrap from casting processes or used zinc material, e.g. sheets can be
melted and reused.
• no such high demands as for Cu
• several conditioning methods possible: distillation, rotate processes,
• DIN-EN 13283:
Page 157
FACH
LÜBECK
Zinc-alloys
• starting material: Z1
• main alloying elements:

Al, Cu, Ti and Mg
Al: lower melt attack on

steel parts, e.g. during
pressure casting,
precipitation hardening,
Cu: increase in strength
Ti: dispersion strengthening by TiZn15
Mg: up to 0,006 weight.% for compensation of the harmful influence

of Sn, Pb, Sn
Page 158
FACH
LÜBECK
Zinc-casting alloy - DIN 1774
pressure casting
preferred
pressure casting alloy
Sand and chill
difficult sand and
chill casting
sand, chill and pressure

casting
good castability and
strength
Page 159
53
FACH
LÜBECK
Zinc-casting alloys - DIN 1774
• ZnCu1CrTi – “Titanzinc”
• „in situ“ dispersion strengthened with TiZn15
• further processing to sheets for roof building
• the only Zn wrought alloy
Page 160
FACH
LÜBECK
Zinc-cast pats - DIN 12844 Titanzinc
Page 161
FACH
LÜBECK
Application – corrosion protection

• zinc rod in ion conductive fluid - electrolyte – zinc ions are dissolved
• voltage between cations and electrons promotes the reverse reaction
• equilibrium between oxidisation and reduction.

Zn
Zn → Zn2+ + 2e- oxidisation
Zn2+ + 2e- → Zn reduction
Cu For a more noble metal,

Cu → Cu2+ + 2e- the tendency to oxidisation
is lower,
Cu2+ + 2e- → Cu the potential is lower.
Page 162
54
FACH
LÜBECK
Application -
corrosion protection
• the electrochemical series
sorts the elements according
to their tendency to oxidise
• a negative potential with a

high absolute value means
a high tendency to
oxidise
Page 163
FACH
LÜBECK
Application – corrosion protection - zincing
• continuous zincing – for steel sheets-

or dip zincing of parts
Zn
• formation of alloys between the
steel and the zinc
• used material: FeZn17

mostly Z4 and Z5
FeZn13
Fe5Zn21
steel
Page 164
FACH
LÜBECK

continuous zincing
• steel sheets are winded up from the coils and
welded together to a tape,
continuous process
• tape storage works as a puffer for the change
to a new coil
tape
• Zinc bath at 400-465°C storage
• velocity of the tape: up to 200 m/min
• layer thickness: 7 - 40 μm
• special alloys e.g.
„Galfan“ 5% Al, 0,1% SE Zinc bath
„Galvalume“ 55% Al, 1,0% Si
Page 165
55
FACH
LÜBECK
Application – corrosion protection – continuous zincing
ThyssenKrupp - Dortmund
general view tape storage

Page 166
FACH
LÜBECK

- continuous zincing
ThyssenKrupp - Dortmund
Quality control after the zinc bath
Page 167
FACH
LÜBECK
Sacrificial anodes in ship

building industry
ZS with activating
additions, e.g. Al, Cd
dip zincing of parts

mostly ZS
Titanzink-sheets
Jewry museum, Berlin
ZnCu1CrTi
Page 168
56
FACH
HOCHSCHULE Titanium Alloys
LÜBECK
Page 169
FACH
LÜBECK
Ti-alloys TiO2
6% pigments 90%
Quelle: Mining Weekly July 2001

Page 170
FACH
LÜBECK
Ore mining
• mainly in open pitch
• Australia, Norway, Brazil, Malaysia and Ukraine
Raw material
• total of ca. 140 different Ti-minerals, but only two
are commercially important
• Rutile - TiO2, 92-98% TiO2
world wide approx 30 Mio. t TiO2
• Ilmenite - (Fe, Mn, Mg)TiO3 37-62% TiO2
world wide approx 270 Mio. t TiO2
Further processing
• accumulation of the ore by flotation and sifter,
• separation of rutile and ilmenite by magnetic and electrostatic separation:
- Rutile: directly processed to titanium sponge
- Ilmenite: further processing to titanium slag or synthetic rutile
Page 171
57
FACH
LÜBECK
Metallurgy Ilmenite-ore Rutile-ore
physical preparation physical preparation
pyrometallurgical hydrometallurgical
TiO2-accumulation TiO2-accumulation
TiO2
cast iron chlorination Cl2, coke, Mg
TiCl4
Mg/Na, H2O, Ti-sponge-

HCl, HNO3 production, Kroll- o.
Hunter-method
electric arc furnace
Titanium
Page 172
FACH
LÜBECK
pyrometallurgical
TiO2-accumulation
• separation of the Fe-content by
reduction with coal at 1200-1600°C
• the iron is used as cast iron
• TiO2-content in the slag 70-85%
• slag is cooled under air exclusion
and broken
FeO•TiO3 (s) + C (s) TiO2 + Fe + CO (g)
Page 173
FACH
LÜBECK
oxidation reduction
hydrometallurgical precipitation
leaching
TiO2-accumulation
• purpose: separation of the
iron-content, several possible methods
• general: separation of the iron
with chlorine or sulphuric acid
• methods based on chlorine:
- oxidation of the iron to
open the Fe•TiO2-compounds
- reduction of hematite - solubility
- leaching
- precipitation
oxidation 2FeO • TiO2+1/2O2 Fe2O3+TiO2
reduction Fe2O3+4H2 2FeO+4H2O
leaching 2FeO+4HCl 2FeCl2+2H2O
precipitation 2FeCl2+2 H2O+1/2O2 Fe2O3+4HCl
Page 174
58
FACH
LÜBECK
Chloride methods - Chlorination

• purpose: transformation of TiO2 to TiCl4
- Titaniumtetrachloride -
separation of the inclusions
• reason: during a direct reduction the inclusion are reduced too, but chlorides have
a low boiling point, so they can be separated by distillation.
• division in: - Chlorination
- Distillation
• raw material: - Titanium slag,
- natural Rutile,
- synthetic Rutile
- oil coke as reducing agent 250-300kg /t TiO2
TiO2 + x C + 2 Cl2 TiCl4 + y CO + zCO2

Page 175
FACH
LÜBECK
Chloride method
• Chlorination is exothermal,
air is used for cooling
• TiCl4 and VOCl3 only a difference of 9°C
between the boiling points
• separation of VOCl3 not possible without a
huge loss of TiCl4
precipitation with H2S and Cu-powder
• purity of TiCl4: 99,9%
99,9 %
Page 176
FACH
LÜBECK
Kroll method
• purpose: reduction of TiCl4 to Ti and separation of
inclusions
• Exothermal reaction, reaction temperature is adjusted
by addition of TiCl4 to 850-950°C
TiCl4 + 2Mg Ti + 2MgCl2

Titanium sponge
ΔH900°C = -521 kJ
Page 177
59
FACH
LÜBECK
Kroll method
• charging and melting of Mg
• charging of TiCl4 over a few
days possible
• the produced liquid MgCl2
is removed continuously from
the bottom of the reactor
• the titanium sponge deposits at
the walls of the reactor
• Distillation of Mg and MgCl2
after finished reduction
• decomposition of MgCl2 to Mg and Cl2,
reused in the chlorination or reduction reactor
• size of one charge: 1,5-7 t depending on the size of the furnace
Page 178
FACH
LÜBECK
Remelting of the titanium sponge - EB-equipment
vacuum lock and intake

of the titanium sponge
electron beam gun
• Titan tends to oxidise, molten metal

remelting in vacuum
• remelting with guided electron beams,
Ti-block molten metal
Electron-Beam-method
Page 179
FACH
LÜBECK
Remelting of the titanium sponge - VAR-equipment

• Vacuum-Arc-Remelt
• pressing and welding of the sponge
to a pre-electrode current entry
vacuum pump
melting electrode,
pre-electrode vacuum chamber
melt drops electric arc
molten metal
block water cooling
Page 180
60
FACH
LÜBECK
Material properties
Titanium steel Aluminium Magnesium
stainless
Density [g/cm3] 4,51 7,92 2,70 1,74
tensile strength [N/mm2] 1200 ! 500-800 520 260
Thermal conductivity 21,6 16,3 238 155,5

[W/(m*K)]
Thermal expansion 8,4 14,8 23,6 25,2
[104/K]
Young‘s modulus 10,4 20,8 6,2 4,0
[104N/mm2]
corrosion attack [mm/s] 0,0 0,001 0,005 no data
(industrial atmosphere)
Page 181
FACH
LÜBECK
Applications – famous example

• ISS
• super sonic bomber SR-71 Blackbird

Monocoque-construction Ti-13V-11Cr-3Al β-alloy
93% of the basic weight is Titanium
• Atom-U-boat OSCAR II - class (Kursk)

body made from a Titanium (also didn’t helped)
alloy
Page 182
FACH
LÜBECK
β/α – transformation
• the plurality in the orientations can

be seen in the microstructure
• within the old β-grains packets of
α-lamellae
• same orientation in one α-lamellae
packet
• 12 different orientations are possible,
repetitions in the orientation of the lamellae packets
• very characteristic microstructure (basketweave)
Page 183
61
FACH
LÜBECK
Classification of the alloys
Influence of the alloying elements on the phase diagram
Page 184
FACH
LÜBECK
α-titanium alloys
• usage: primary in the chemical industry and process engineering
• good corrosion resistance and deformability
• commercial pure titanium differs mainly in the oxygen content

(interstitial alloying element)
high increase in strength at the expense of ductility
- oxygen added on purpose

- all other elements like iron or carbon are inclusions
due to the processing
• classification in grade 1 to 4 (strength from 290 to 740 MPa)
Page 185
FACH
LÜBECK
Near-α-titanium alloys
• classical high-temperature alloys, application temperatures 500...550°C
• combine the good creep properties of the α-alloys and the high strength
of the (α+β)-alloys
• development:
- Ti-8-1-1: Al leads to stress corrosion problems
- Ti-6-2-4-2 (Ti-6Al-2Sn-4Zr-2Mo) lower Al content
- Ti-6-2-4-2-S (Ti-6Al-2Sn-4Zr-2Mo-0,1Si)
0,1%Si dramatic increase in the
creep properties; used up to 0,5% Si
• first commercial Si-containing Ti-alloy: (UK) IMI 679 followed by IMI 685
(Ti-6Al-5Zr-0,5Mo-0,2Si)
• latest high-temperature alloy: (USA) TIMETAL 834

nearly 600°C Tusage
(Ti-5,8Al-4Sn-3,5Zr-0,5Mo-0,7Nb-0,35Si-0,06C)
Page 186
62
FACH
LÜBECK
(α+β)-titanium alloys:
• most often used Ti-alloy Ti-6Al-4V, more than 50% of all alloys
• best investigated alloy

mainly used in the aerospace industry
• further (α+β)-alloys developed to increase strength:

Ti-6-6-2 and IMI 550 Ti-6Al-6V-2Sn
Ti-6-2-4-6 Ti-6Al-2Sn-4Zr-6Mo
high-temperature alloys up to 400°C

Ti-6-Q2
Ti-55-24-S
Ti-17 Ti-5Al-2Sn-2Zr-4Mo-4Cr
Page 187
FACH
LÜBECK
Applications - Ti-6Al-4V
piston rod
fuselage rip - airplane
turbocharger wheel
Quelle: OTTO FUCHS
Page 188
FACH
LÜBECK
Metastable β-titanium alloys:

• became more important
• can reach extreme high strength (1400 Mpa)
• complex microstructure enables optimisation of the ratio of strength to

ductility
• restrictions because of high specific weight, moderate weldability and

bad oxidisation behaviour
- TIMETAL 10-2-3, Beta C (Ti-3Al-8V-6Cr-4Mo-4Zr)
- TIMETAL 15-3; (Ti-15V-3Cr-3Al-3Sn) deformable at RT down to thin foils
- TIMETAL 21S; special oxidisation resistant alloy for foil production, for use in
the production of longfibre reinforced Ti-alloys
- TIMETAL LCB (low cost beta) for applications beside aerospace industry
- SP 700 (Japan) (Ti-4,5Al-3V-2Mo-2Fe), good superplastic behaviour

Page 189
63
FACH
LÜBECK
Applications - β-alloy
rotorhead, forged,
Ti-10V-2Fe-3Al,
156 kg,
origin: OTTO FUCHS
Page 190
FACH
LÜBECK
Wrought and casting alloys
Mechanical
properties
yield strength ductility

tensile strength
Page 191
FACH
LÜBECK
Application - TiAl
γ-TiAl
sheet structures
sheet from Plansee,
Austria
targeted application as heat

shield in the reusable
carrier rocket
“VentureStar”
source: www.lerc.nasa.gov
Page 192
64
FACH
HOCHSCHULE Metal Fabrication
LÜBECK
How do we fabricate metals?

Blacksmith - hammer (forged)
Molding - cast
Forming Operations
Rough stock formed to final shape
Hot working vs. Cold working

• T high enough for • well below Tm recrystallization
• work hardening
• Larger deformations • smaller deformations
Page 193
FACH
HOCHSCHULE Metal Fabrication Methods - I
LÜBECK
FORMING CASTING JOINING

• Forging (Hammering; Stamping) • Rolling (Hot or Cold Rolling)
(wrenches, crankshafts) (I-beams, rails, sheet & plate)
force
die roll
Ad
A o blank A d often at Ao
elev. T
roll
force
• Drawing • Extrusion
(rods, wire, tubing) (rods, tubing)
Ao
die Ad container
tensile die holder
Ao force
force ram billet extrusion Ad
die
container die
die must be well lubricated & clean ductile metals, e.g. Cu, Al (hot)
Page 194
FACH
HOCHSCHULE Extrusion
LÜBECK
• processing procedure for approx. 30% of all

wrought products
• principle: under high pressure the material is

pressed through a steel die
• under compression much higher stresses possible

as under tension
• starting material: cast bolt,
• Technical Data
- Force: 6-150 MN
- Velocity: up to 100 mm/s
- Temperature: 425-520°C
Page 195
65
FACH
LÜBECK
• microstructure development
- elongated grains, even after heat treatment
- increase in strength by deformation strengthening
• cooling from forming temperature

- profiles are very sensitive as long as they are hot,
fast cooling by fan, water bath or spray nozzle
-quenching from forming temperature
e.g. for AlMgSi possible, no annealing treatment
• stretching
- reduction of stresses
• cold or hot aging

- annealing, quenching, aging
Page 196
FACH
LÜBECK
three methods
•direct extrusion
- strong friction
- the core is ahead of the rest behind
- cooling directly behind the die possible
•indirect extrusion
- 30% less friction, bigger bolts
- cross-section limited by the punch
- more difficult in handling and cooling
•Hydrostatic extrusion
- fluid - 200 bar – transfers the pressure
- adjustment of the bolts required
- only small bolts possible
- screw-like bars possible
Page 197
FACH
LÜBECK
Page 198
66
FACH
HOCHSCHULE Metal Fabrication Methods - II
LÜBECK
• Casting- mold is filled with metal

– metal melted in furnace, perhaps alloying
elements added. Then cast in a mold
– most common, cheapest method
– gives good production of shapes
– weaker products, internal defects
– good option for brittle materials
Page 199
FACH
LÜBECK

• Sand Casting
(large parts, e.g.,
• trying to hold something that is hot
auto engine blocks)
• what will withstand >1600ºC?
Sand Sand • cheap - easy to mold => sand!!!
molten metal • pack sand around form (pattern) of

desired shape
Page 200
FACH
LÜBECK

• Sand Casting
(large parts, e.g.,
auto engine blocks) Investment Casting
• pattern is made from paraffin.
Sand Sand
• mold made by encasing in
molten metal plaster of paris
• melt the wax & the hollow mold
• Investment Casting is left
(low volume, complex shapes
e.g., jewelry, turbine blades) • pour in metal
plaster
die formed
around wax wax
prototype
Page 201
67
FACH
HOCHSCHULE Casting
LÜBECK
Precision/investment casting
1 production of wax models
2 assembling of the models into structures

like bunches of grapes or trees
3 dipping into slurry
4 cover the models with a fireproof

material
5 melting of the wax and sintering
6 casting
7 cutting the parts off
Page 202
FACH
LÜBECK

• Sand Casting • Die Casting
(large parts, e.g., (high volume, low T alloys)
auto engine blocks)
Sand Sand
molten metal
• Continuous Casting
• Investment Casting (simple slab shapes)
(low volume, complex shapes
molten
e.g., jewelry, turbine blades)
plaster solidified
die formed
around wax wax
prototype
Page 203
FACH
HOCHSCHULE Casting
LÜBECK
continuous casting
Page 204
68
FACH
HOCHSCHULE Casting
LÜBECK
sand casting
1 upper box
2 guiding and fixing pins
3 feeder
4 upper half model
5 lower half model
6 assembled half model with
feeder and downsprue
7 downsprue
8 lower box
9 core
10 burr (from the gap between
the model halves)
11 cast part
Page 205
FACH
HOCHSCHULE Casting
LÜBECK
chill casting by gravity
start casting tilting filling of the form
Page 206
FACH
HOCHSCHULE Casting
LÜBECK
casting rolled wire

downsprue
SOUTHWIRE-
procedure
casting wheel steel belt

ASARCO-
toploader oven
HAZELETT-
procedure rolling train
HAZELETT-Caster
steel belt
Page 207
69
FACH
HOCHSCHULE Casting
LÜBECK
centrifugal casting
drive mould cast part melt channel
cooled
mould rotating mould
drive
melt
tilted mould channel
mould movable and water cooled

Page 208
FACH
HOCHSCHULE Pressure Die Casting
LÜBECK
Application – pressure casting cold chamber

diecasting
• refined zinc most often base for zinc alloys
• casting alloys
mostly Zn-Al-alloys
processing mainly by pressure casting,
wall thickness down to 0,3 mm
casting temperature ca. 425°C not over 450°C
• casting alloy ZA27 with 25-28% Al

alloy with highest strength
used for sand, chill and pressure casting,
good castability
hot chamber
diecasting
Page 209
FACH
HOCHSCHULE Pressure Die Casting
LÜBECK
Page 210
70
FACH
HOCHSCHULE Metal Fabrication Methods - III
LÜBECK

• Powder Metallurgy • Welding
(materials w/low ductility) (when one large part is
impractical)
pressure
filler metal (melted)
base metal (melted)
fused base metal
heat
heat affected zone
area unaffected unaffected
contact piece 1 piece 2
densify
• Heat affected zone:
point contact densification
by diffusion at
(region in which the
at low T
higher T microstructure has been
changed).
Page 211
FACH
HOCHSCHULE Joining
LÜBECK
Page 212
FACH
HOCHSCHULE Joining
LÜBECK
Page 213
71
FACH
HOCHSCHULE Thermal Processing of Metals
LÜBECK
Annealing: Heat to Tanneal, then cool slowly.

• Stress Relief: Reduce • Spheroidize (steels):
stress caused by: Make very soft steels for
-plastic deformation good machining. Heat just
-nonuniform cooling below TE & hold for
-phase transform. 15-25 h.
Types of • Full Anneal (steels):

Make soft steels for
Annealing good forming by heating
to get γ, then cool in
furnace to get coarse P.
• Process Anneal:
Negate effect of
cold working by • Normalize (steels):
(recovery/ Deform steel with large
recrystallization) grains, then normalize
to make grains small.
Page 214
FACH
HOCHSCHULE Heat Treatments
LÜBECK
800
a) Annealing Austenite (stable)
T(°C) TE
A
b) Quenching P
c) Tempered 600
Martensite
B
400 A
10
0%
50
0% %
0%
200 M+A
50%
M+A
90%
b) a
-1 3 ) 5 c)
10 10 10 10
Page 215
time (s)
FACH
HOCHSCHULE Hardenability--Steels
LÜBECK
• Ability to form martensite

• Jominy end quench test to measure hardenability.
flat ground
specimen
(heated to γ
phase field) Rockwell C
24°C water hardness tests
• Hardness versus distance from the quenched end.

Hardness, HRC
Distance from quenched end

Page 216
72
FACH
HOCHSCHULE
LÜBECK
Schematic time-temperature sequence for hardening and

tempering of alloyed and unalloyed tool steels over 900°C
1000 hardening temperatur

Temperatur [°C]
800
quenching
600
400
tempering
200
time
Page 217
FACH
HOCHSCHULE Why Hardness Changes W/Position
LÜBECK
• The cooling rate varies with position.

Hardness, HRC
60
40
20 distance from quenched end (in)

0 1 2 3
T(°C) 0%
600 P 100%
→
A
400
M(start)
200
A→M
Pe Fine ens
0 M(finish)
ar P ite
M
M ens
lite ea +
ar
ar ite
t
t
rli Pe
te ar
0.1 1 10 100 1000

Time (s)
lite
Page 218
FACH
HOCHSCHULE Hardenability vs Alloy Composition
LÜBECK
100 10 3 2 Cooling rate (°C/s)

• Jominy end quench
60
Hardness, HRC
results, C = 0.4 wt% C 100
4340 80 %M
50
40 4140
8640
10
40
5140
20
0 10 20 30 40 50
Distance from quenched end (mm)
• "Alloy Steels" 800

(4140, 4340, 5140, 8640) T(°C) TE
600 shift from
--contain Ni, Cr, Mo A B A to B due
(0.2 to 2wt%) 400 to alloying
--these elements shift
the "nose". M(start)
200
--martensite is easier M(90%)
to form. 0 -1
10 10 103 105 Time (s)
Page 219
73
FACH
HOCHSCHULE Quenching Medium & Geometry
LÜBECK
• Effect of quenching medium:

Medium Severity of Quench Hardness
air low low
oil moderate moderate
water high high
• Effect of geometry:
When surface-to-volume ratio increases:
--cooling rate increases
--hardness increases
Position Cooling rate Hardness
center low low
surface high high
Page 220
FACH
HOCHSCHULE Precipitation Hardening
LÜBECK
• Particles impede dislocations.

• Ex: Al-Cu system 700
T(°C) L CuAl2
• Procedure: 600
--Pt A: solution heat treat
α α+L
θ+L
A
(get α solid solution) 500 θ
--Pt B: quench to room temp. C α+θ
400
--Pt C: reheat to nucleate
small θ crystals within 300
0 B 10 20 30 40 50
α crystals. (Al) wt% Cu
composition range
• Other precipitation needed for precipitation hardening
systems:
• Cu-Be Temp.
Pt A (sol’n heat treat)
• Cu-Sn
• Mg-Al
Pt C (precipitate θ)
Time
Pt B
Page 221
FACH
HOCHSCHULE Summary
LÜBECK
• Steels: increase TS, Hardness (and cost) by adding

--C (low alloy steels)
--Cr, V, Ni, Mo, W (high alloy steels)
--ductility usually decreases w/additions.
• Non-ferrous:
--Cu, Al, Ti, Mg, Refractory, and noble metals.
• Fabrication techniques:
--forming, casting, joining.
• Hardenability
--increases with alloy content.
• Precipitation hardening
--effective means to increase strength in
Al, Cu, and Mg alloys.
Page 222
74

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FACH

Dr.-Ing. Norbert Hort

Magnesium Innovations Center (MagIC)

α800 727°C Fe3C

ferrite Eutectoid: cementite

Low Alloy High Alloy

a) Amount of Carbon (wt.-%/100)

 E.g: 15 Cr 3, 25 CrMo 56, 22 S 20

Factor Alloying elements

4 Wo Sieht Man CroCodil? Am Nil.

 Iron containing – Steels - cast irons

 Nomenclature AISI & SAE

 where xx is wt% C x 100

 Stainless Steel -- >11% Cr

 Ferrous alloys with > 2.1 wt% C

 Cementite decomposes to ferrite + graphite

 generally a slow process

Reaction C-content wt%

Austenite: γ-Fe (fcc) max. 2,06 at 1147°C

Ferrite: α-Fe (bcc) max. 0,8 at 723°C

Cementite: Fe3C 6,67

Secondary cementite:foms because of the decreasing

Tertiary cementite: foms because of the decreasing C-

α-solid solution (bright) + pearlite (dark)

α-solid solution (bright) + pearlite (dark)

α-solid solution (bright) + pearlite (dark)

MS = 550 - 350% C - 40% Mn - 35% V

All elements in percent by weight

annealed microstructure with spherical Cementite

hardened microstructure (Martensite, Bainite)

According to their effect on the microstructure you distinguish between:

 Al: fine grain, forms nitrides

 Ni: increases toughness, stabilises austenite

 N: embrittlement by precipitations (nitrides), sensitive to ageing

 Hardeness potential: maximal achievable hardness (dependent

distance from the surface

The critical cooling rate decreases with increasing content of

1) Relatively high density

• Discovery: 1808 durch Sir Humphry Davy

Applications wrought alloys

shipbuilding: superstructures: AlMgMn

boatbuilding: mast for sailboats (replaced wood totally)

Automotive: sheets - extrusions:

Applications automotive body shell

Audi A8 from 1994 to 2002

Applications aircraft construction Boeing 777

Applications aircraft construction A340 (65% Al-alloys)

Applications aircraft construction A340

Applications extruded profiles

Capalex extrudes a lot of Otto Fuchs extruded profiles for

Applications train construction

Applications structural material in the building industry

Applications packing industry

maximum performance by minimum material

Aluminothermy: welding of rails,

4 Al + 3 O2 2 Al2O3 ΔHR = 3352 kJ/mol

powder metallurgical production of aluminium high performance materials

Primary processing - Bauxite

• product of the weathering of aluminium silicate stones,

• composition has a wide range:

• 90 % of the Bauxite is found in the tropes

• further processing mostly in the industrialised countries because of the low

Primary extraction Bauxite [Al(OH)3, Al2O3, AlOOH]

E.g: 15 Cr 3, 25 CrMo 56, 22 S 20

Iron containing – Steels - cast irons

Nomenclature AISI & SAE

where xx is wt% C x 100

Stainless Steel -- >11% Cr

Ferrous alloys with > 2.1 wt% C

Cementite decomposes to ferrite + graphite

generally a slow process

Al: fine grain, forms nitrides

Ni: increases toughness, stabilises austenite

N: embrittlement by precipitations (nitrides), sensitive to ageing

Hardeness potential: maximal achievable hardness (dependent