Metals

VII. Nonferrous alloys

Aluminium alloys
Production
Production of aluminium by electrolytically
reducing Al2O3 in liquid salt (cryolite = sodium
aluminum fluoride Na3AlF6) to liquid metal. This
process is very energy consuming and
encourages recycling, which requires only a
fraction of the energy for reducing Al2O3 (HallHeroult process)

Fig. 7.1 Production of Al in an electrolytic cell

7.1

Properties of Al and Al alloys

Al = 2.70 g/cm3 (Fe = 7.87 g/cm3)

High electrical and thermal conductivity

Excellent oxidation and corrosion resistance (passivation)

Nonmagnetic

Low Tm = 660 C

Low hardness low wear resistance

Low endurance limit (failure by fatigue even at low stresses)*

This is due to the formation of Al2O3 at the slip edges, which prevents reversibility of slip in cyclic loading.

7.2

Strengthening mechanisms
Table 7.1 The effect of strenthening mechanism in Al and Al alloys

7.3

Al designation systems
Wrought alloys

Casting alloys

(shaped by plastic deformation)

- Heat-treatable

- Heat-treatable

- Nonheat-treatable

- Nonheat-treatable

Numbering system
1st number specifies the principle alloy element
Other numbers refer to the specific composition of the alloys

Temper Designations
F: As-Fabricated

W: Solution treated

O: Annealed

T: Age hardened

H: Cold worked

7.4

Examples
Wrought alloys
- 1xxx: Commercially pure Al

- 3xxx: Al-Mn

- 2xxx: Al-Cu and Al-Cu-Li

- 4xxx: Al-Si and Al-Mg-Si

Casting alloys
- 1xx: Commercially pure Al

- 3xx: Al-Si-Cu and Al-Mg-Si

- 2xx: Al-Cu

- 4xx: Al-Si

To see more examples please refer to:

D. R. Askeland The Sience and Engineering of Materials

7.5

Wrought alloys
a) Not age-hardenable

Single-phase (1xxx, 3xxx)

Two-phase (4xxx, 5xxx)

Single-phase
Strain hardening
Solid-solution strengthening (limited due to limited solubility)
Grain size control

7.6

Two-phases
Al-Mg (5xxx): Al-Mg solid solution solid-solution hardening
Fine dispersion of intermetallic compound Mg2Al3
Dispersion hardening*
also: - Strain hardening
- Grain size control
Al-Si (4xxx): +
: almost pure Si dispersion hardening

The Mg2Al3 phase is incoherent and does not lend itself for age hardening because
precipitates nucleate heterogeneously resulting in a coarse distribution.

7.7

b) Age-hardenable alloys

Al-Si-Mg (6xxx)
- + (as in Al-Si alloys) + age-hardening by Mg2Si precipitates
Al-Cu (2xxx), Al-Mg-Zn (7xxx)
- Age-hardenable excellent specific strength = strength/density
- Limited solubility limited amount of precipitates limited total
strength
- Overaging for > 175 C

7.8

Al-Cu age hardening

Quenching from into the two
phase region to form
supersaturated .
Since supersaturated is not
stable, the extra copper
precipitates.
Sufficient time @ T aging the +
will form
Fig. 7.2 Al-Cu phase diagram and typical heat
treatment for age hardening.

7.9

Guinier-Preston zones
Fig. 7.3. Crystal structures of the equilibrium phases
(a) and (b). Open and solid circules represent Al
and Cu atoms, respectively. is completely
incoherent, and the resulting high interfacial energy
gives rise to a very high nucleation barrier. Therfore,
only nucleates heterogeneously at grain
bounadaries in a coarse distribution not suitable for
hardening. Because of the high nucleation barrier of
several metastable phases exist. The so-called
Guinier-Preston zones GP I (e) are precipitations of
Cu atoms on 100 planes. They form already below
100C by homogeneous nucleation via diffusion
mediated by quenched-in vacancies*. GP II or (d)
is a superstructure of GP I and forms similarly. The
tetragonal phase (c) is partially coherent, and
dislocations are needed to compensate the
mismatch along the c-direction. Consequently, the
nucleation barrier is higher than for GP I and GP II,
and nucleates heterogeneously at dislocations.

7.10

Effect of Temperature and Time

Fig. 7.4 Isothermal hardening
curves for an Al-4 wt% Cu-1wt%
Mg alloy. At 100C the phase
sequence is GPI, GPII and
resulting in a good hardness. At
higher temperatures the
particles coarsen by Ostwald
ripening at prolonged heat
treatment. This overaging leads to
a drop of hardness. At 300C the
stable phase forms by
heterogeneous nucleation at grain
boundaries. Due to its coarse
distribution it does not lend itself for
hardening.

7.11

Casting alloys
Many alloys contain enough Si to cause eutectic reaction
low Tm good fluidity and castability

Al-Si alloys:

Solid-solution strengthening of -Al

Dispersion strengthening by -phase

Solidification conditions
- Grain size and shape
- Nature of eutectic microstructure

7.12

Al-Li alloys

Li: only element (beside Be) that increases the elastic module of Al
at the same time reduces its density

Max. solubility 4 wt.% 10 % reduction in density

Attractive Al-Li interaction increase in Youngs modulus > 20%

Excellent strength due to age-hardening

Improved fatigue resistance (slow fatigue crack growth rate)

Good toughness at cryogenic temperature (fcc structure)

7.13

Modern manufacturing of Al alloys

Rapid solidification: liquid alloy broken into drops that quickly solidify

Combined with powder metallurgy to incorporate tiny dispersoids

e.g., intermetallic compounds with Fe (e.g. Al6Fe) or Cr
high Tm - No overaging (as for age-hardening)
- Recrystallization retarded fine grains

Thixocasting

7.14

Thixocasting
Stirring during solidification
dentritic structure broken up
rounded primary Al grains
+eutectic
2. Reheating in + L region
fluidity like liquid
3. Casting under pressure
Uniform microstructure
Minimum of casting defects due to
small liquid fraction
For automotive parts: pistons, wheels

Fig. 7.5. Dendritic structure in hypoeutectic AlSi casting alloy (a) can be broken up by the
stirring action and forms primary aluminum
phase forms a round (b)
7.15

Mg alloys
Extracted electrolytically from MgCl2 in seawater
= 1.74 g/cm3
Tm = 649 C
hcp structure much less ductile than Al
Alloying increases number of active slip planes
More active slip planes also at elevated temperature ( formability)
Low strain hardening coefficient
Small degree of solid solution strengthening
No corrosion resistance in presence of salts (seawater!)

7.16

Advanced alloys
- High purity: > 5 wt.% Ce or other RE
Protective MgO film: improved corrosion resistance
- Rapid solidification Larger amount of alloying elements dissolved
Further improvment in corrosion resistance

Hazard during casting and maching: Mg burns easily in air.

Mechanical properties of Mg alloys

- Specific strength comparable with Al alloys
- Low Youngs modulus
- Poor resistance to fatigue, creep and wear
- Limited solubility small degree of solid-solution strengthening
- Age hardening or dispersion hardening
7.17

Mg-Al alloys
Age hardening: up to 10 wt.% Al
1. Alloying Zr, Th, Ag, Ce overaging
resistance at 300 C
2. Alloying up to 9% Li extremely
light weight alloys
3. Strengthening by ceramic particles or
fillers, e.g., SiC
4. Applications: aerospace industry high
speed machinery (e.g., printer carrier
unit)

Fig. 7.6. The Al-Mg phase diagram

7.18

Be alloys

Fig.7.7. A comparison of the strength-to-weight (a) and modulus of elasticity-to-weight (b) ratios
of beryllium and other nonferrous alloys.
7.19

 hcp limited RT ductility

Limited availability of ores expensive
Reactive: oxidates to BeO at elevated temperature
Vacuum casting and forging (expensive!),
powder metallurgy (Tm = 1278 C)
Toxic, carcinogenic for some people
Complicated production
Ore BeS Be(OH)2 dissolved and precipitated as a
fluoride reacted with Mg to produce metal
Applications

Where elastic deformation must be minimal

Aerospace, racing cars, ...
Detector windows (Z = 4!)

7.20

Copper alloys
Production
Cu-Fe ore containing S

oxygen
T

Cu-Fe sulfide high

Fe oxide + pure Cu

Purification: e.g.,electrolytically
Properties
fcc: excellent ductility and strain hardening coefficient
(12 slip systems) good formability
= 8.93 g/cm3: specific strength < as for Al and Mg alloys
Excellent corrosion resistance
Excellent electrical and thermal conductivity
Soldering and brazing ability

7.21

Table 7.6. Properties of typical copper alloys obtained by different strengthening mechanisms.

Applications
- Electrical components, electronics (< 1% impurities)
- Plumbing parts, ...
- Decoration: Pure Cu (red), Zn add (yellow), Ni add (silver colour)
7.22

Leaded Cu alloys

Up to 4.5 wt.% Pb in wrought alloys,

even more Pb in casting alloys

Pb forms monotectic reaction with Cu:

production of tiny Pb spheres since Pb is
the last liquid to solidify

Effect of Pb spheres
Improvement of machining characteristics

Fig.7.8. Schematic Cu-Pb phase diagram.

From : http://www.metallurgy.nist.gov/phase/solder/cupb.html

Minimization of wear
- Lubrication
- Embedding of hard particles in soft lead spheres
Health problems with Pb
Good machinability also obtained with P additions.
7.23

Cu-Be alloys
Age hardened
High strength
High stiffness Application in springs
Nonsparking

Fig.7.9. Binary phase diagram or the copperberyllium system.

7.24

Ni and Co alloys
General properties of Ni and Co alloys
Ni fcc good formability
417C
Co hcp fcc: polycrystals more brittle below 417C

High Tm (Ni: 1455 C, Co: 1495 C) high temperature resistance

Corrosion resistance even in salt water and at elevated temp.
Co superalloys: resistance to human body fluids protetic devices
Ni, Co: ferromagnetic used in magnetic alloys

7.25

Ni and Ni-Cu alloys (Monels)

Max. strength at 60% Ni:
solid-solution hardening
Additions of Ti, Al
precipitation hardening by :
coherent Ni3(Ti,Al)
intermetallic compounds
resistance to overaging at
425C
Ni50Ti50: shape-memory alloys
Ni64Fe36:Invar alloys, 0,
used in bimetallic composite
materials

Fig.7.10. Effect of T on tensile strength of

different Ni-Base alloys

7.26

Table 7.7. Composition, properties and applications for selected Ni and Co alloys.

7.27

Superalloys
Ni, Ni-Fe and Co alloys + large amount of alloying elements
High strength at elevated temperature
High creep resistance up to 1000C
Corrosion resistance even at elevated temperature
Application
- Vanes and blades for turbine and gas engines
- Heat exchangers
- Components for chemical reaction vessels
- Heat-treating equipment

7.28

a) Solid-solution hardening
Large amount of Cr, Mo, W
- Mo, W: large elements slow diffusion high T creep stability
- Cr: also oxide scale and carbide former
- Smaller additions of Ta, Zr, Nb, B
B segregates at grain boundaries of Ni3Al*
- Increase in coherent strength of GB
- Disordering of GB region no superdislocations
Relief of dislocation pile-up stess by slip across the boundary
(see Hall-Petch process)
Strongly reduced crack formation at GB
B also softens the grains, e.g., by segregation to dislocations thus preventing superdislocation
dissociation.

7.29

b) Carbide dispersion strengthening

Small amounts of C carbides with:Ti, B, Zr, Ta, Cr, Mo, W
often containing several elements
Fine dispersion of stable carbides: obstacles for dislocations
Preferential nucleation of some carbides at grain boundaries
prevents grain boundary sliding

c) Precipitation hardening
Ni3Al, Ni3Ti or Ni3(Ti, Al) during aging
Coherent low interfacial energy small driving force for overaging
good strength even at high temperature

7.30

Various aging temperatures

High T: large particles,

Low undercooling few nuclei, fast diffusion

Intermediate T: evolution of desired GB microstructure of

carbide particles envelop in a film of
Low T: fine dispersion of
Large undercooling many nuclei, slow diffusion

Best combination of strength at intermediate and high temp.

(a)

(b)

Fig. 7.11. (a) Microstructure of

a superalloy, with carbides at
the grain boundaries and
precipitates in the matrix
(15,000). (b) Microstructure of
a superalloy aged at two
temperatures, producing both
large and small cubical
precipitates (10,000). The
orientation and shape of the
particles arises from their
coherent growth.
7.31

Ti alloys
Kroll process: TiO2

TiCl4: reduced to Ti by Na or Mg

Excellent corrosion resistance below 535 C by TiO2 film

T > 535 C: TiO2 film brakes down embrittlement by
carbon, oxygen, nitrogen, hydrogen, ...
High specific strength: = 4.51 g/cm3
Good high-temperature properties: Tm = 1660 C
Low thermal conductivity and thermal expansion
Some Ti alloys have excellent superplastic forming characteristics

7.32

882C

-Ti: hcp
-Ti: bcc
(martensitic transformation)
Transformation temperature changed by
alloying!
-stabilizers: Al, oxygen*, hydrogen*
(high manufacture cost to minimize gas!)
-stabilizers: V, Ta, Mo, Nb
Sn, Zr: - do not affect - transformation
- Provide solid-solution strengthening.
Mn, Cr, Fe: produce eutectoid reaction
- Reduction of - transition temp.
- Two-phase structure at room temp.

*In the close packed structures the interstices are larger than in bcc.

Fig. 7.13. Effect of alloying elements

on Ti alloy phase diagrams
7.33

Applications
Chemical processing equipment
Marine components
Biomedical implants
Airframe and jet engine components
Ni-Ti: shape-memory alloys

Table 7.8. Properties of

selected Ti alloys

7.34

Commercially pure Ti
Used for its superior corrosion resistance
Impurities (e.g.,oxygen) increase yield strength
Applications
Heat exchangers
Piping
Reactors
Pumps
Valves for chemical and petrochemical industries

7.35

-Ti alloys
Typ. alloy: Ti - 5wt.% Al - 2.5 wt.% Sn Solid-solution hardening of hcp
Annealing in region:
Rapid cooling acicular or Widmansttten grain structure: provides good fatigue
resistance
Furnace cooling more platelike structure provides better creep resistance
(larger features)

Hcp basal planes ||

{110} bcc

Fig. 7.14. (a) Annealing and (b) microstructure of rapidly cooled -Ti alloys (
100). The -phase first nucleates at grain boundaries and then extends into the
bulk in the form of Widmansttten plates.
7.36

-Ti alloys
Rich in stabilizers rapid cooling produces 100%

metastable

Strengthening:

- solid-solution hardening by stabilizers

- age-hardening metastable precipitates

Applications:

e.g., fittings for aerospace applications

7.37

--Ti alloys
Proper balance of and stabilizers mixture of and at RT
Ti - 6% Al - 4% V: most common Ti alloy, used up to 350 C
Annealing just below -transus temp.
small amount of remains grain growth in prevented
Slow cooling equiaxed grains of
hcp plates form with basal planes parallel to 110 of bcc matrix
- Good ductility and formability (compared to basket weave
structure)
- Nucleation of fatigue cracks difficult

7.38

Faster cooling from above - transus temp.

acicular or basket weave
- Low fatigue crack growth rate

Fatigue cracks may nucleate more easily but must follow tortuous path
along / boundaries
- Good fracture toughness
- Good creep resistance

Shape, size and distribution of and are controled by thermomechanical

processing

7.39

Fig. 7.15. Annealing of an - titanium alloy.

(a) Annealing is done just below the -
transus temperature, (b) slow cooling gives
equiaxed grains ( 250), and (c) rapid
cooling yields acicular grains ( 2500).

(a)

(b)

(c)
7.40

Quenching

Ti martensite () upon crossing MS

Ti martensite: soft supersaturated phase
Tempering: + precipitates
precipitates initially increase the strength compared to
(opposite to tempering of steel martensite!)
Tempering at high temp. softening

Fig. 7.16. Heat treatment of -

Ti alloys: Quenching from high
temperatures at moderate V
content leads to martensite
formation. Tempering of the soft
Ti martensite gives rise to
precipitation of fine particles
which improve strength. At
higher V content quenching from
a rich partion of the two-phase
region produces a microstructure
consisting of primary and SS,
which is supersaturated in Ti.
When SS is aged, precipitates
in a Widmansttten structure,
improving the strength and
fracture toughness. (Fig.9.18)

7.41

Age-hardening of more highly alloyed - alloys

1. Quenching from + :
primary + SS: supersaturated in Ti
2. Aging: SS + precipitates
: Widmansttten structure: (hcp basal plane 110 bcc)
improved strength and fracture toughness

Fig. 7.17. Microstructure resulting from agehardening of - Ti alloys according to Fig.

9.17: The large white grains are primary and
the dark regions are matrix with needles of
formed during aging of supersaturated SS (
250)

7.42

Refractory Metals
W, Mo, Ta, Nb: high Tm > 1925 C high temp. service
Applications: filaments, rocket nozzles, electronic capacitors, chem.
processing equipment, ...
High density limited specific strength
Table 7.9. Properties of refractory metals

7.43

Oxidation: starts between 200 and 425 C!

Special precautions required during casting, hot working, welding or powder
metallurgy
Operation in vacuum (e.g., W filament in light bulk)
Coating with silicide or aluminide for T >1650 C
Requirements:

- High Tm
- Good adhesion
- Diffusion barrier for contaminants
- Low thermal expansion mismatch

7.44

Forming characteristics
Nb, Ta: ductile-to-brittle transition (bcc structure) below RT
good formability
Mo, W: transition temperature > RT
hot working fibrous microstructure with lower transition temperature

Alloys
W: alloying of Hf, Re, C operation up to 2100 C solid-solution strengthening
W-Mo: complete solute solubility solid-solution strengthening
W - 2% ThO2: dispersion strengthening to prevent grain boundary sliding,
(e.g., in filaments),
Oxide particles incorporated during powder metallurgy processing.
Nb reinforced with W fibers improved high-temp. properties.
7.45