1

Objective Microstructure­Properties: II
Age­
hardening Age Hardening
Al­Cu
Al­Ag 27-302
steels Lecture 9
mecha­ Fall, 2002
nisms
Prof. A. D. Rollett
 2

Materials Tetrahedron
Processing
Performance

Objective
Age­
hardening
Al­Cu
Al­Ag
steels
mecha­
nisms Microstructure Properties
 3

Objective
• The objective of this lecture is to
describe the relationship between
Objective
precipitation and hardness as an
Age­
example of a key microstructure-
hardening property relationship.
Al­Cu
Al­Ag
steels
mecha­
nisms
 4

References
• Phase transformations in metals and alloys,
D.A. Porter, & K.E. Easterling, Chapman &
Hall.
Objective • Materials Principles & Practice, Butterworth
Age­ Heinemann, Edited by C. Newey & G. Weaver.
hardening • Mechanical Metallurgy, McGrawHill, G.E.
Al­Cu Dieter, 3rd Ed.
Al­Ag • Hull, D. and D. J. Bacon (1984). Introduction
steels to Dislocations. Oxford, UK, Pergamon.
mecha­ • Courtney, T. H. (2000). Mechanical Behavior
nisms of Materials. Boston, McGraw-Hill.
 5

Notation
a := lattice parameter
 := strain, misfit (or similar quantity to
describe a hardening mechanism)
Objective
G := shear modulus
b := Burgers vector
Age­
r := Particle size (radius)
hardening
f VV() :=volume fraction (of precipitates)
Al­Cu
 := stress (macroscopic)
Al­Ag  := shear stress (critical value, in some cases)
steels  := boundary energy, e.g. anti-phase boundary
mecha­ <L3> := mean intercept length (of
nisms precipitates)
 := mean spacing (of precipitates)
 6

Age Hardening Curves
• The most quoted age
hardening curve is that
for Al-Cu alloys
performed in the late
Objective 40s. Keep in mind that
Age­ age hardening was
hardening known empirically
(Alfred Wilm) as a
Al­Cu
technologically useful
Al­Ag treatment from the early
steels days of aluminum alloys.
mecha­ • Higher Cu contents
nisms result in higher
maximum hardnesses
because larger volume
fractions of precipitate
are possible.
 7

Al­Cu precipitation sequence
• The sequence is:
0  1 + GP-zones  2 + “ 3 + ’ 4 + 
• The phase are:
Objective n - fcc aluminum; nth subscript denotes
Age­
each equilibrium
hardening GP zones - mono-atomic layers of Cu on
(001)Al
Al­Cu
“ - thin discs, fully coherent with matrix
Al­Ag ’ - disc-shaped, semi-coherent on (001)’
steels bct.
mecha­  - incoherent interface, ~spherical,
nisms complex body-centered tetragonal (bct).
 8

Al­Cu ppt 
structures
Objective
Age­
hardening
Al­Cu
Al­Ag
steels
mecha­
nisms

GP zone structure
 9

Al­Cu microstructures
• This tableau shows which of the different
ppt types are associated with which part
of the hardening curve.
Objective
GP zones
Age­
hardening
’
Al­Cu
Al­Ag
steels ”

mecha­
nisms
 10

Al­Cu driving forces
• Each precipitate has a different free energy curve
w.r.t composition. Exception is the GP zone, which
may be regarded as continuous with the alloy
(leading to the possibility of spinodal
Objective decomposition, discussed later).
Age­ • P&E fig. 5.27 illustrates the sequence of
hardening successively greater free energy decreases and
Al­Cu also successively greater ∆G*.
Al­Ag • P&E fig. 5.28 illustrates the point that the
nucleation barriers are much smaller for each
steels
individual nucleation step when the next
mecha­ precipitate nucleates heterogeneously on the
nisms previous structure.
 11

Al­Cu phase relationships
• The explanation of age hardening
depends on understanding the metastable
phases that can appear.
Objective
Age­
hardening
Al­Cu
Al­Ag
steels
mecha­
nisms
 12

Nucleation sites, reversion
• The nucleation sites vary depending on
circumstances.
• “ most likely nucleates on GP zones by adding
additional layers of Cu atoms.
Objective
• Similarly, ’ nucleates on “ by in-situ transformation.
Age­ • However, ’ can also nucleate on dislocations, see
hardening
P&E fig. 5.31a.
Al­Cu • The full sequence is only observable for annealing
Al­Ag temperatures below the GP solvus. Any of the
steels intermediate precipitates can be dissolved, reverted,
by increasing the temperature above the relevant
mecha­ solvus, fig. 5.32.
nisms
 13

Al­Ag: example 2
• The age hardening curve has the same
double peak as for the Al-Cu series, but
the separation is more pronounced.
Objective
Age­
hardening
Al­Cu
Al­Ag
steels
mecha­
nisms

Shewmon
 14

Al­Ag, contd.
• GP zones are spherical (Ag atom is larger than Al).
•  ’ is hcp with OR (0001)//(111) and [1120] //[110];
heterogeneously nucleated on the stacking faults
of dislocations which provide sites of local
Objective
hexagonal packing.
Age­
hardening •
  is also hcp with the same OR; forms plate-like
precipitates. A cellular mechanism can also
Al­Cu occur.
Al­Ag
steels
mecha­
nisms

Shewmon
 15

Age hardening in steel: example 3
• It is important to understand that age hardening
occurs in almost any system in which the solid
solubility decreases appreciably with decreasing
temperature. Ferrite has a very low solubility for
Objective carbon and therefore age hardening (also called
quench hardening) occurs here too. To avoid it,
Age­
hardening the soluble carbon levels must be reduced, which
is a common objective of the IF or interstitial-free
Al­Cu
steel grades. These have additions of carbide
Al­Ag formers such as Ti or Nb to sequester the C.
steels
mecha­
nisms Shewmon
 16

Cutting versus Bowing
• At small sizes, the dislocation cuts through the
particle at a lower stress than the Orowan bowing
stress (and so this is what is observed). Larger
particles mean higher cutting stresses.
Objective
• At large sizes, the dislocation bows around the
Age­ particle more easily than it cuts through it (so no
hardening cutting is observed). Larger particles mean fewer
Al­Cu particles (via coarsening) hence lower flow
stresses. Fewer and fewer particles, 
Al­Ag
Particles becoming stronger further apart
steels
mecha­
nisms
 17

Breaking Angle: c
Courtney

Objective Gb  c 
 cos  
Age­ L   2 
hardening
Al­Cu
Al­Ag
steels
mecha­
nisms

Strong Obstacles:  ~ 0° Weak Obstacles:  ~ 180°
 18
Hardness ­microstructure 
relationships
• In order to understand the relationship between microstructure
and hardness, we need to delve into the subject of hardening
mechanisms.
• The central concept is that the strength of a ductile material is
governed by dislocation flow past obstacles. Therefore
Objective strength can be designed by controlling the density and nature
Age­ of the obstacles to dislocation motion. Most technological
hardening (metallic) alloys rely on precipitation hardening in one form or
another to achieve high strengths. Ceramics, on the other
Al­Cu hand, are intrinsically harder and therefore the main objective
of strengthening is to increase their fracture toughness and
Al­Ag
thereby increase their (reliable) load carrying capacity. The
steels objective of this discussion is therefore to bring your attention
to a number of ways in which we can understand and predict
mecha­ the contributions to strength of different types of obstacle.
nisms
 19

Strengthening Methods
• Microstructural Feature:
strength dependence.
• Dislocations: strain/work hardening (discussed
in 301): (dislocation spacing)1/2.
Objective • Internal Boundaries: grain boundaries can have
Age­ a strong strengthening effect, i.e. the Hall-
hardening Petch effect (discussed in 301): (grain size)-1/2.
Al­Cu
• Dislocation Boundaries (low angle boundaries):
Al­Ag (subgrain size)-1.
steels • Second Phase Particles: particle spacing.
mecha­ • Solutes: (concentration)1/2.
nisms
 20

Mechanisms of particle strengthening
1) Coherency Hardening: differences in density between the
particle and the matrix give rise to elastic stresses in the vicinity
of the particle.
2) Chemical Hardening: creation of new surface when a
particle is sheared increases the area of the interphase
Objective boundary, which increases the energy associated with the
interface and hence an additional force must be exerted on the
Age­
dislocation to force it through the particle.
hardening
3) Order Hardening: passage of a dislocation through an
Al­Cu ordered particle, e.g. Ni3Al in superalloys, results in a disordered
lattice and the creation of antiphase boundaries.
Al­Ag
4) Stacking-fault Hardening: a difference in stacking fault
steels energy between particle and matrix, e.g. Ag in Al, increases flow
mecha­ stress because of the different separation of partial dislocations
in the two phases.
nisms
5) Modulus Hardening: a large difference in elastic modulus
results in image forces when a dislocation in the matrix
approaches a particle. Consider, e.g., the difference between
silver particles (nearly the same shear modulus) and iron
particles (much higher shear modulus) in aluminum.
 21

Dislocations
• A re-statement of the governing equation
for strength controlled by obstacle
spacing:
Objective   M  0  Gb /  
Age­ Parameter Description Comments
 flow stress Experimentally accessible through mechanical
hardening tests
<M> Average Taylor factor Magnitude ~3 for tension or compression;
Al­Cu depends on the nature of the deformation, the
texture and the crystal structure, e.g. <M>~1.73
Al­Ag
  Athermal stress
for torsion (cubic metals)
Contributions from grain size hardening,
steels solutes, etc.
 Geometrical factor This term accounts for both geometrical factors,
mecha­ and for thermal activation
G Shear Modulus Must choose appropriate shear modulus for the
nisms slip plane used;
Temperature dependent
b Burgers vector Derived from the force on a dislocation (Peach­
Koehler Eq.)
¦ dislocation density Equivalent to the reciprocal of a mean obstacle
spacing; depends on work hardening
 obstacle spacing Given a number density of particles, the mean
spacing, =N1/2
 22

crss versus density

Objective
Age­
hardening
Al­Cu
Al­Ag
steels
mecha­
nisms

Courtney
 23

Dislocation Boundaries
• At large strains and higher temperatures, low angle
boundaries appear as a subgrain network forms. We
distinguish this microstructural feature from the first
two categories because the [lattice] misorientations
Objective are much smaller (2-5°) than grain boundaries (15°+)
Age­ and they are distinct from statistically stored
hardening dislocations. This strengthening method is most
important at high temperatures where other
Al­Cu
microstructural features such as solutes are weak.
Al­Ag • The contribution to the flow strength is typically
steels found to be proportional to (grain size)-1; this is in
mecha­ contrast to the 1/√d dependence of the Hall-Patch
nisms effect.
 24

Solutes
• Solutes in a crystal act as obstacles to
dislocation motion through their elastic
and/or chemical interactions with
Objective dislocations. Most solutes are weak
Age­ hardeners except for the (technologically)
hardening important class of interstitial solutes that
Al­Cu induce anisotropic distortions of the
Al­Ag lattice, e.g. tetragonal distortions of C in
steels Fe.
mecha­
nisms
 25

Substitutional solutes
• Most Solutes have only a rather weak effect on strength. In
other words, even if you put several per cent of a soluble atom
into another element, you will not see a dramatic increase in
flow stress. These remarks can be quantified by going back to
the Orowan equation, i.e. the force balance between the forward
motion and the resisting force:
Objective
Age­ crss = µb/.
hardening
Al­Cu • For substitutional solutes, the numerator in the RHS, i.e. the
reaction force from the solute atoms is of order Gb 2/120, which
Al­Ag is a small number. This is so because the small differences in
size between solute and matrix atoms results in a small
steels interaction energy with dislocations. Thus they are weak
mecha­ obstacles and dislocations remain nearly straight when
nisms interacting with solutes (“weak obstacles”, 7slides before this).
 26

Interstitial solutes
• Interstitials in bcc, however, can exert forces on the
order of Gb2/5 to Gb2/10, which are large values. In
this case, the dislocations bow out significantly
between the atoms, and the breaking angle
Objective deviates significantly from 180°. In this case, the
Age­ concentration dependence is easy to obtain. The
hardening spacing between interstitials is inversely
Al­Cu proportional to the (square root of the)
concentration, and so we can insert a spacing into
Al­Ag the standard (Orowan bowing) formula to get the
steels following, where A is a constant of order unity:
mecha­
nisms  = Gb(√c/b) = G√c.
 27

Strength vs. solute content: examples
Examples:

a)
Substitutional
Objective solutes in Cu
Age­
b) Interstitial
hardening
solutes in
Al­Cu Nb, Fe
Al­Ag
steels c) Ca in NaCl
mecha­ [Courtney]
nisms
 28

Second Phase Particles
• Whether introduced as insoluble particles in
powder compaction, or as precipitates in a solid
state reaction, second phase particles are
generally the most potent strengthening agent in
Objective practical high strength engineering materials.
Age­ Iron-base, aluminum, nickel, titanium alloys all
hardening employ second phases to achieve high strength.
Al­Cu • Quantitative relationships: from previous
Al­Ag stereological analysis (301 - lecture 4):
steels 4r 1  VV(  )
L3  ;   L3 ( ) ;
mecha­ 3 VV
nisms
4r 1  VV(  ) 4r1  f  4r
 ()  
3 VV 3f 3f
 29

Mechanisms of particle strengthening
1) Coherency Hardening: differences in density
between the particle and the matrix give rise to elastic
stresses in the vicinity of the particle.
2) Chemical Hardening: creation of new surface when
a particle is sheared increases the area of the interphase
boundary, which increases the energy associated with the
Objective interface and hence an additional force must be exerted on
Age­ the dislocation to force it through the particle.
hardening 3) Order Hardening: passage of a dislocation through
an ordered particle, e.g. Ni3Al in superalloys, results in a
Al­Cu disordered lattice and the creation of antiphase boundaries.
Al­Ag 4) Stacking-fault Hardening: a difference in stacking
steels fault energy between particle and matrix, e.g. Ag in Al,
increases flow stress because of the different separation of
mecha­ partial dislocations in the two phases.
nisms 5) Modulus Hardening: a large difference in elastic
modulus results in image forces when a dislocation in the
matrix approaches a particle. Consider, e.g., the difference
between silver particles (nearly the same shear modulus)
and iron particles (much higher shear modulus) in aluminum.
 30

Coherency hardening
Differences in density between the particle and the matrix
give rise to elastic stresses in the vicinity of the particle.
This has been analyzed on the basis of the elastic
stresses that exist in the matrix adjacent to a particle
Objective that has a different lattice parameter than the matrix.
Ignoring differences in modulus for now, and setting a
Age­ parameter, , that approximates a strain to characterize
hardening the magnitude of the effect. For
Al­Cu
 = (aparticle – amatrix )/ amatrix
Al­Ag
steels  = 7||3/2 G(rf/b)1/2
mecha­ • This mechanism applies to the early stages of
nisms precipitation, e.g. strengthening by GP zones.
 31

Chemical hardening
• Cutting through a particle with a dislocation
displaces one half relative to the other by b,
thereby creating new interfacial energy of 2πrb, 
where  is the interfacial energy between the
Objective matrix and the particle. The distance over which
Age­ this energy has to be created occurs at the entry
hardening and exit points and so the characteristic distance
Al­Cu is of order b. Thus the force is dE/dx, or,
Al­Ag
F  =  2πrbbπr
steels
mecha­
nisms
 32

Chemical hardening, contd.
• If the dislocations are straight, we can approximate the spacing
between particles as L=2r/f. Dividing the force by bL to find the
stress,

 = πf/2b.
Objective
Age­ • A more realistic approach produces the following relationship.
hardening
Al­Cu  = 2G{/Gr}3/2(fr/b)1/2
Al­Ag • Courtney defines a chemical hardening parameter, ch = /Gr, related
steels to the interfacial energy, modulus and particle size. This parameter
is precisely analogous to the same parameter used, e.g. in APB
mecha­ hardening. Chemical hardening applies only in the early stages of
nisms precipitation.
 33

Order Hardening
• The hardening depends on the product of the antiphase-
boundary energy (APBE) and the area swept by a dislocation in a
particle. Thus the increase in flow stress is given by:
 = πf{APBE}/2b
Objective • In general, low values of the APBE not only predict small
increments in hardness, but also the result that the dislocations
Age­ can move through the particles independently of one another. A
hardening more detailed analysis, not presented here, shows a square root
dependence on volume fraction, with particle size,
Al­Cu
 = 0.7 G3/2 √(fr/b)
Al­Ag ord= APBE/Gb
steels
• Important for
mecha­
Ni-based superalloys
nisms
 34

Modulus hardening
• The line length in the particle is 2r and the change in tension is
(Gparticle-Gmatrix)b2/2, assuming the same Burgers vector in matrix
and particle. Multiplying the two together and dividing by the
distance, i.e. the radius, we get:
F= b2(Gparticle-Gmatrix) = Gb2,
Objective
Age­ where  = (Gparticle-Gmatrix)/Gmatrix, a measure similar to that used in
hardening solution hardening.
• More realistic estimates of modulus hardening lead to the
Al­Cu following formula:
Al­Ag
 = 10-2 G 3/2 √{fr/b}
steels
• Think of modulus hardening as being caused by a temporary
mecha­
increase in dislocation line energy while it resides within a
nisms particle.
 35

Summary
• A great variety of hardening mechanisms exist.
• Their functional dependence on parameters such as
particle size, spacing, volume fraction, are similar. It is
difficult therefore, to distinguish experimentally between
the mechanisms.
Objective
• Microscopy is required in order to determine which
Age­ mechanism is operative.
hardening • Particle growth results in stronger particles; in most
Al­Cu cases, however, coarsening takes place simultaneously
which increases the particle spacing. Orowan bowing
Al­Ag takes over from particle cutting at some point in the
steels aging process.
mecha­ • Particle hardening is essential to technological alloys, at
nisms least for structural applications.
 36

Sample Problem
• From Dieter, p219 (adapted):
• Question: Al-4%Cu (by wt.) has a yield stress of 600MPa. Estimate the
particle size and spacing.
• Solution: recognize that this stress relates to age hardening beyond the
peak hardness. Therefore use the Orowan bowing stress to estimate the
stress.
<M>crss = <M> Gb/
Objective
• G=27.6GPa; b=0.25nm; <M>=3.1:
Age­ spacing = 3.1*27,600*0.25.10-9/ 600= 35.7 nm
hardening • Now we must estimate the volume fraction of particles for which we use
the phase diagram, assuming that we are dealing with the equilibrium
Al­Cu phase, , which is 54 w/o Cu, and the  in equilibrium with it, 0.5 w/o Cu.
• Wt. % Al = (54-4)/(54-0.5) = 93.5; wt. %  = 4-0.5/(54-0.5)=6.5
Al­Ag • Volume of  = 93.5gm/2.7 gm/cm3 =34.6 cm3
steels • Volume of  = 6.5/ 4.443 gm/cm3 = 1.5 cm3
• Volume fraction of  = 0.96; volume fraction of  = 0.04.
mecha­ • Use =4r(1-f)/3f (slide 22): r =3*0.04*35.7/4/(1-0.04) = 1.12 nm.
nisms