1

Objective Microstructure-Properties: II
Age-
hardening Age Hardening
Al-Cu
Al-Ag 27-302
steels Lecture 9
mecha- Fall, 2002
nisms
Prof. A. D. Rollett
 2

Materials Tetrahedron
Processing
Performance

Objective
Age-
hardening
Al-Cu
Al-Ag
steels
mecha-
nisms Microstructure Properties
 3

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

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

Notation
a := lattice parameter
 := strain, misfit (or similar quantity to
describe a hardening mechanism)
Objective G := shear modulus
Age- b := Burgers vector
hardening r := Particle size (radius)
Al-Cu f VV() := volume fraction (of precipitates)
Al-Ag  := stress (macroscopic)
steels  := shear stress (critical value, in some cases)
mecha-  := boundary energy, e.g. anti-phase boundary
nisms <L3> := mean intercept length (of 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 40s. Keep in mind that
Objective
age hardening was known
Age- empirically (Alfred Wilm) as
hardening a technologically useful
Al-Cu treatment from the early
Al-Ag days of aluminum alloys.
steels • Higher Cu contents result in
higher maximum hardnesses
mecha-
nisms
because larger volume
fractions of precipitate are
possible.
 7

Al-Cu precipitation sequence

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

Al-Cu ppt
structures
Objective
Age-
hardening
Al-Cu
Al-Ag
steels
mecha-
nisms

GP zone structure
 9

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

Al-Cu 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 decomposition, discussed later).
Objective
• P&E fig. 5.27 illustrates the sequence of successively greater
Age- free energy decreases and also successively greater ∆G*.
hardening
• P&E fig. 5.28 illustrates the point that the nucleation barriers
Al-Cu are much smaller for each individual nucleation step when the
Al-Ag next precipitate nucleates heterogeneously on the previous
steels structure.
mecha-
nisms
 11

Al-Cu phase relationships

• The explanation of age hardening depends on
understanding the metastable phases that can
appear.
Objective
Age-
hardening
Al-Cu
Al-Ag
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 P&E fig.
hardening 5.31a.
Al-Cu • The full sequence is only observable for annealing
temperatures below the GP solvus. Any of the intermediate
Al-Ag
precipitates can be dissolved, reverted, by increasing the
steels temperature above the relevant solvus, fig. 5.32.
mecha-
nisms
 13

Al-Ag: 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
Al-Cu
Al-Ag
steels
mecha-
nisms

Shewmon
 14

Al-Ag, 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 hexagonal packing.
Objective
•  is also hcp with the same OR; forms plate-like precipitates.
Age-
hardening
A cellular mechanism can also occur.

Al-Cu
Al-Ag
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 carbon and therefore age hardening (also
Objective called quench hardening) occurs here too. To avoid it, the
soluble carbon levels must be reduced, which is a common
Age-
hardening
objective of the IF or interstitial-free steel grades. These have
additions of carbide formers such as Ti or Nb to sequester the
Al-Cu C.
Al-Ag
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 particle more
Age- easily than it cuts through it (so no cutting is observed).
hardening Larger particles mean fewer particles (via coarsening) hence
Al-Cu lower flow stresses.
Fewer and fewer particles,
Al-Ag
Particles becoming stronger further apart
steels
mecha-
nisms
 17

Breaking Angle: c
Courtney

Objective Gb ⎛φ c ⎞
τ= cos⎜ ⎟
Age- L′ ⎝2⎠
hardening
Al-Cu
Al-Ag
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
Objective governed by dislocation flow past obstacles. Therefore strength can
Age- be designed by controlling the density and nature of the obstacles to
hardening dislocation motion. Most technological (metallic) alloys rely on
precipitation hardening in one form or another to achieve high
Al-Cu strengths. Ceramics, on the other hand, are intrinsically harder and
Al-Ag therefore the main objective of strengthening is to increase their
fracture toughness and thereby increase their (reliable) load carrying
steels
capacity. The objective of this discussion is therefore to bring your
mecha- attention to a number of ways in which we can understand and
nisms predict the contributions to strength of different types of obstacle.
 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 a strong
Age- strengthening effect, i.e. the Hall-Petch effect (discussed
hardening
in 301): (grain size)-1/2.
Al-Cu
• Dislocation Boundaries (low angle boundaries): (subgrain
Al-Ag 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 boundary, which increases the
energy associated with the interface and hence an additional force must be
Objective
exerted on the dislocation to force it through the particle.
Age- 3) Order Hardening: passage of a dislocation through an ordered particle,
hardening e.g. Ni3Al in superalloys, results in a disordered lattice and the creation of
Al-Cu antiphase boundaries.

Al-Ag 4) Stacking-fault Hardening: a difference in stacking fault energy

between particle and matrix, e.g. Ag in Al, increases flow stress because of
steels the different separation of partial dislocations in the two phases.
mecha- 5) Modulus Hardening: a large difference in elastic modulus results in
nisms 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 σ = M (τ 0 +α Gb / λ )
Age- Parameter Description Comments
σ fl
ow st ress Exper imentally acce ssible hroughm
t echanical
hardening tests
<M > Average Taylorfactor M agnitude ~3 fo rtension orcom pre ssion;
Al-Cu depend s onthe atnure ofthedeformati on, he
t
texture and thecry stalst ructure, e.g. <M >~1.73
Al-Ag for orsi
t on (cubic metals)
€ τ0 A thermalstress Contributions from grain si zehardening,
steels solutes, te c.
α Geom etri calfactor This term accounts f or both geom etri calfactors,
mecha- andfortherm alacti vati on
G ShearM odulus Mustchoose appropri ate shearm odulus forthe
nisms slip planeused;
Tem per ature dependen t
b Burgers vector Deri vedfrom theforceon a dis locati on (Peach -
KoehlerEq.)
√ρ dislocation density Equivalentto the reciprocal ofa m ean obstacle
spacing; dependson work ha rdening
λ obstacle spacing G ivena num berdens iyt of particles,the mean
spacing, λ=N 1/2
 22

crss versus density

Objective
Age-
hardening
Al-Cu
Al-Ag
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 are much
Objective
smaller (2-5°) than grain boundaries (15°+) and they are
Age-
distinct from statistically stored dislocations. This
hardening
strengthening method is most important at high
Al-Cu temperatures where other microstructural features such as
Al-Ag solutes are weak.
steels • The contribution to the flow strength is typically found to be
mecha- proportional to (grain size)-1; this is in contrast to the 1/√d
nisms dependence of the Hall-Patch effect.
 24

Solutes
• Solutes in a crystal act as obstacles to dislocation
motion through their elastic and/or chemical
interactions with dislocations. Most solutes are
Objective weak hardeners except for the (technologically)
Age- important class of interstitial solutes that induce
hardening anisotropic distortions of the lattice, e.g. tetragonal
Al-Cu distortions of C in Fe.
Al-Ag
steels
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
Al-Cu • For substitutional solutes, the numerator in the RHS, i.e. the reaction
force from the solute atoms is of order Gb 2/120, which is a small number.
Al-Ag This is so because the small differences in size between solute and
steels matrix atoms results in a small interaction energy with dislocations.
Thus they are weak obstacles and dislocations remain nearly straight
mecha- when interacting with solutes (“weak obstacles”, 7slides before this).
nisms
 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 deviates significantly from 180°. In
Objective
this case, the concentration dependence is easy to obtain.
Age-
The spacing between interstitials is inversely proportional
hardening
to the (square root of the) concentration, and so we can
Al-Cu insert a spacing into the standard (Orowan bowing)
Al-Ag formula to get the following, where A is a constant of order
steels unity:
mecha-
nisms  = Gb(√c/b) = G√c.
 27

Strength vs. solute content: examples

Examples:

a) Substitutional
solutes in Cu
Objective
Age- b) Interstitial
hardening solutes in
Al-Cu Nb, Fe
Al-Ag
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 practical high strength engineering materials. Iron-
Objective base, aluminum, nickel, titanium alloys all employ second
Age- phases to achieve high strength.
hardening • Quantitative relationships: from previous stereological
Al-Cu analysis (301 - lecture 4):
Al-Ag
steels 4r 1 − VV(α )
L3 = ; λ = L3 (α ) ;
mecha- 3 VV
nisms
4r 1 − VV(α ) 4r(1 − f ) 4r
λ = (α ) ≡ ≈
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,
Objective which increases the energy associated with the interface and hence
an additional force must be exerted on the dislocation to force it
Age- through the particle.
hardening
3) Order Hardening: passage of a dislocation through an
Al-Cu ordered particle, e.g. Ni3Al in superalloys, results in a disordered
Al-Ag lattice and the creation of antiphase boundaries.

steels 4) Stacking-fault Hardening: a difference in stacking fault

energy between particle and matrix, e.g. Ag in Al, increases flow
mecha- stress because of the different separation of partial dislocations in the
nisms two phases.
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 that has a different lattice parameter
Objective than the matrix. Ignoring differences in modulus for now, and
Age- setting a parameter, , that approximates a strain to characterize
hardening the magnitude of the effect. For

Al-Cu  = (aparticle – amatrix )/ amatrix

Al-Ag
steels
 = 7||3/2 G(rf/b)1/2

mecha- • This mechanism applies to the early stages of precipitation, e.g.

nisms 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
matrix and the particle. The distance over which this energy
Objective has to be created occurs at the entry and exit points and so
Age- the characteristic distance is of order b. Thus the force is
hardening dE/dx, or,
Al-Cu
Al-Ag 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
• A more realistic approach produces the following relationship.
Age-
hardening
Al-Cu  = 2G{/Gr}3/2(fr/b)1/2
Al-Ag
• Courtney defines a chemical hardening parameter, ch = /Gr, related to the
steels interfacial energy, modulus and particle size. This parameter is precisely
mecha- analogous to the same parameter used, e.g. in APB hardening. Chemical
nisms hardening applies only in the early stages of 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 can move through the
Age-
particles independently of one another. A more detailed analysis, not
hardening presented here, shows a square root dependence on volume fraction, with
Al-Cu particle size,

Al-Ag  = 0.7 G3/2 √(fr/b)

ord= APBE/Gb
steels
mecha- • Important for
nisms Ni-based superalloys
 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:
Objective F= b2(Gparticle-Gmatrix) = Gb2,

Age-
where  = (Gparticle-Gmatrix)/Gmatrix, a measure similar to that used in solution
hardening
hardening.
Al-Cu • More realistic estimates of modulus hardening lead to the following formula:
Al-Ag
 = 10-2 G 3/2 √{fr/b}
steels
mecha- • Think of modulus hardening as being caused by a temporary increase in
dislocation line energy while it resides within a particle.
nisms
 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 mechanism is
Age- operative.
hardening • Particle growth results in stronger particles; in most cases,
Al-Cu
however, coarsening takes place simultaneously which increases
the particle spacing. Orowan bowing takes over from particle
Al-Ag cutting at some point in the aging process.
steels • Particle hardening is essential to technological alloys, at least for
mecha- structural applications.
nisms
 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:
spacing = 3.1*27,600*0.25.10-9/ 600= 35.7 nm
Age- • Now we must estimate the volume fraction of particles for which we use the phase
hardening diagram, assuming that we are dealing with the equilibrium phase, , which is 54 w/o
Cu, and the  in equilibrium with it, 0.5 w/o Cu.
Al-Cu
• Wt. % Al = (54-4)/(54-0.5) = 93.5; wt. %  = 4-0.5/(54-0.5)=6.5
Al-Ag • 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