Precipitation hardening in metals

T. Gladman

Precipitation hardening has long been used to increase the strength of commercial alloys, such as quenched and tempered steels
and the duralumin type aluminium alloys. T he theoretical treatments of precipitation hardening are briefly considered. T he
equations for strengthening by ‘hard’ indeformable particles and by ‘soft’ deformable particles are presented, and the implications
are discussed. T hese lead to the concept of an optimum particle size for a given system, but the optimum can vary from system to
system depending upon the particle characteristics. A broad comparison is made between the increments in strength that occur
due to precipitation in commercial alloys and the predictions of the theories; an important contribution to these increments in
strength is shown to derive from variations in the volume fraction of precipitated particles that can be employed in the various
systems. MST /4157

T he author has recently retired from the Department of Materials, University of L eeds, L eeds L S2 9JT , UK. T his paper
formed part of the A
‘ dvances in physical metallurgy’ sessions of Materials Congress ’98 organised by T he Institute of Materials
and held at Cirencester on 6–8 April 1998.
` 1999 IoM Communications L td.

As F increases, so the bowing of the dislocation increases,

Introduction
Precipitation strengthening has been used extensively for a
considerable period of time, and in a wide range of metallic
systems. Essentially, precipitation strengthening is achieved
by producing a particulate dispersion of obstacles to
dislocation movement, the particulate dispersion being
achieved by a second phase precipitation process. The
degree of strengthening obtained is highly dependent upon
the metallic system involved, the volume fraction and size
of the particles, and the nature of the interaction of the
particles with dislocations. Precipitation strengthening is
used extensively in ferrous systems as, for example, in the
quench aging of low carbon steels, in microalloyed steels,
and in the tempering of martensite. This strengthening
mechanism is arguably more important in non-ferrous
systems, the most widely known being the Al–Cu and
Al–Si based alloys, and more recently the Al–Li based
alloys, where the opportunities for structural refinement
are restricted by the absence of allotropic changes. The
detailed interactions of the precipitated particles with dis-
locations is important to the magnitude of strengthening
observed. Various mechanisms have been proposed, involv-
ing particle bypassing by Orowan looping, or bypass slip,
or particle shearing. Theoretical treatments of these mechan-
isms are available and can be used, albeit with varying
degrees of success, to predict the degree of strengthening
to be expected from a given volume fraction of particles
and precipitated particle size. In practice, complications
arise from coherent particles with their attendant coher-
ency strains.
The purpose of the present paper is to examine
the nature of the various precipitation processes and
their attendant effects on the strength of the metal, and
to compare experimental observations with theoretical pre-
dictions.
i.e. h increases. The magnitude of the resistance force is
important in controlling the sequence of events. The
dislocation line tension force is a maximum when sin h=
1, or h=p/2 radians. If the particle is hard, such that the
resistance force F can be greater than 2T , then dislocations
will bypass the particle either by Orowan looping or cross-
slip and the particle will remain unchanged, i.e. non-
deformed (Fig. 2). The actual strength of the particle under
these circumstances becomes irrelevant, as the bypassing
operation becomes dependent only upon the interparticle
spacing. If, however, the strength of the particle is such
that the maximum resistance force is attained before sin h=
1, then particles will be sheared and the dislocation will
pass through the particle (Fig. 3). It therefore follows that,
for a given interparticle spacing (given volume fraction and
particle size), hard particles will give the maximum
precipitation strengthening, and this condition defines the
maximum degree of strengthening attainable. Soft particles
will give a lesser degree of strengthening.
HARD PARTICLES AND THE
OROWAN RELATIONSHIP
Consideration of the relationship between the applied stress
and the dislocation bowing, following Orowan,1 leads to
the Orowan equation
Dt =Gb/L . . . . . . . . . . . . . . (1)
y
line
tension particle
T T
dislocation

Precipitation hardening mechanisms

DISLOCATION–PARTICLE INTERACTION
The forces acting on a mobile dislocation in a stressed
metal containing a dispersion of second phase particles are
shown schematically in Fig. 1. Consideration of the balance
of forces between the line tension of the dislocation T and resisting
the resistance force of the second phase particle F shows force F
that 1 Balance of forces acting during particle resistance to
F=2T sin h dislocation movement

30 Materials Science and Technology January 1999 Vol. 15 ISSN 0267–0836

 Gladman Precipitation hardening in metals 31

4 Ashby–Orowan relationship

particle size, are virtually independent of the system

2 Dislocation meets hard undeformable second phase
particles: dislocation release at higher stresses may
occur by Orowan looping or by cross-slip
where Dt is the increase in yield stress due to the particles,
y
G the shear modulus of the matrix, b the Burgers vector of
the dislocation, and L the particle spacing. The value of L
in the Orowan equation is usually considered to be the
distance between particles arranged on a square grid in the
slip plane.
Ashby2 further developed this equation to take into
account the interparticle spacing, and the effects of
statistically distributed particles (after Foreman and Makin3
and Kocks4). The Ashby–Orowan relationship is given as
Dt =0·84(1·2Gb/2pL ) ln(x/2b) . . . . . . . (2)
y proportional to the product Gb in equation (3) for any
Application of the Taylor factor for polycrystalline mater-
ials, expressing the microstructural parameters in terms of
the volume fraction and real diameter and converting shear
stress to tensile stress, yields5
Ds =(0·538Gbf 1/2/X) ln(X/2b) . . . . . . . (3)
y strengthening varies by a factor of 4, from the lowest
where Ds is the increase in yield strength (MPa), G is the
y
shear modulus (MPa), b is the Burgers vector (mm), f is
the volume fraction of particles, and X is the real (spatial )
diameter of the particles (mm).
In the case of hard particles, therefore, the system
parameters involved are the shear modulus of the matrix
and the Burgers vector of the slip dislocations. The
microstructural parameters, i.e. the volume fraction and
provided that the particle shape remains essentially spheri-
cal. Geometric considerations may introduce changes in
the proportionality factors for needle or plate shaped
precipitates.
The increases in yield strength to be expected from small
volume fractions ( less than 0·5%) of particles of various
sizes in an iron matrix are illustrated in Fig. 4. The root
dependency of yield strength on the volume fraction is
reflected by the slope of 0·5 in logarithmic coordinates. The
dominant effect of the reciprocal of particle diameter in
equation (3) over the logarithmic term is clearly shown in
the diagram. Also shown in Fig. 4 is a comparison of the
predictions of the Orowan and Ashby–Orowan equations.
The effect of using the effective spacing in the Ashby–
Orowan equation rather than the minimum spacing in the
Orowan equation is to reduce the predicted precipita-
tion strengthening contribution. Experimentally observed
precipitation strengthening levels in microalloyed steels
have shown excellent agreement with the predictions of
the Ashby–Orowan equation.6
The implications of equation (3) for the precipitation
strengthening of other metals by hard particles is that the
magnitude of the strengthening contribution will be almost
given metal matrix (Table 1).
It can be seen that the major source of strengthening
variation derives from variations in the elastic rigidity
modulus, the Burgers vector being very similar for all
of the metals given in Table 1. Broadly, the degree of
modulus metal shown (magnesium) to the highest shown
(iron). Some variation in the degree of strengthening can
be expected from variations in the Burgers vector in the
logarithmic term in equation (3). Given a very small
particle diameter of, say, 10 nm, variations between the
Table 1 Shear moduli G and Burgers vectors b in
metal matrixes

G, b, Gb,
Matrix MPa nm Slip system MPa mm

Al 26200 0·286 (111) 110 7·5

Cu 48300 0·255 (111) 110 12·3
Fe 81600 0·248 (110) 111 20·2
Mg 17300 0·321 (0001) 112: 0 5·6
Ni 76500 0·249 (111) 110 18·9
3 Dislocation motion may continue through second Ti 45600 0·295 (0001) 112: 0 13·5
phase particles (particle cutting)

Materials Science and Technology January 1999 Vol. 15

32 Gladman Precipitation hardening in metals
5 Low energy position of flexible dislocation
Burgers vectors given in Table 1 would affect the degree of
strengthening only by about 9%, and with larger particles
this effect is reduced. Bearing in mind the opposing effects
of the Burgers vector in the linear and the logarithmic
terms, the elastic modulus of the matrix becomes even
more dominant than the data in Table 1 would suggest.
SOFT PARTICLES AND PRECIPITATION
STRENGTHENING
If the particle is ‘soft’, i.e. it is sheared by the dislocation,
as shown in Fig. 3, there are several effects which may be
involved in raising the stress level required for plastic
yielding. The deformation of a particle results in an increase
in the particle/matrix interfacial energy. The passage of a
dislocation through a particle may produce an antiphase
boundary with an associated disordering energy, or may
produce a stacking fault within the particle with its
associated stacking fault energy. The latter effect would
naturally require the stacking fault energy in the particles
to be significantly different from that of the matrix,
and must take into account the changes in the width
of the stacking fault from the matrix to the particle.
These strengthening effects are generally termed chemical
hardening.
A further important effect observed in precipitation
hardened alloys is associated with the strain fields around
coherent particles, particularly in the early stages of
precipitation. The atomic displacements associated with
the dislocation interact with the coherency strain fields
thus providing a greater strengthening effect than would
be expected from the precipitates/zones/clusters alone. Mott
and Nabarro7 have described the features involved in this
type of hardening. Briefly, a dislocation will bend to lie in
low energy positions with respect to the strain fields
(Fig. 5), and consequently any force applied must overcome
an enhanced number of obstacles without the assistance of
segments of dislocation in high energy positions before
stressing. The introduction of coherency strain hardening
introduces complications into the interpretation of age
hardening curves, as the effective obstacle volume fraction
is greater than the volume fraction of second phase particles.
These mechanisms have been reviewed extensively8,9 and
attention has been drawn to the effect of the maximum
restraining force (that can be exerted by a particle) on the
angle through which the dislocation can be turned (Fig. 1).
The significance of the critical angle to the increase in yield
stress is quite obvious, but a second and less obvious effect
is in the definition of the particle spacing. With a very
weak restraining force from the particle, the angle h (see
Fig. 1) approaches zero, and the number of particles per
unit length, n is given by
L Dt =4·1Ge3/2(rf /b)1/2 . . . . . . . . . . . (8)
n =3f/4r . . . . . . . . . . . . . . . (4)
L In the case of larger particles, where considerable flexing
or the mean spacing between particles L is given by
L =n−1 =4r/3f . . . . . . . . . . . . . (5)
L cation will have to overcome a larger number of obstacles
As the restraining force increases, so the convolutions of
the dislocation increase up to the limit where Orowan
looping occurs. The models developed for strengthening
must therefore relate the effective particle spacings to the
general parameters of the dispersoid, e.g. volume fraction
and particle size.
Materials Science and Technology January 1999 Vol. 15
6 Coherency strain hardening
In the case of chemical hardening the microstructure/
property relationships derived are typified by that for
order hardening10
Dt =(c1/2/b)(4r f/pT )1/2 . . . . . . . . . . (6)
y s
where c is the antiphase boundary energy, the boundary
resulting from the disordering effect of the penetrating
dislocation, and r is the mean radius of the particle in the
s
slip plane.
The variable T is the free line tension (De Wit–Koehler)
of the dislocation in an isotropic matrix,9 and is pro-
portional to the product Gb2. Equation (6) thus contains
parameters relevant to the matrix, arising from the effects
of the dislocation and the attendant force exerted by the
dislocation on the particle, and parameters relevant to the
nature of the particle (in this case the antiphase boundary
energy), as well as the geometric terms relevant to
the dispersion (particle size r ) and volume fraction. The
s
importance of this equation lies in the increase in strength
that accompanies an increased particle size at a given
volume fraction. A similar form of equation also applies to
stacking fault strengthening, but not to the simple increase
in interfacial area between the particles and matrix due to
particle shearing11 where
Dt =2(c /b)3/2/(bL T )1/2 . . . . . . . . . . (7)
y s
The equation indicates an increase in strengthening as the
particle size decreases (i.e. as L decreases). In general,
however, the interfacial energy is often regarded as being
small, when compared with antiphase boundary energies,
and is therefore neglected.
In the case of coherency strain hardening, the dislocation
interacts with the coherency strain field in the matrix
around the (coherent) particle. When the particles are
relatively small, one solution, relevant to very limited
dislocation bending, yields
y
of the dislocations occurs as a result of the spacing of
individual particles (Fig. 5), any movement of the dislo-
per unit length
Dt =0·7Gf 1/2e1/4(b/r)3/4 . . . . . . . . . . (9)
y
In both Equations (8) and (9), the misfit strain e is the
fractional dilation of the coherent lattice irrespective of
sign. For small particles, coherency strain hardening

Work hardening rate MPa
Shear proof stress MPa
contraction
Contraction %
shear
proof stress
work
hardening
rate
as quenched Aging time h
7 Variation of shear proof stress (tensile 0·1%PS/3) and
initial work hardening ((tensile 0·1%PS–0·05%PS)/3)
with time for Ni–Fe–Cr alloy containing L1 type
2
particles
increases with increasing particle size, whereas for larger
particles, the coherency strain hardening decreases with
increasing particle size, giving rise to a maximum in the
strengthening at a critical particle size which is of the
order of
r/b=Be−1 . . . . . . . . . . . . . . (10)
irrespective of the volume fraction. As pointed out pre-
viously,9 the upper limit of this form of strengthening is
imposed by the transition to the classical Orowan looping
process (Fig. 2). Again, this process is not only dependent
upon the matrix properties and geometric feature of the
dispersion, but also on the nature of the precipitated
particle – in this case, the fractional misfit strain.
The net effect of increasing the particle size in these
systems is illustrated in Fig. 6, using the ‘small particle’ and
‘large particle’ coherency strengthening equations. Initially
the shear strength in the slip plane increases with increasing
size, and this would be true not only for fine particle
coherency strain hardening, but also for stacking fault
hardening, and for order hardening. At some transitional
stage, e.g. as defined by equations (8)–(10), the mechanism
changes and the precipitation strengthening is reduced,
whether this is by the ‘large particle’ model shown in Fig. 6,
or by the classical Orowan looping process described
above. As illustrated in Fig. 6, a maximum strengthening
will be attained at the critical particle size, and the
magnitude of this maximum will be dependent upon
the magnitude of the fractional coherency strain and the
volume fraction of particles. As each of the strengthening
mechanisms show a square root dependency of the strength
increment on the volume fraction of particles, the peak
strength will occur at a given particle size (all other things
being equal) irrespective of the volume fraction. Enhanced
hardening by increasing the coherency strain will reduce
the particle size at which the maximum strength occurs
and will therefore increase the maximum strength attainable
at a given volume fraction. Similar effects are predicted for
the other dispersion strengthening mechanisms involving
‘soft’ particles, together with the limiting strength imposed
by the ‘hard’ particle Orowan looping mechanism, which
is independent of the particle type.
The strength of the dislocation–particle repulsion force
in connection with ‘soft’ particle strengthening is important
in dictating the critical particle size at which the transition
to ‘hard’ particle strengthening occurs and, therefore, the
magnitude of the strengthening contribution at this tran-
sitional particle size. Nicholson12 has suggested that,
irrespective of the ‘hardness’ of hard particles, there will be
a transition to particle cutting mechanisms at very small
particle sizes.
One other consequence of the change from particle
cutting to Orowan looping is found in the work hardening
characteristics of the material. When particle cutting occurs,
Gladman Precipitation hardening in metals 33
°C
Temperature
Cu wt-%
8 Aluminium rich Al–Cu binary diagram
the dislocation interactions may be increased only slightly
giving rise to little difference in the work hardening rate.
However, with Orowan looping and cross-slip, a consider-
able enhancement of work hardening can be found due to
the enhanced dislocation interactions (Fig. 7).
Precipitation hardening processes
The precipitation hardening process requires that the
second phase is sufficiently soluble to allow extensive
dissolution at an elevated temperature – the solution
treatment temperature – and that the solubility is consider-
ably reduced at lower temperatures – the aging temperature.
The extent of precipitation is thus dependent on the
equilibrium phase diagram for the alloy system which
controls the extent of dissolution and precipitation at
appropriate solution and aging temperatures, and hence
controls the volume fraction of fine precipitated particles
that contribute to precipitation hardening by the various
mechanisms described above.
The variations in permissible volume fractions of particles
in different systems can be about 2 orders of magnitude.
For example, in the Al–Cu system, up to 4 wt-%Cu can be
dissolved in the aluminium at near eutectic temperatures,
giving rise to about 5 vol.-% of h (CuAl ) phase after
2
precipitation. In the case of microalloyed steels, however,
the solubility of most of the microalloy carbides and
nitrides is limited, generally to less than 0·1 wt-%, giving
rise to 0·1 vol.-% of carbide or nitride after precipitation.
Thus the extent of precipitation hardening in the peak aged
condition can not be judged from the shear modulus of the
matrix alone (see Table 1), but depends on the solubility of
the second phase.
CLASSICAL PRECIPITATION HARDENING
SYSTEMS
The development of the microstructure is not often confined
to simple precipitation of the equilibrium phase. The classic
precipitation sequences in the case of Al–Cu alloys have
been established for at least 60 years, and the story of the
development of Guinier–Preston zones, followed by h◊, h∞,
and the equilibrium h, is well established. The solvus
temperatures of these metastable phases (Fig. 8) provides a
firm basis for successful heat treatment of the duralumin
type alloys. These complex precipitation sequences are seen
in virtually all precipitation hardened alloys. In Al–Cu–Mg
alloys, GP zones are formed, followed by the ordered S∞,
Materials Science and Technology January 1999 Vol. 15
34 Gladman Precipitation hardening in metals

before the equilibrium S (Al CuMg) phase. In Al–Mg–Si when tempering is carried out at temperatures above 300°C.
2
alloys, GP zone formation is followed by the ordered b∞, The volume fraction of e-carbide would be somewhat less,
before the formation of the equilibrium Mg Si precipitate. about 2%, when tempering is carried out at low temper-
2
A similar sequence is also observed in Cu–Be alloys, where atures (100–200°C) due to the relatively high solubility of
c (CuBe) is the stable intermetallic compound. A direct e-carbide, but of course the particle size is much finer and
consequence of the formation of these intermediate meta- capable of very large precipitation strengthening contri-
stable stages is that the age hardening curve may reflect butions. One of the main problems in assessing the degree
these changes, giving rise either to multistage hardening of precipitation hardening in these steels is the coincident
or to a single hardening stage, depending on the aging variation in effective grain size, whether this is the
temperature relative to the solvus temperature for a martensite plate dimension or the subgrain structure, and
particular intermediate stage. in dislocation density.
The role of vacancies has long been acknowledged in the From the standpoint of precipitation, microalloyed steels
precipitation process. The enhanced vacancy concentration provide an illustration of the development of a dispersoid
formed by quenching from the solution temperature leads which is exclusively confined to metals showing allotropic
to an enhanced rate of solute diffusion, and therefore an transformation, i.e. interphase precipitation. The microalloy
increased rate of clustering. As the vacancy concentration carbides/nitrides are wholly or partially dissolved at
decreases, so the rate of clustering decreases. The vacancies elevated temperatures in the austenite temperature range,
may eventually condense to form dislocation loops, which usually 1150–1300°C. The solubilities of the various micro-
can act as nucleation sites for precipitation or may escape alloy carbides and nitrides are defined by the solubility
to various sinks, such as grain boundaries. The loss of product
vacancies at these sinks can give rise to precipitate free
k =a a /a . . . . . . . . . . . . . (10)
zones. The effect of solute additions to these systems, e.g. s M X MX
the addition of lithium13 or of beryllium,14 is to retard the where a is the activity of the microalloy in solution and
M
escape of vacancies and also to reduce the rate of formation a is the activity of the interstitial in solution, in equilibrium
X
of dislocation loops by forming solute–vacancy pairs, with the compound MX. The activity coefficients ( f and
M
thereby changing the rates of clustering and of precipitate f ), and the activity of the reaction product (MX), are
X
formation. In the case of lithium, additions of 0·7 wt-%Li commonly assumed to be unity, and the solubility product
introduce an additional precipitated phase, AlLiSi, which can be written as
can coexist with Si–Mg solute clusters.
k =[M][X] . . . . . . . . . . . . . (11)
Double aging treatments can be used to produce a fine s
distribution of GP1 zones at a temperature below the zone where [M] and [X] are solute concentrations (in wt-%).
solvus, followed by zone coarsening at a higher temperature. The solubility product increases with increasing temper-
Such treatments are important in reducing precipitate free ature according to the Arrhenius equation
zones, and the decision to use double aging treatments or
log k =B−(A/T )
to use alloying in order to optimise the structures and s
properties may well be influenced by economic factors. where B and A are constants and T is the absolute
The complexities of the many classic precipitation temperature. The values of A and B for various microalloy
hardening sequences have been well documented, but the carbides and nitrides are shown in Table 2, together with
coexistence of clusters, and of one or more coherent or the solubility products in austenite at 1200°C. It can be
semicoherent intermediate phases, can lead to difficulties in seen that most of the simple compounds have a solubility
relating the change in properties to the microstructure in a product of 10−3–10−2, but exceptions are vanadium carbide
quantitative manner. with a solubility product in excess of 1, and titanium nitride
with a value less than 10−6.
In commercial steels, due account has to be taken of the
PRECIPITATION HARDENING IN simultaneous presence of carbon and nitrogen, and also
ALLOTROPIC SYSTEMS the fact that many steels may contain more than one
Although there are examples of classic precipitation microalloy together with aluminium. Aluminium nitride,
hardening reactions in ferrous systems, such as the with its hcp structure, forms a separate precipitate, while
precipitation of iron carbides in a-Fe during the quench the microalloy carbides and nitrides enjoy mutually com-
aging of ferrite, and the use of c∞ (Ni Al Ti ) in austenitic plete solid solubility, all the structures being fcc with similar
3 x 1−x
stainless steels, the allotropic changes in transformable but not identical lattice parameters. Treatments of the
steels introduce variants in the development of precipitation initial solid solubility have been presented by Hudd et al.16
hardened microstructures. One of the most extensively used and by Adrian,17 and have been considered elsewhere.5
classes of steels involving precipitation hardening has the On cooling through the austenite range, precipitation
tempered martensitic structure. These transformable engin- of microalloy carbonitrides (and aluminium nitride) is
eering steels are heated into the austenitic temperature extremely sluggish, and can be neglected at most practical
range, where the solubility of iron carbide is increased cooling rates. However, during the austenite to ferrite, or
dramatically ( by a factor of at least 40) when compared austenite to pearlite, transformation there is a step change
with the maximum solubility of 0·02 wt-%C in the bcc in solubility, all microalloy carbides and nitrides being less
a-Fe. Quenching to avoid ferrite formation allows the soluble in the ferrite than in the austenite at these low
development of the hard but brittle bct martensitic
structure, which is effectively a heavily supersaturated
solution of carbon in a-Fe. Tempering such structures Table 2 Solubility products k of microalloy carbides and
s
nitrides in austenite at 1200?C
allows the precipitation of the metastable hexagonal
e-carbide (Fe C), or the stable cementite (Fe C), or, in Component A B k (1200°C) Structure
2·4 3 s
the case of secondary hardening steels, alloy carbides such
as Mo C or V C . In many ways, these precipitation VC 9500 6·72 1·9 fcc
2 4 3 VN 8700 3·63 5·2×10−3 fcc
systems mirror those described for the aluminium alloys, NbC 7900 3·42 1·1×10−2 fcc
i.e. from supersaturated solution, through solute clusters NbN 8500 2·80 1·1×10−3 fcc
and metastable phases, to the equilibrium phase. TiC 10475 5·33 1·7×10−2 fcc
Ultrahigh strength steels usually contain about 0·4 TiN 15020 3·82 4·2×10−7 fcc
AlN 6770 1·03 2·7×10−4 hcp
wt-%C which will allow precipitation of some 6%Fe C
3

Materials Science and Technology January 1999 Vol. 15


9 Interphase precipitation as result of ferrite growth by
‘ledge’ mechanism
temperatures. Also, the mobility of the various solutes in
ferrite is much higher than that in austenite at the same
temperature. The result of these changes is the precipitation
of microalloy carbonitrides at the austenite/ferrite inter-
face, giving the characteristic interphase distribution with
rows of fine and relatively uniform precipitated particles.
Honeycombe and his co-workers18 have suggested that the
interphase morphology arises as a result of the ledgewise
growth of the ferrite grains (Fig. 9), the size and spacing of
the particles being dependent upon the transformation
temperature and the rate of advance of the ferrite ledges
(or growth rate of the ferrite). The particles developed in
this way are fairly uniform in size, and the sizes commonly
range from 5 to 20 nm. The particle size can be controlled
by controlling the temperature, and rate of transformation.
It is interesting to note that this same interphase precipi-
tation can be seen in higher carbon steels where the
austenite transformation product is the eutectoid, pearlite,
rather than the ferrite of low carbon steels.
Strengthening increments
In general, the observed strengthening increments observed
in ‘hard’ particle systems are described by the Ashby–
Orowan relationship (equation (3)). In ‘soft’ particle sys-
tems, although particle shear is clearly observed, there is
often some considerable doubt as to the detailed mechanism
of strengthening. The experimental evidence for the smaller
particles often shows the root dependency on the volume
fraction, and an increase in strength as the particle size
increases (after the completion of precipitation), often with
the root radius dependency. In the case of aluminium alloy,
for example, with a volume fraction of particles of about
0·05 and a coherency strain of 0·01 (a 1% misfit), the
maximum yield stress (in shear) that would be expected
from coherency strengthening is of the order of 130 MPa.
Conversion to a tensile strength in polycrystalline material
would produce an expected proof stress increment of some
200–300 MPa. An examination of data from the specifica-
tions for aluminium alloys allows an assessment of the
strengthening increment to be obtained from the difference
in proof stress between the annealed and the age hardened
Table 3 Strengthening increments in aluminium alloys
0·2% proof stress, MPa
Alloy Annealed Age hardened Difference
2024 75 395 320
2219 75 290 215
Gladman Precipitation hardening in metals 35
10 Dispersion strengthening in low carbon steels
conditions (Table 3). Obviously these estimates are very
crude, neglecting the changes in solute concentration, and
the possible changes in coherency strain as particles grow
(due to the incorporation of interface dislocations), but
show some reasonable agreement with the prediction. More
precise comparisons would require specific knowledge of
the strengthening mechanism and the parameters relevant
to that mechanism, e.g. coherency strains, surface energies,
stacking fault energies, disorder energies, or modulus
differences.
Again, with martensitic steels, the prediction of yield
strength is difficult. In the early stages of carbide precipi-
tation, the strength changes are clouded by the dramatic
loss of strength to be expected from carbon depletion in
the matrix; because carbon is an interstitial solute giving a
large tetragonal distortion, precipitation hardening causes
only a marginal increase in strength over the solid solution
(martensite). One may also question the additivity of
strengthening mechanisms in such structures with their
submicrometre plate sizes, forest dislocations, and varying
solute contents. Further complications may arise in very
lightly tempered martensite due to the transition to carbide
cracking and/or brittle fracture. In more heavily tempered
martensites, the particle spacing is increased dramatically
and yielding occurs by the Orowan mechanism, the yield
stress decreasing with increasing particle size. Some indi-
cations of the possible contribution in martensitic steels
may be obtained from the absolute strength level of
ultrahigh strength lightly tempered martensitic steels, where
0·2% proof stress levels of 1·4–1·7 GPa are obtained. In a
0·4%C steel, the formation of 6 vol.-%Fe C ( f =0·06),
3
would produce a precipitation strengthening contribution
of some 0·8 GPa, with a similar contribution arising from
the fine submicrometre grain size.
Precipitation hardening is used to great advantage in
microalloyed steels. Although very fine particles can be
sheared, as pointed out by Nicholson, the strengths of these
fine alloy carbonitrides and their small volume fraction are
such that the transition from particle deformation to
Orowan looping must occur at extremely small particle
sizes. Thus 5 nm particles are capable of resisting deforma-
tion, or require near looping stresses to cause shear. The
yield stresses of these steels therefore contain a contribution
from the precipitation strengthening which is described
quantitatively by the Ashby–Orowan equation. The small
volume fractions and particle sizes are indicated in Fig. 10,
which illustrates the magnitude of the precipitation contri-
bution. The increase in yield strength for the low carbon
Materials Science and Technology January 1999 Vol. 15
36 Gladman Precipitation hardening in metals
11 Precipitation strengthening in medium carbon steels: after Sawada et al.19
miroalloyed steels shows a remarkable agreement with the
Ashby–Orowan equation to the extent that the equation is
used directly in alloy design to produce steels of given
properties.6 Interestingly, the use of vanadium microalloying
in medium and high carbon steels produces very similar
levels of precipitation hardening,19 as shown in Fig. 11,
when due account is given to secondary effects such as
fraction of pearlite, pearlite spacing, and ferrite grain size.
Summary
Precipitation strengthening in metals has long been a
common strengthening method. This brief overview has
discussed the theoretical approaches which make the
distinction between so called ‘hard’ particles, which are
bypassed by dislocations, and the ‘soft’ particles, which
become deformed when plastic yielding occurs. The
Ashby–Orowan equation describes the precipitation
strengthening due to ‘hard’ particles, the strength incre-
ment being controlled by the matrix characteristics and
the particle distribution. Other relationships exist for the
strengthening contributions of ‘soft’ particles, and these are
dependent on the characteristics of the precipitates as well
as the above factors. Soft particle strengthening increases
with increasing particle size, whereas hard particle strength-
ening decreases with increased particle spacing (increasing
particle size). This gives rise to the noted transition from
particle shearing to dislocation looping at some critical
size. The critical size of the precipitated particles is
decreased as the stiffness of particles increases, so that
the transition to Orowan looping occurs with very small
particles in the case of alloy carbides in steel, but at a
significantly larger critical particle size when the particles
are soft, such as is the case for many classic precipitation
hardening aluminium alloys.
The extent of precipitation hardening generally increases
as the square root of the volume fraction of particles (other
things being equal), and phase equilibrium becomes
important from the standpoint of solubility at solution and
Materials Science and Technology January 1999 Vol. 15
precipitation temperatures. Consideration is given to broad
classes of commercial alloys, showing the very significant
yield strength increments that can arise from precipitation
hardening.
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