What Is Behind The Inverse Hall-Petch Effect in Nanocrystalline Materials?
What Is Behind The Inverse Hall-Petch Effect in Nanocrystalline Materials?
What Is Behind The Inverse Hall-Petch Effect in Nanocrystalline Materials?
www.elsevier.com/locate/actamat
Materials Science and Engineering Program, University of Texas at Austin, Austin, TX 78712, USA
Abstract
An inverse Hall–Petch effect has been observed for nanocrystalline materials by a large number of researchers. This effect implies that
nanocrystalline materials get softer as grain size is reduced below a critical value. Postulated explanations for this behavior include dis-
location-based models, diffusion-based models, grain-boundary-shearing models and two-phase-based models. In this paper, we report
an explanation for the inverse Hall–Petch effect based on the statistical absorption of dislocations by grain boundaries, showing that the
yield strength is dependent on strain rate and temperature and deviates from the Hall–Petch relationship below a critical grain size.
Ó 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
1359-6454/$30.00 Ó 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2007.02.021
3750 C.E. Carlton, P.J. Ferreira / Acta Materialia 55 (2007) 3749–3756
namely dislocation-based models [13–17], diffusion-based dence related with the IHPE has indicated that many of
models [18,19], grain-boundary-shearing models [20–23] the proposed models may be inadequate for explaining
and two-phase-based models [24–29]. the IHPE. Among of the most important experimental
The dislocation-based models assume that dislocation findings in this regard are several in situ transmission elec-
motion is the primary agent for plastic flow in nanocrystal- tron microscopy (TEM) observations of dislocation
line materials and explain the IHPE by taking into account motion during tensile deformation and nanoindentation
the ways that very small crystallite sizes can affect the of nanocrystalline materials [38–45]. This is relevant
behavior of dislocations. For example, one model considers because many of the models listed above are based on
how the energy of a dislocation may be reduced by a very the assumption that dislocation motion does not play a sig-
small crystal and how the change in the dislocation’s nificant role in the deformation of nanocrystalline materi-
energy could affect its motion and lead to the IHPE [13]. als. In addition, many of the same TEM studies have
Another dislocation-based model considers how a nano- also shown that plastically deformed nanocrystalline mate-
crystalline grain could affect the operation of Frank–Reed rials contain a very low accumulated dislocation density.
dislocation sources [14]. Additionally, molecular dynamics These observations are contrary to models that rely on
simulations of some metals indicate that deformation of strain hardening as the means to understand the Hall–
nanocrystalline materials can occur via a dislocation mech- Petch relationship [13,15].
anism [16]. Finally, a recent experiment, where the strain rate sensi-
The diffusion-based models assume various diffusion tivity of nanocrystalline copper was determined by nanoin-
processes to explain the IHPE. In one model, the IHPE dentation, revealed that nanocrystalline materials should
is attributed to the effect of Coble creep in strain rate be more strain-rate sensitive than their microcrystalline
regimes and temperature ranges where it is not normally counterparts, but not as sensitive as Coble creep models
seen [18]. Some models use diffusion processes in combina- would suggest [46].
tion with other mechanisms to explain the IHPE. For In the context of this lively and continuing discussion,
example, one model explains the IHPE using a combina- the purpose of this paper is thus to suggest a model for
tion of dislocation motion and creep [15], while another the IHPE in nanocrystalline materials based on the nature
model explains the IHPE as being due to grain-boundary of dislocation absorption by grain boundaries. The paper
shear by a thermally activated grain-boundary-shearing will show that below a critical grain size, typically at the
mechanism [19]. nanoscale, dislocations are more easily absorbed by grain
A third set of models suggest that grain-boundary shear- boundaries. The model matches in situ TEM observations,
ing is the dominant cause for the IHPE behavior. Grain- which show that dislocations remain relatively active in
boundary shearing has been observed in various molecular nanocrystalline materials [38–45], while the dislocation
dynamics simulations [20,22,23]. In these simulations, density remains considerably low.
grain-boundary shearing begins to dominate dislocation
motion as the primary means of deformation at very low 2. A model for the inverse Hall–Petch behavior
grain sizes. There are also analytical models that use
grain-boundary shearing to explain the IHPE. In one of Let us start by considering that dislocations are line
these models, grain boundaries and crystalline grains are defects with length l. As we will see later, from an atomistic
considered to be separate phases, much like the two-phase point of view, this length becomes increasingly important
models mentioned below. In this model the grain boundary as the material’s grain size reaches the nanoscale. Next,
is assumed to deform by an athermal grain-boundary-shear we shall assume that the nature of grain boundaries is
mechanism while the grain interior behaves normally [21]. not scale dependent. In fact, several investigations have
Finally, another set of models explain the IHPE by con- revealed that the structure and width of grain boundaries
sidering a nanocrystalline material to be a composite mate- is essentially the same for nanocrystalline materials and
rial with at least two phases, namely a grain-boundary coarser-grained materials [47–49]. Finally, we shall con-
phase and a grain-interior phase [23–28]. In one of these sider that any grain boundary exhibits a specific probability
models, the grain boundary is considered a continuous to absorb a dislocation, on an atom by atom basis, as the
material that is strengthened by nanocrystalline grains in dislocation approaches the grain boundary. However,
much the same way that conventional materials can be instead of considering the particular crystallography of a
strengthened by precipitates [27]. In another model, the grain boundary, the model proposed herein acknowledges
grain-boundary material and the lattice material are the existence of distinct grain-boundary structures by
assumed to have different yield strengths [26]. A third assuming that each grain boundary exhibits a specific acti-
model assumes quite special mechanical properties for the vation energy for dislocation absorption. This assumption
grain boundary [28]. will be discussed later in the paper in greater detail.
Considering the aforementioned volume and good qual- Assuming the probability of a dislocation being
ity of the work completed on explaining the IHPE in met- absorbed by the grain boundary to be Pdis and the proba-
als, it is necessary to justify the publication of a new model. bility of an individual atom on the dislocation core making
This motivation arises because recent experimental evi- the jump to be Patom, a relatively simple analysis using a
C.E. Carlton, P.J. Ferreira / Acta Materialia 55 (2007) 3749–3756 3751
Bernoulli distribution function can made. The Bernoulli boundaries is fast enough to be relevant at reasonable
function is a discrete distribution having two possible out- strain rates. Assuming that the strain in the material is
comes, labeled by n = 0 and n = 1, in which n = 1 (‘‘suc- accommodated by the motion of dislocations, it is possible
cess’’) occurs with probability p and n = 0 (‘‘failure’’) to determine the average time t during which an individual
occurs with probability (1 p), where 0 < p < 1. Thus, p dislocation is able to traverse the entire grain. As the strain
is the probability of an atom successfully jumping into rate associated with the motion of one single dislocation is
the grain boundary in a single attempt, whereas (1 p) is given by
the probability of an atom failing to make the jump in a
x b
single attempt. With this, we can write for Pdis, the follow- e_ ¼ t ð5Þ
d d
ing equation:
N J where x is the average distance moved by the dislocation
P dis ¼ P Jatom ¼ ½1 ð1 pÞ ð2Þ
during the time t, then the average time t taken by each dis-
where J is the total number of atoms on the dislocation location to cross the entire grain (x ¼ dÞ is given by
core jumping into the grain boundary. A value for J t ¼ b=ð_edÞ. Hence, the N factor can be rewritten as
can be determined by multiplying the atomic linear den- N ¼ ðbC / mÞ=_ed ð6Þ
sity f of the dislocation core by the length l of the dislo-
cation line. As the length of the dislocation line is where the symbols have the same meaning as before. As a
proportional to the grain size d, the variable J is thus re- result, Eq. (4) shows that the probability of dislocation
lated to the grain size. N is the number of attempted absorption by grain boundaries is strongly dependent on
jumps by dislocation core atoms to the grain boundary the grain size d and the strain rate e_ . As the absorption
during an average time t between absorption of disloca- of dislocations by grain boundaries will obviously interfere
tions. N is defined by the product of the Debye frequency with grain-boundary strengthening, Eq. (4) predicts that
m, the time t and the Schmid factor Cu. Thus, the (1 p)N the greater the grain-boundary absorption that can occur,
term in Eq. (2) represents the chance for one atom failing the more deviation from the Hall–Petch behavior (Eq.
to make the jump after N attempts and the term (1)) should be expected.
[1 (1 p)N] describes the chance of one or more jump We are left with the task of establishing a correlation
attempts succeeding. The probability p is thus a modified between the probability of dislocations being absorbed
Boltzmann factor that represents the chance of an atom’s by grain boundaries and the classical Hall–Petch equa-
single jump attempt succeeding, when assisted by a shear tion. To start, consider that the leading dislocation, in a
stress s. Hence, p is given by pile-up of n dislocations, experiences a force due to (i)
the resolved shear stress, s, (ii) the other (n 1) disloca-
p ¼ exp DG þ sb3 =k B T ¼ expðMÞ ð3Þ tions and (iii) a backward force due to the internal stress
where DG is the activation energy for atomic migration, b is s0 produced by the grain boundary. According to the clas-
the Burgers vector, kB is Boltzmann’s constant and T is sical Hall–Petch equation, the internal stress s0 is consid-
temperature. M is thus a mobility factor. As we are describ- ered from the point of view of a rigid grain boundary,
ing the jump of atoms from the dislocation core to the where dislocations pile up. This is the case where Pdis = 0
grain boundary, DG is strongly dependent on the specific in Eq. (4). But, what happens when Pdis 6¼ 0? In this case,
structure of the grain boundary, thereby implicitly taking the grain boundary is no longer a rigid barrier and thus
into account the crystallographic nature of the grain the internal stress s0 should be reduced to a term
boundary. Therefore Eq. (2) can be rewritten as s0(1 Pdis). Assuming that the leading dislocation moves
N J
forward towards the grain boundary by a distance dx, the
P dis ¼ f1 ½1 eM g ð4Þ work done by the resolved shear stress can be described
From Eq. (4), immediate physical insight is possible. Be- by W1 = nbsdx. Therefore, the motion of the leading
cause the term in the curly brackets is always less than 1, dislocation results in an increased interaction with the
higher values of J will lower the probability Pdis of a dislo- grain boundary, which can be described by W2 =
cation being absorbed by the grain boundary. Hence, the bs0(1 Pdis)dx. At equilibrium, W1 = W2 and, hence,
larger the grain size d, the larger the value of J will be, the resolved shear stress acting on the leading dislocation
and the lower will be the probability Pdis. On the other of a pile-up composed of n dislocations equals the back-
hand, as N is increased, the probability of all jump at- ward force due to the internal stress s0 produced by the
tempts failing decreases and thus the probability Pdis is in- grain boundary. This can be expressed by
creased. The reason for this behavior is due to the fact that ns
N is the number of attempted jumps by dislocation core s1 ¼ s0 ¼ ð7Þ
ð1 P dis Þ
atoms to the grain boundary during an average time t be-
tween absorption of dislocations. Hence, as the time t is in- where the symbols have the same meaning as before.
creased, N increases and thus the probability Pdis of Assuming n = ds/lb [35,36], where d is the grain size, s is
dislocation absorption increases. In other words, this is a the resolved shear stress, l is the shear modulus and b is
question of whether the absorption of dislocations by grain the Burgers vector, Eq. (7) can be rewritten as
3752 C.E. Carlton, P.J. Ferreira / Acta Materialia 55 (2007) 3749–3756
an inverse Hall–Petch behavior. In fact, a linear regression There are several possible explanations for this. It is pos-
performed on all the data, except for the data reported by sible that the samples indicating an IHPE were flawed in
Wang et al. [9], gives a correlation factor R2 = 0.93. For some way, for instance incomplete densification or the pres-
some of the reported data [58,59] a linear regression fit ence of an additional amorphous phase. It is also possible
gives correlation factors of R2 = 0.98 and R2 = 0.84, that, due to differences in the microstructure, some of the
respectively. materials exhibited IHPE behavior while others did not.
According to our model, a lack of inverse Hall–Petch The theory presented above can rationalize this anomaly if
behavior in Ni would not be surprising. In fact, due to the samples can be shown as having grain boundaries with
the high melting temperature of Ni and consequent high substantially different activation energies of absorption.
activation energy, we could expect it effectively to halt Overall, the data obtained from individual research
grain-boundary absorption of dislocations at reasonable groups and shown in Fig. 4 seem to support the IHPE.
strain rates. However, as mentioned above, polycrystalline However, when the data from single research groups are
materials exhibit a distribution of grain sizes and grain- combined and viewed as a whole, the result is still
boundary structures, which may lead to some form of devi- ambiguous.
ation from the classical Hall–Petch relationship. In the future, to overcome this ambiguity, it will become
The model also suggests that the variation of results, important to report the strain rate and the temperature
such as those in Fig. 3, may differ due to differences in used in the experiments, as well as to characterize the grain
experimental conditions. If the strain rates used in the size distribution and grain-boundary structure.
experiments differed significantly, or different methods for
producing nanocrystalline materials lead to dissimilar 4. Conclusions
grain-boundary distributions and grain size distributions,
this in turn could result in distinct abilities for absorbing The model presented herein uses a simple argument to
dislocations. produce a simple equation that can be used to make some
In the context of this discussion, it is valuable to con- interesting and useful predictions about the effects of grain-
sider the expected behavior of nanocrystalline copper, boundary strengthening in nanocrystalline materials. Sim-
which has been widely investigated in the open literature ply, the model assumes a probability for atoms on a dislo-
[2,4,7,8,46,61–73], According to the model outlined above, cation core to be absorbed by the grain boundary. The
copper would be more likely to exhibit an inverse Hall– larger the grain size, the larger must be the number of
Petch effect and/or exhibit a lower CYS than nickel. This atoms absorbed by the grain boundary, if the dislocation
is because the activation energy for dislocation absorption is also to be absorbed. Thus, for larger grain sizes, the
by grain boundaries for copper is lower than that of nickel. probability for dislocation absorption by the grain bound-
However, upon examination of the experimental results ary is lowered. The predictions provided by the model can
obtained for nanocrystalline copper (Fig. 4), the results be tested in the laboratory, keeping in mind that the strain
reported are even more difficult to interpret than the results rate, the temperature, grain-boundary distribution and
for nickel. As shown in Fig. 4, the two sets of data reported grain size distribution are all important parameters to be
by Sanders et al. [8] appear to support the IHPE for a crit- considered. The results of future experiments dealing with
ical grain size of 16 nm. On the other hand, the remainder these effects will help confirm this model and lead to an
of the data combined are highly inconclusive. increase in our understanding of the mechanical properties
of nanomaterials.
Acknowledgements
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