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Relationship between the parting limit for de-

alloying and a particular geometric high-density
site percolation threshold

D.M. Artymowicz, J. Erlebacher & R.C. Newman

To cite this article: D.M. Artymowicz, J. Erlebacher & R.C. Newman (2009) Relationship between
the parting limit for de-alloying and a particular geometric high-density site percolation
threshold, Philosophical Magazine, 89:21, 1663-1693, DOI: 10.1080/14786430903025708

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Philosophical Magazine
Vol. 89, No. 21, 21 July 2009, 1663–1693

Relationship between the parting limit for de-alloying and a

particular geometric high-density site percolation threshold
D.M. Artymowicza*, J. Erlebacherb and R.C. Newmana
a
Department of Chemical Engineering and Applied Chemistry, University of Toronto,
200 College Street, Toronto, Ontario, M5S 3E5 Canada; bDepartment of Materials
Science and Engineering, Johns Hopkins University, MD 21218, USA
(Received 6 October 2008; final version received 7 May 2009)

The parting limit or de-alloying threshold for electrolytic dissolution of the

more reactive component from a homogeneous fcc binary alloy is usually
between 50 and 60 at%. The system that has been most studied, dissolution
of Ag from Ag–Au, shows a parting limit close to 55 at% Ag. Here, Kinetic
Monte Carlo (KMC) simulations of ‘Ag–Au’ alloys and geometric
percolation modeling are used to study the relationship between this
parting limit and the high-density site percolation thresholds pc(m) for an
fcc lattice, subject to the rule that atoms with coordination greater than
nine are prevented from dissolution. The value of pc(9) is calculated from
geometric considerations to be 59.97  0.03%. In comparison, using KMC
simulations with no surface diffusion and no dissolution allowed for ‘Ag’
atoms with more than nine total neighbors, the parting limit is found to be
slightly lower (58.4  0.1%). This slight discrepancy is explained by
consideration of the local atomic configurations of ‘Ag’ atoms – a few of
these configurations satisfy the percolation requirement but do not sustain
de-alloying, while a larger number show the converse behavior. There is
still, however, an underlying relationship between the parting limit and the
percolation threshold, because being at pc(9) guarantees a percolation path
in which successive ‘Ag’ atoms share at least one other ‘Ag’ neighbor. With
realistic kinetics of surface diffusion for ‘Au’, the parting limit drops to
54.7  0.3% because a few otherwise inaccessible dissolution paths are
opened up by surface diffusion of ‘Au’.
Keywords: alloys; atomistic simulation; clusters; corrosion

1. Introduction
De-alloying is the selective electrolytic dissolution of one or more reactive elements
from a homogeneous alloy. It has profound historical and scientific importance,
playing a role in such diverse contexts as pre-Columbian metallurgy (in which copper
was de-alloyed from Au–Cu alloys to create gold-rich skins [1]) to corrosion
(including its discovery in US Civil War-era brass dezincification [2]), to a recent
discovery [3] that Ag–Au artists’ leaf may be de-alloyed of Ag to create nanoporous

*Corresponding author. Email: dorota.artymowicz@utoronto.ca

ISSN 1478–6435 print/ISSN 1478–6443 online

ß 2009 Taylor & Francis
DOI: 10.1080/14786430903025708
http://www.informaworld.com
1664 D.M. Artymowicz et al.

gold membranes (in the 15th century artists’ handbook, Il Libro del Arte, Cennino
Cennini warns against using leaf with a too-high silver content in outdoor
environments [4]). Around 1980, A.J. Forty and others carried out the first
systematic TEM study of de-alloying, which showed that the more-noble metal was
transported by surface diffusion, and presented a microscopic model of the parting
limit (see below) based on the stability of a dissolution tunnel [5–8]. Recently, there
has been a resurgence of interest in de-alloying [9,10], particularly in the formation of
nanoporous noble metals, driven by potential technological applications and the
remarkable properties of the nanoporous products, such as near-theoretical strength
in compression [11] a scale-dependent elastic modulus [12] and, under a particular
alloy composition and de-alloying procedure, the formation of a material with an
unusual combination of exceptionally low modulus and relatively good mechanical
integrity [13]. Many potential applications of de-alloyed materials are under
investigation, particularly in the areas of catalysis [14–16] and sensing [17,18].
A notable feature of de-alloying in noble-metal alloys is the presence of a sharp
compositional threshold or parting limit in the range of 50–60% of the more reactive
alloy component [19]. This is a true discontinuity, at least in the Au–Ag and Au–Cu
systems [20], and not just the composition where the electrode potential required for
rapid de-alloying (the critical potential) happens to exceed the gold oxidation
potential. In principle, the parting limit is the percentage of reactive element below
which de-alloying vanishes, irrespective of how oxidizing is the electrode potential.
The parting limit applies at large electrode potentials, where the value or pairwise
variation of bonding energies is less influential and in the limit becomes negligible
compared with electrode potential. Appendix 1 outlines some electrochemical basics
applicable to this problem.
Early theories of the parting limit appealed to geometric thresholds in a
compositionally ordered alloy lattice. More recently, the connectivity of reactive
atoms in the more usual case of a disordered alloy such as Ag–Au has been the focus
of attention [21]. Such ‘percolation’ models easily explain the 20% threshold seen in
a few special cases of de-alloying such as Zn from Cu–Zn in copper-containing
solutions [22] because this is the ordinary site percolation threshold for the fcc lattice.
The more common ‘55%’ threshold seen, for instance, in Ag–Au alloys, was
suggested [21] to be controlled by a two-dimensional (2D) layer-by-layer de-alloying
process, because the 2D site percolation threshold within a close-packed plane is
exactly 50%. This idea now seems to be incorrect – three-dimensional porosity
requires dissolution from terrace sites, and 2D percolation cannot sustain continued
dissolution past the first few surface layers of an alloy [23–25]. Therefore, the ‘55%’
parting limit must be a 3D problem, mathematically.
The formation of porosity has been explored extensively by atomistic computer
simulation. Erlebacher [25] used the simulation code MESOSIM to explore the
kinetics and thermodynamics of nanoporosity evolution using the kinetic Monte
Carlo (KMC) method. KMC tracks the diffusion and dissolution of individual
atoms in a large cluster of atoms in three dimensions. More details about the
modeling technique are described below. MESOSIM has been primarily applied to
study porosity evolution, and a successful model has now been developed which
reproduces experimental trends in the critical potential versus time, temperature and
composition. Ultimately, it has been found that the evolution of porosity is due to a
 Philosophical Magazine 1665

kinetic competition between the rate of atom dissolution, and the rate of
re-organization of the more noble alloy component enriched on the surface. Most
recently, the results of the MESOSIM simulations have been used to argue for the
existence of an ‘intrinsic’ critical potential, a thermodynamically defined potential
below which selective dissolution is not favored [24].
Unlike the critical potential, the parting limit is not sensitive to experimental
conditions such as applied potential. In fact, measurements of the parting limit are
quite insensitive to these kinds of parameters, and the quantity seems intrinsically
geometric in nature. As such, the evaluation of the parting limit is connected to other
geometric models associated with surface reactivity, such as the ability to form
passive oxide networks (or not) at Fe–Cr alloy surfaces [26]. In the present paper, we
explore the relationship between the parting limit, primarily using KMC simulation,
and the geometry of so-called high density percolation (hdp) networks in face-
centered cubic (fcc) alloy lattices, as discussed already in [21], where it was suggested
that the critical potential might vary near hdp thresholds. We broaden the discussion
of the parting limit from normal percolation models, which include one-atom wide
channels in the network structure, to hdp models, which exclude channels in width
less than some lower limit, to probe the physically relevant idea that if atoms are too-
highly coordinated, then they are unable to be solvated and dissolved. We
demonstrate that the parting limit is controlled in simulation primarily by geometric
parameters, and not kinetic parameters such as surface diffusion. We also show that
simply excluding dissolution from 10- and 11-coordinated sites gives a simulated
parting limit close to the ‘55%’ seen in many noble metal fcc alloys. Finally, we
rigorously explore the relationship between rules that exclude particular dissolution
events and the high-density percolation thresholds. Our results also give some insight
into the special conditions that are required to give the unusual ‘20%’ threshold.

2. Kinetic Monte Carlo simulations of de-alloying

The original simulation model – MESOSIM – is presented in [25]. The model
describes dissolution in binary fcc alloys by considering atomistic events that occur
on the alloy–electrolyte interface. The model is based on the following assumptions:
(1) Two types of site-coordination dependent transitions – dissolution and
surface diffusion – are possible in the system.
(2) All atoms having at least one un-coordinated bond, which corresponds to at
least one vacancy among their 12 nearest neighboring sites, are capable of a
transition. Later, we will further analyze the physically relevant details of
such transitions.
(3) Atoms of the less noble (LN) element, i.e. ‘Ag’, can diffuse on the surface or
dissolve, while atoms of the more noble (MN), i.e. ‘Au’, can only diffuse.
(4) Rates of dissolution and/or diffusion events of an individual atom are
calculated as follows:
 
nEb
ratediffusion ¼ diffusion  exp , ð1Þ
kT
1666 D.M. Artymowicz et al.

and
 
nEb  
ratedissolution ¼ dissolution  exp  : ð2Þ
kT
Here, n is the number of nearest neighbors of the atom, Eb is the interatomic
bond energy,  is the applied electrochemical overpotential (Appendix 1) in
energy units, k is the Boltzmann constant and T is the absolute temperature.
In all simulations reported here, the bond energy was set to 0.15 eV and equal
for any of the pairs: LN–LN, LN–MN and MN–MN (this assumption can
be relaxed of course). The pre-exponential factor diffusion is an attempt
frequency of the order of the Debye frequency (1013 s1). The pre-
exponential factor dissolution is set to 104 s1 for all alloy compositions [25].
These rules yield simulated porosity evolution on realistic experimental
timescales at a temperature of T ¼ 300 K, which unless noted was used for all
simulations. The rules also satisfy the general trend that more highly-
coordinated atoms diffuse slower than less-coordinated atoms. More detailed
values for transition energies could be calculated from first principles, but
this is a complex problem as it involves diffusional processes at interfaces
with liquid electrolytes. Our purpose here is to examine generic trends.
(5) A particular transition i occurs with probability:
ratei
Pi ¼ , ð3Þ
P
M
ratej
j¼1

where M is the total number of transitions currently possible in the system.

(6) The average time for a single transition to happen (the time elapsed during
one iteration) is
!1
X
M
Dt ¼ ratei : ð4Þ
i¼1

One iteration of the simulation consists of one atomic-scale diffusion or

dissolution event. The particular event is chosen from all M possible transitions at
random, according to its weighted probability, and the elapsed time is then
incremented according to Equation (4). As a result of a transition (for example, an
atom diffusing across a terrace) the list of possible transitions needs to be updated
because the coordination of the atoms in the neighborhood of the atom participating
in the transition has changed. Once updated, the event selection process starts again
and the simulation progresses by another time increment.
The standard output of the program is the number of Ag ions (NAgþ) removed per
time interval (Dt), which is later translated to an electrochemical current density (i) for
comparison with experiment (see Appendix 1) according to the following formula:
NAgþ  F
i¼ , ð5Þ
Dt  S  NA
 Philosophical Magazine 1667

where S is the surface area (cm2) of the simulation cell exposed to the electrolyte at
the start of the simulation, F is the Faraday constant (coulombs mol1) and NA is the
Avogadro number.
In the original presentation of MESOSIM, [25], atoms were allowed to diffuse or
dissolve for all coordination numbers 512. While effective in studying alloy
compositions and potentials that led to porosity evolution, when diffusion was
turned off, the simulations predicted a parting limit at the site percolation threshold
of the fcc lattice, 20% ‘Ag’ – significantly lower than the usual experimentally
observed threshold (see below). This observation also correlated with the onset of
dissolution from 10- and 11-coordinated sites. It is likely that such transitions are
unphysical, even without considering the necessity of ion solvation – the hard-sphere
radius of the unsolvated Ag ion in a 10- or 11-nn site, after electron transfer, is too
large for it to be removed without drastic energy input. Thus, in the version of
MESOSIM used here, we require an atom to have at least three un-coordinated
bonds, i.e. no more than nine neighbors, before it is allowed to diffuse or dissolve. In
other words, the most highly coordinated Ag atom that can dissolve is one in
an ordinary terrace site. This rule captures the idea that dissolution from 10- and
11-coordinated sites is particularly difficult.
We have also experimented with different values of the pre-exponential
parameter in the diffusion rate equation, including a value of zero, i.e. no diffusion
permitted. All the other assumptions and parameters in MESOSIM are left
unchanged.
The samples used in the simulations were fcc rhombohedra bounded by {111}
planes. We usually talk about them as though they are cubes, for clarity. The sample
dimension (b) varies from 16 to 128 atoms per edge. For de-alloying simulations, the
‘electrolyte’ is assumed to be in contact, initially, with only one (the ‘upper’) x–y face;
de-alloying proceeds, on average, in the –z direction. The ‘lower’ x–y face is isolated
from the ‘electrolyte’, but is eventually reached by the de-alloying front penetrating
through the sample, at which point the simulation is over. Periodic boundary
conditions in x and y gave a slab-like character to these simulations. For percolation
calculations, various types of boundary condition were used, including one similar to
the de-alloying procedure; this is described in more detail later on. The simulation
cell is defined in Figure 1.

3. Results
3.1. Simulation results
3.1.1. Current-potential curves with no coordination-dependent exclusions for
dissolution
Figure 2 shows current–potential curves for de-alloying, obtained using MESOSIM
with no coordination-dependent exclusions for dissolution (i.e. dissolution allowed
for 11 neighbors). The potential is ramped in the positive direction, as in many
experiments. The curves reproduce the features seen in practice: a region where the
current is fairly independent of potential, followed by a steep increase in current
above a ‘critical potential’. The critical potential increases steadily as the Ag
content is lowered to 20%, at which point macroscopic de-alloying vanishes.
1668 D.M. Artymowicz et al.

Figure 1. The gray rhombohedron shows the initial simulation cell having x, y and z
directions along its edges. The upper xy face (patterned) is the sample’s surface, which is
in contact with the electrolyte. The lower xy face is the bottom of the sample, and is
considered to be insulated from the electrolyte. Upon removal of the first atom from the
bottom plane, the sample is considered perforated. The transparent rhombohedra to the right
and left of the initial simulation cell represent the periodic boundary conditions that can be
applied in x and y.

1
10

Ag concentration
0 (atomic %)
61 57 41 37 22
10
Current density (mA/cm2)

−1
10

−2 19
10

−3
10

−4
10

0.9 1 1.1 1.2 1.3 1.4 1.5 1.6

Potential (V) SHE

Figure 2. Dynamic current–voltage curves generated by the unmodified MESOSIM

code for the indicated Ag contents in Ag–Au (at%). Dissolution from 10- and
11-coordinated sites is allowed. Potential ramping rate is 20 mV s1. Edge of the simulation
cell is 128 atoms.

This composition corresponds to the ordinary site percolation threshold, which for
the fcc lattice has been calculated to be 0.1992365(10) [27]. For the 19% Ag
composition, two peaks are observed at 1.25 and 1.5 V in Figure 2, and
these correspond to the onset of dissolution of Ag from sites with 10 and 11
neighbors.
 Philosophical Magazine 1669
0
10
Ag concentration 61 60 59
(atomic %)
58
−1
Current density (mA/cm 2) 10 57

−2
10

56
−3
10

−4
55
10
54

−5
10
0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8
Potential (V) SHE

Figure 3. Dynamic current–voltage curves generated by the modified MESOSIM

code for the indicated Ag contents in Ag–Au (at%). Dissolution from 10- and 11-
coordinated sites is prohibited. Potential ramping rate is 2 mV s1. Edge of the simulation
cell is 128 atoms.

3.1.2. Current–potential curves with 10- and 11-coordinated atoms excluded

from dissolution
Figure 3 shows dynamic current–voltage curves for differing compositions over the
same potential range as in Figure 2, but generated using the modified dissolution rule
where Ag sites with 10 or 11 neighbors are not allowed to dissolve, however,
oxidizing the potential. In each case, after an initial rise in current due to the
dissolution of surface Ag, then there is a decay as dissolution penetrates into the bulk
of the alloy. For all compositions greater than or equal to 56% Ag, the dissolution
current eventually increases again at a high enough potential. However, near 55%
Ag, one observes only a current decay, which means that dissolution is stifled
progressively with time.
The marked change in dissolution behavior close to 55% Ag was further probed
using potentiostatic measurements, where the potential is fixed at a highly oxidizing
value. Figure 4 shows the current decays at 1.5 V. As shown in Figure 2, this value
should easily cause de-alloying of alloys with composition much lower than 55% Ag,
were the behavior shown in Figure 2 to be followed; however, for compositions
below 55%, only a current decay was observed. This establishes that for the
particular dissolution rule applied, there is a sharp change in the kinetics of de-
alloying close to 55% Ag.
The current densities for (Ag) 555% in Figure 3 do not decay to zero within the
timescale of the simulation, because surface diffusion is uncovering new sites for
dissolution, though at a decreasing rate. Simulations run with no diffusion
1670 D.M. Artymowicz et al.
−2
10

−3
10 56 Ag concentration
(atomic %)
Current density (mA/cm2)

−4 55
10

54

−5
10
53

−6
10
52

51
−7
10
50

−8
10
0 2 4 6 8 10
4
Time (s) x 10

Figure 4. Current decays at a fixed potential of 1.5 V for the case of Figure 3. The 10- and
11-coordinated atoms are prohibited from dissolution. Edge of the simulation cell is 128
atoms.

(not shown but analyzed later) did show currents decaying to zero within the
timescale of a simulation.
Bulk porosity does not evolve for [Ag] 555%, but even a thin nanoporous layer
could be important for stress corrosion cracking (SCC) due to the ability of a brittle
de-alloyed layer to trigger a crack that penetrates the ductile bulk. In SCC, only a
few tens of nanometers of a nanoporous layer may be required to trigger a crack
advance event [13]. Maier et al. [20] had a very different view of the mechanism of
SCC from the present authors, but did show slight SCC in Ag–Au alloys down to
50% Ag. This composition is below the ostensible 55% parting limit of the Ag–Au
alloys, and our simulations suggest that the results can be explained by the formation
of a near-surface region that has been attacked, but unable to propagate into the
bulk. Other effects may be in order, too, such as a change in the kinetics of de-
alloying at a crack-tip surface with dynamic plastic deformation. In any case, this is a
relatively small shift in the parting limit from that for macroscopic de-alloying.

3.1.3. Effects of surface diffusion kinetics on the parting limit

The simulation results shown in Figures 2–4 were all performed at a temperature of
T ¼ 300 K. At this temperature, there is copious surface diffusion of Au, which can
lead to porosity evolution at appropriate potentials where dissolution rates compare
to surface diffusion rates. It is reasonable to expect an effect of surface diffusion on
the parting limit, because surface diffusion dynamically changes the surface fraction
 Philosophical Magazine 1671

0.9

Fraction of perforated samples 0.8

0.7

13
0.6 n = 10

0.5

n = 1011
0.4

0.3 n=0

0.2

0.1

0
52 53 54 55 56 57 58 59 60
[Ag] (atomic percent)

Figure 5. Fraction of samples perforated by de-alloying as a function of the Ag content

with dissolution of 10- and 11-coordinated atoms prohibited and surface diffusivity set
to high, intermediate and negligible values by changing . Samples were 64 atomic layers
thick and simulations were run for a maximum time of 105 s. Perforation was defined as
dissolution of the first atom from the bottom layer. Simulations stopped at perforation or
when the elapsed time exceeded 105 s.  is the value of the pre-exponential constant diffusion
in Equation (1). Edge of the simulation cell is 64 atoms.

of sites with particular coordination values. For instance, a 10-coordinated silver

atom can become 9-coordinated (and thus allowed to dissolve) if one of its
neighbors diffuses to a second near-neighbor configuration. It is thus important
to de-convolute from the kinetic effect of surface diffusion with any geometric
percolation structures we consider to control the parting limit.
To examine the effect of surface diffusion on the parting limit, we introduce a
new assay. A simulation slab 64 atoms thick was constructed, and de-alloying was
allowed to proceed from the top surface. A ‘perforation’ of the slab was defined
when dissolution of an atom from the bottom layer of the slab was measured. The
thickness of the slab was chosen to be sufficiently thick so as to avoid the ‘skin de-
alloying’ effect described above. In this way, perforation of the slab thus corresponds
to de-alloying above the parting limit.
Perforation simulations were performed at differing levels of surface diffusion by
adjusting the attempt frequency in Equation (1) to values of 0 s1 (‘no diffusion’),
1011 s1 (‘slow diffusion’) and 1013 s1 (‘fast diffusion’), respectively. Figure 5 shows
the fraction of perforated samples versus the Ag fraction, averaged over 10–100
simulation runs. The parting limit for perforation was defined as the concentration at
which 50% of samples are perforated. Over the range of fast diffusion to no
1672 D.M. Artymowicz et al.

diffusion, the parting limit changes only from 54.7% (fast diffusion) to 58.1%
(no diffusion). The slow diffusion condition gives intermediate behavior. Given the
small change in parting limit, we conclude that there is only a small effect of surface
diffusion kinetics on the parting limit. Furthermore, there is a geometric parting limit
(58.1% – a more accurate value is calculated later) when dissolution from 10 and
11-coordinated sites is disallowed and surface diffusion is turned off. The effect of
diffusion is to expose a small number of dissolution paths that would otherwise be
prohibited.
The ‘55%’ parting limit should be universal within a certain family of binary
noble-metal fcc alloys. Currently, there are data for only a limited number of
alloys, and precise parting limits near 55% are only known for Ag–Au and
mostly at room temperature. However, the trend of the critical potential with Pt
content (0–30%) in CuPt alloys is consistent with that seen in AgAu and we can
expect a similar parting limit [28]. Early work of Tammann, discussed by Evans
[29] suggested – to him – that there was a cluster of parting limits near 75% as
well as one near 50%, but it is likely that these values are obtained when there is
insufficient difference in reactivity between the alloy components (e.g. Pd–Au), so
that one is measuring the conditions where the critical potential equals the open-
circuit potential, and not a true parting limit. This suggestion would require
confirmation, of course.
More experimental data should be generated, perhaps also including metastable
solid solution alloys made using sputter-deposition on cold substrates. In principle, a
detailed measurement of the parting limit compared with the 58.1% value may
actually tell us the value of the surface self-diffusion coefficient.
What of the ‘20%’ threshold? It was proposed in the original paper on this topic
[22] that the presence of Cu ions in the electrolyte was the critical feature enabling the
20% percolation limit to be revealed in Cu–Zn alloys (Cu–Al alloys show a limit
slightly below 20%, perhaps because the extreme reactivity of Al enables it to
dissolve from highly occluded geometries, or because non-ideality in the solid
solution leads to like-with-like atom clustering). When Cu in the alloy is equilibrated
with Cu ions in the solution, the exchange of atoms and ions gives a different,
enhanced type of surface mobility from ordinary surface diffusion. A copper
atom can dissolve from a particular site, a neighboring zinc atom that formerly
had 10 neighbors can now be dissolved, then a copper ion can plate out on or next to
the site, so the net effect is that the 10-neighbor restriction has been bypassed.
Simulations are under way to explore this situation.

3.2. High-density site percolation calculations

3.2.1. Requirements to interpret the intrinsic parting limit of 58%
Because the effect of surface diffusion on the parting limit is small, we conclude that
the primary determinant of the parting limit is the probability that Ag atoms are
arranged in clusters penetrating into the bulk. While obviously related to simple
percolating clusters, there is an added constraint here that each Ag atom must have
sufficient Ag neighbors to allow continued dissolution from nine or less coordinated
sites. For instance, a linear chain of atoms following any close packed direction in an
 Philosophical Magazine 1673

fcc lattice will not dissolve at any potential when excluding dissolution from 10- and
11-coordinated sites. The percolation model required here is called high-density (hd)
or correlated percolation [21,30–32]. A hd percolation threshold pc(m) denotes
that a percolation path exists composed of Ag atoms with at least m Ag neighbors.
Informal consideration of possible atomic arrangements suggests that two high-
density site percolation thresholds may be of interest: pc(8) and pc(9). Accordingly,
since it is difficult to find reliable high density percolation data in the literature,
especially for fcc lattices, we determined our own values of these thresholds.

3.2.2. Formation of high density clusters and consideration of boundary conditions

To build a site percolation model, one starts with an empty lattice whose sites are
then filled or left empty with probability p or (1–p), respectively. Let us call the filled
sites gray. In a standard (uncorrelated) percolation problem, the focus is on random
clusters of gray sites. To define a high-density percolation model, each gray site is
revisited and checked for its number of gray nearest neighbors. Gray sites with at
least m gray neighbors are changed to black sites. Gray sites with less than m gray
neighbors are left gray. The percolation properties of the system are determined by
analysis of the black clusters (high density clusters) as a function of the original
filling probability p. The typical analysis of the created system includes assignment of
identification labels to all the individual clusters. Atoms belonging to one cluster
have identical labels. The clusters may then be checked for spanning or the cluster
information may be used to calculate, for example, the largest cluster size, the
average cluster size, or percolation probability (the fraction of sites belonging to the
percolating cluster) [33–35]. Spanning can be defined in many different ways. For
example, one may be interested in clusters spanning in a fixed direction – let us say x,
or in clusters that span in x, y and z directions simultaneously. Spanning definitions
used in this work are listed in Table 1. In addition, clusters can also be checked for
wrapping [36].
The number m can have any value equal to or less than the coordination number
of the lattice. However, for m ¼ 0, 1 or 2, the high-density and standard percolation
models are equivalent. In other words, in standard percolation, every atom in a
percolation path has, as a minimum, one like neighbor ‘behind’ and one ‘in front’.
When identifying Ag atoms with m like neighbors, periodic boundary conditions
in x, y and z were used. This assured that atoms on the faces of the sample, as well as
those inside the sample, all have 12 nearest neighbor sites. When checking for cluster
spanning, two sets of boundary conditions were considered. In the first set, upon
intercepting a sample face, the hd clusters terminated there and were not checked for
continuity in a periodic fashion. This is called ‘non-periodic boundary conditions’ or
npbc later in the text.
The other set of boundary conditions was dictated by the dissolution code
MESOSIM, to facilitate accurate comparison of the hdp calculation with the
dissolution results (one can also use MESOSIM directly to estimate high-density as
well as ordinary percolation thresholds). Here, the lattice continued periodically in x
and y directions but was limited to its nominal dimension b in the z direction. All Ag
atoms located at the top z face were counted as members of a high-density cluster,
independently of their actual number of like neighbors, to parallel their ability to
1674 D.M. Artymowicz et al.

dissolve independently of their number of neighbors. All other Ag atoms were

checked for the number of like nearest neighbors in the usual fashion. High density
clusters intersecting the x or y faces were allowed to continue across these faces, since
again this is how the dissolution code operates. This set of conditions is referred to as
periodic or slab boundary conditions later in the text.
Dissolution simulations were also performed with bc equivalent to npbc.
The periodicity in x and y directions was turned off by plating the side surfaces of the
sample with Au, which prevented dissolution channels from penetrating the side
surfaces.
The difference between non-periodic and slab boundary conditions is shown in
Figure 6. As will be shown later, the choice of boundary conditions or spanning rule
does not affect the value of percolation threshold when extrapolating to infinite
lattice dimensions (infinite b).

Table 1. Rules used when clusters were checked for spanning. A given series of simulations
was continued until a cluster spanning according to the R3 rule was identified. At this
composition, all other rules were already satisfied.

Rule name Rule description

R0 Cluster spanning either x, y or z direction

Rx Cluster spanning in x direction; spanning in y and z are irrelevant and could
happen at lower or higher value of [Ag]
Ry Cluster spanning in y direction; spanning in x and z are irrelevant and could
happen at lower or higher value of [Ag]
Rz Cluster spanning in z direction; spanning in x and y are irrelevant and could
happen at lower or higher value of [Ag]
R1 Cluster spanning in a fixed direction (average value of Rx, Ry and Rz)
R3 Cluster spanning in all three directions

Figure 6. Two sets of boundary conditions used in identification of clusters and propagation
of dissolution channels during de-alloying: (a) non-periodic boundary conditions and
(b) slab boundary conditions. In the case of ‘non-periodic bc’, the clusters AB and CD are
labeled as two separate entities. In the case of de-alloying, the dissolution channel stops
at point B rather than reappearing at point C and continuing towards D. In the case of
‘slab bc’, the CD cluster is a continuation of an AB cluster. The dissolution channel upon
impinging on B resurfaces at point C and continues towards D.
 Philosophical Magazine 1675

3.2.3. Determination of thresholds

High-density percolation threshold calculations were based on consideration of
spanning probability according to a procedure described by [35]. The focus was on
the m ¼ 9 case (percolation of Ag atoms with at least nine Ag neighbors), but
sufficient data were obtained for m ¼ 8 to confirm that this was not the most relevant
threshold. For completeness, less precise values were calculated for all the other hdp
thresholds (see Figure 14 later in the paper).
First, lattice points in a rhombohedron of edge length b were randomly filled with
Ag and Au atoms with the value of p low enough so that the high-density Ag clusters
were not spanning. The concentration was then increased in steps of 0.05% until a
spanning high-density Ag cluster was first detected. This procedure was repeated
between 155 and 8000 times depending on b. The numbers of realizations N are listed
in the first column in Tables 2–7. Figure 7 shows the distribution L(b:p) of p values
at which spanning first occurred according to rules R0, R1 and R3 for m ¼ 9 and
non-periodic boundary conditions. The underlying distribution functions were
approximated by Gaussian curves and are shown in Figure 7 as solid lines. The
average value at which spanning occurred, P bav , was defined as the mean hPib of the
distribution and is b-dependent (other definitions are also possible). As b increases,
the distribution function becomes narrower. At b ¼ 1, the distribution becomes a
delta function and P bav approaches an asymptotic value pc, which defines the
percolation threshold. This dependence on b is expressed in Equation (6):
  1
pc  pbav  b  : ð6Þ

Table 2. Simulation results for high-density percolation for m ¼ 8 and non-periodic boundary
conditions.

Spanning rule

B Parameter R0 R1 R3

16 (N ¼ 8000) h pi 0.5299 0.5440 0.5589

p* 0.5327 0.5470 0.5619
 20.6 18.8 22.6
32 (N ¼ 3930) h pi 0.5295 0.5368 0.5444
p* 0.5308 0.5381 0.5453
 42 39 47
64 (N ¼ 2300) h pi 0.5301 0.5337 0.5375
p* 0.5307 0.5343 0.5453
 84 82 107
128 (N ¼ 240) h pi 0.5322 0.5323 0.5340
p* 0.5308 0.5324 0.5340
 167 164 191
Final results  1.007(5) 1.05(1) 1.04(5)
p1c 0.5304(4) 0.5301(3) 0.5299(5)
1676 D.M. Artymowicz et al.

Table 3. Simulation results for high-density percolation for m ¼ 9 and non-periodic boundary
conditions.

Spanning rule

b Parameter R0 R1 R3

16 (N ¼ 8000) h pi 0.5993 0.6130 0.6275

p* 0.5906 0.6032 0.6191
 20.7 18.6 22.2
32 (N ¼ 2000) h pi 0.5991 0.6062 0.6138
p* 0.5948 0.6013 0.6092
 43 39 45
64 (N ¼ 1280) h pi 0.5997 0.6031 0.6068
p* 0.5978 0.6007 0.6048
 93 83 103
128 (N ¼ 1200) h pi 0.6001 0.6017 0.6034
p* 0.5989 0.6004 0.6023
 184 172 212
Final results  1.06(2) 1.072(4) 1.10(3)
p1c 0.6000(3) 0.5995(3) 0.5989(3)

Table 4. Simulation results for high-density percolation for m ¼ 8 and slab boundary
conditions (pbc in x and y but not z). Rule Rz was used when checking for spanning.

B Parameter

16 (N ¼ 8000) h pi 0.5255
p* 0.5275
 16.5
32 (N ¼ 8000) h pi 0.5276
p* 0.5287
 34
64 (N ¼ 2334) h pi 0.5292
p* 0.5295
 73
128 (N ¼ 398) h pi 0.5301
p* 0.5392
 134
Final results  1.01(4)
p1c 0.5306(3)

Here,  is a critical exponent and, for a 3D lattice and non-correlated percolation, is

somewhat below 0.9 [34]. The values of  for 3D high-density percolation on cubic
lattices estimated by [32] are close to 1. In the paragraphs below, a method of
evaluating  is explained.
 Philosophical Magazine 1677

Table 5. Simulation results for high-density percolation for m ¼ 9 and slab boundary
conditions (pbc in x and y but not z). Rule Rz was used when checking for spanning.

b Parameter

16 (N ¼ 2372) h pi 0.5942
p* 0.6001
 16.5
32 (N ¼ 8000) h pi 0.5972
p* 0.5998
 44
64 (N ¼ 1020) h pi 0.5986
p* 0.5998
 97
128 (N ¼ 180) h pi 0.5997
p* 0.6002
 204
Final results  1.01(2)
p1
c 0.6004(2)

Table 6. Simulation results for de-alloying code and ‘slab’ boundary conditions.

b Parameter

16 (N ¼ 1000) h pi 0.5573
p* 0.5591
 37
32 (N ¼ 490) h pi 0.5718
p* 0.5723
 87
64 (N ¼ 240) h pi 0.5790
p* 0.5790
 170
128 (N ¼ 150) h pi 0.5818
p* 0.5813
 307
Final results  1.01(6)
p1c 0.5853(4)

The spanning probability p0 is defined as the total probability that the sample will
span at p and is calculated according to Equation (7):
Zp
p0 ð pÞ ¼ Lðb : pÞdp: ð7Þ
0

Examples of spanning probability deduced from data presented in Figure 7b are

shown in Figure 8. In the b ¼ 1 limit the spanning probability is a step function.
1678 D.M. Artymowicz et al.

Table 7. Simulation results for de-alloying code and non-periodic boundary conditions.

b Parameter

16 (N ¼ 127,000) h pi 0.5791
p* 0.5828
 25.4
32 (N ¼ 20,000) h pi 0.5803
p* 0.5816
 63
64 (N ¼ 2100) h pi 0.5817
p* 0.5819
 140
128 (N ¼ 350) h pi 0.5830
p* 0.5828
 241
Final results  1.03(6)
p1c 0.5828(6)

The spanning probability curve intercepts the p ¼ p0 line (dashed line in

Figure 8) at p ¼ p*. The quantity p* is called the fixed point for the transformation R
and can be understood as follows. Let us imagine that one cell of linear dimension b
is transformed to a lattice point in a ‘super cell’. The lattice point of the ‘super cell’ is
filled if the cell was spanning and left empty if it was not. Then, a second cell is
turned into a second lattice point in the ‘super cell’ and again the lattice point in the
super cell is occupied or left empty depending on the spanning of the original cell. We
continue and build a super cell of linear dimension b. If filling probability in the
original cell p ¼ p*, the super cell and original cell are self-similar as the filling
probability and spanning probability are equal to one another at p ¼ p*.
The point where all the curves cross, at p ¼ 0.31, is related to the site percolation
threshold for a simple cubic lattice, according to a cube-stacking argument. For hdp
with large m, this argument appears to work better than for ordinary percolation –
presumably due to the greater degree of connectivity generally at such compositions
– hdp shows less orphaned material, close to pc, than ordinary percolation.
The universal constant  is related to spanning probability p0 through
Equation (8):

lnðbÞ lnðbÞ
¼ ¼ , ð8Þ
lnðdp0 =dpÞp lnðÞ

where  is the spanning probability at p ¼ p* or the value of the distribution function

L at p ¼ p*.
Figure 9 shows the determination of  according to Equation (8) and numerical
data shown in Figure 8. Once  is known, the percolation threshold pc can be
1
estimated according to Equation (6) by plotting pbav versus b and extrapolating the
1
linear fit to b  ¼ 0. This procedure is shown in Figure 10 for m ¼ 9 and four
 Philosophical Magazine 1679

(a) 250
a: rule R0
b =16
b =32
200 b =64
b =128

150
L(b:p)

100

50

0
0.57 0.58 0.59 0.6 0.61 0.62 0.63 0.64 0.65

p (atomic fraction)

(b) 250

b: rule R1 b =16
b =32
200 b =64
b =128

150
L(b:p)

100

50

0
0.57 0.58 0.59 0.6 0.61 0.62 0.63 0.64 0.65
p (atomic fraction)

Figure 7. Probability density functions, L(b : p) for spanning according to the rules R0 (a), R1
(b) and R3 (c) and non-periodic boundary conditions for cells with edge length b from 16 to
128. Data points are the results of Monte Carlo simulations; solid lines are Gaussian fits to the
experimental data.
1680 D.M. Artymowicz et al.

(c) 250
b = 16
c: rule R3 b = 32
b = 64
200 b = 128

150
L(b :p)

100

50

0
0.57 0.58 0.59 0.6 0.61 0.62 0.63 0.64 0.65
p (atomic fraction)
Figure 7. Continued.

combinations of spanning rules and boundary conditions. The values of pc for all
four combinations are listed in bottom rows of Tables 3 and 5. The average pc is
59.97(3).
A parting limit for perforation was calculated using the modified MESOSIM
code in the same manner as the percolation threshold described above. Owing to the
directional nature of the MESOSIM code only the Rz rule could be applied. The
results are listed in Table 6. In Figure 11, perforation probability is compared with
the percolation threshold obtained for rule R1 and two definitions of high-density
cluster.
Figure 12 is a cumulative plot for determining percolation threshold and parting
limit for all tested code versions, boundary conditions and definitions of high-density
clusters. The numerical values of pc are listed in Table 8.
The form of the cumulative probability functions for de-alloying, Figure 11b, is
different from those found for hdp. This is due mainly to the periodic boundary
conditions in x and y, which ‘enlarge’ samples with small b so that they behave
almost like slabs of large dimension in x and y, especially at higher p values where
propagation of de-alloying across the bounding planes in x and y is very efficient.
For slabs of fixed (large) x and y dimension and varying z dimension, we expect
exactly the kind of result shown in Figure 11b – if the probability of perforation is,
say, 90% for a slab of thickness 128, it must be greater than 90% for any slab of
smaller thickness. This interpretation was supported by carrying out simulations
 Philosophical Magazine 1681

0.9 b =16
b =32
0.8 b =64
b =128
0.7

0.6
p’

0.5

0.4

0.3

0.2

0.1

0
0.57 0.58 0.59 0.6 0.61 0.62 0.63 0.64 0.65
p (atomic fraction )

Figure 8. Probability p0 of spanning a b  b  b cell versus volume fraction p of Ag. These

curves were obtained for the R1 rule and non-periodic boundary conditions and are cumulative
sums of data from Figure 7b. The intercept of the spanning probability with the p ¼ p0 line
(dotted) determines the values of p* and .

where the periodic boundary conditions in x and y directions were turned off.
The cumulative probabilities for perforation by de-alloying (Figure 13) now adopted
a form more similar to those for hdp in Figures 11a and c, though with some
residual asymmetry. The 58.4% threshold did not change significantly (Figure 13
and Table 8).
For completeness, a full set of hdp thresholds for m ¼ 2–12 is shown in Figure 14.
For the higher m values, pc(m) can be estimated quite well by just calculating the
p value at which a randomly chosen ‘Ag’ atom has probability 0.199 of having
at least m like neighbors – more evidence for the highly connected nature of hdp
clusters.

4. Discussion
Our primary result is that the no-diffusion parting limit found using KMC
simulations (58.4%) is close to, but different from, the geometric high-density site
percolation threshold pc(9) for the fcc lattice (59.97%).
1682 D.M. Artymowicz et al.

5.5

4.5
ln(λ)

3.5

2.5
2.5 3 3.5 4 4.5 5
ln(b)

Figure 9. Plot for determining the critical exponent  from the results of Figure 8 and
Equation (2). From this plot  ¼ 1.072(4). Critical exponents for other rules and/or boundary
conditions are listed in Tables 3 and 5.

0.635
R0 p∞
c
=0.6000(3)
0.63 R1 p∞=0.5995(3)
c
∞
R3 p =0.5989(3)
0.625 Rz p∞c =0.6004(2) R3; npbc
c

0.62
R1; npbc
0.615
〈p〉

0.61
R0; npbc
0.605

0.6

0.595

0.59 Rz; slab bc

0.585
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
b−1/n

Figure 10. Plots for determining the percolation threshold p1

c (9) from Equation (6) for all sets
of rules and boundary conditions. p1 c is the extrapolated value of h pi for b ¼ 1.
 Philosophical Magazine 1683

(a) 1

a: hdp; m=8 b =16

0.9
b =32
b =64
0.8
b =128

0.7
Spanning probability

0.6

0.5

0.4

0.3

0.2

0.1

0
0.45 0.49 0.53 0.57 0.61 0.65
p (atomic fraction)

(b) 1

0.9 b: dissolution code

slab bc b = 16
b = 32
0.8
b = 64
b = 128
0.7
Perforation probability

0.6

0.5

0.4

0.3

0.2

0.1

0
0.45 0.49 0.53 0.57 0.61 0.65
p (atomic fraction)

Figure 11. Spanning or perforation cumulative probability from hdp and de-alloying codes. b
is the length of the cell edge. (a) and (c) are for hdp with m ¼ 8 and m ¼ 9, respectively, and
non-pbc. (b) The de-alloying code and slab boundary conditions.
1684 D.M. Artymowicz et al.

(c) 1

0.9
c: hdp; n=9

0.8

0.7
Spanning probability

0.6

0.5

0.4
b = 16
0.3 b = 32
b = 64
0.2 b = 128

0.1

0
0.45 0.49 0.53 0.57 0.61 0.65
p (atomic fraction)

Figure 11. Continued.

Consider the case of an Ag atom sitting on a plane within the bulk of a cluster,
and that this atom only possesses one in-plane Ag neighbor. Normally, this
configuration would cause unidirectional dissolution from one side to reach a dead-
end, because an atom below this Ag atom could never (absent diffusion) acquire
fewer than 10 total neighbors. However, in simulation, the dissolution front can also
approach this plane from below via a physical attack from the opposite side of the
simulation slab. If in this case one of its neighbors is removed from behind, then this
Ag atom now has only nine total neighbors and is allowed to dissolve – even though
it has failed to satisfy the requirement to be a member of a hdp cluster. Is this effect
an artefact? In reality, the fcc lattice is so dense with connections of this sort that
such events can happen without creating (as in our simplified example) an artificial
membrane of atoms hanging in space. Such ‘attacks from behind’ can occur via
meandering clusters that curve back upwards. So the question is: do such relatively
rare events lower the no-diffusion parting limit from a value exactly equal to the hdp
threshold for m ¼ 9 (59.97%), or from some other value that is also not a formal hdp
threshold?
The answer to this question is resolved by calculating the connectivity
properties of thin (usually four atoms-thick), artificially populated slabs of
material bounded by {111} planes. It is immediately apparent that in such
geometries, all Ag atoms in the backbone of a successful de-alloying path must
have at least three in-plane Ag neighbors. Moreover, these three in-plane
 Philosophical Magazine 1685

0.64
hdp(9)

0.62

0.6
dissolution

0.58
〈p〉

hdp(8)
0.56

0.54

0.52

0 0.02 0.04 0.06 0.08 0.1 0.12

−1/n
b

Figure 12. Average concentration h pi at which spanning or perforation occurs as a function

of cell edge b. The points and solid lines are experimental Monte Carlo results and linear fits,
respectively. The y axis intercepts of the fitted straight lines give the value of percolation
threshold p1c in the b ¼ 1 limit. Different spanning rules are coded as follows: diamond – R0
and npbc; circle – R1 and npbc; square – R3 and npbc; down triangle – Rz and slab bc. The
solid and open symbols correspond to m ¼ 9 and m ¼ 8 conditions, respectively. Solid and
open stars are for the de-alloying code with non-periodic and slab boundary conditions,
respectively.

Table 8. Percolation thresholds and parting limits for all applied definitions of high-density
percolation, spanning criteria and boundary conditions.

R0 & R1 & R3 & Rz & Rz & Average

npbc npbc npbc slab bc npbc pc

hdp with m ¼ 9 0.6000(3) 0.5995(3) 0.5989(3) 0.6004(2) NA 0.5997(3)

hdp with m ¼ 8 0.5304(4) 0.5301(3) 0.5299(5) 0.5306(3) NA 0.5306(1)
Dissolution code NA NA NA 0.5853(4) 0.5828(6) 0.584(1)

neighbors must be arranged in a compact (diamond) way (see Appendix 2). These
requirements immediately explain why it is insufficient to be at pc(8). At this
value of p, the percolation path must contain atoms with only two in-plane
neighbors, which must terminate de-alloying.
Given the above consideration, we can construct configurations that de-alloy but
do not satisfy hdp with m ¼ 9, and vice versa. There are 12 ways that we can stack
one ‘diamond’ arrangement of Ag atoms on top of another so that they overlap
1686 D.M. Artymowicz et al.

1
b = 16
0.9
b = 32
b = 64
0.8
b = 128

0.7
Perforation probability

0.6

0.5

0.4

0.3

0.2

0.1

0
0.45 0.49 0.53 0.57 0.61 0.65
p (atomic fraction)

Figure 13. Perforation cumulative probability versus volume fraction p of Ag, as calculated
by de-alloying code with periodic boundary conditions in x and y directions turned off.

0.9

0.8

0.7

0.6
pc(m)

0.5

0.4

0.3

0.2

0.1
2 3 4 5 6 7 8 9 10 11 12
m
Figure 14. High density percolation thresholds pc(m) for different values of m, where m is
number of like neighbors required for an atom to belong to a high density cluster. Vertical
error bars are 0.002 or smaller.
 Philosophical Magazine 1687

Figure 15. Examples of possible arrangements of Ag atoms on three consecutive (111) planes.
Atoms on bottom, middle and top planes are white, gray and black, respectively. Arrangement
(a) is an example of a de-alloying arrangement where none of the atoms in the central plane
has nine like neighbors. Therefore, this arrangement can not be a segment of a hd cluster for
m ¼ 9. Arrangement (b) is a de-alloying arrangement where the top right atom in the middle
plane has nine like neighbors. The leftmost atom from the top plane and the lower right atom
at the bottom plane are candidates for the backbone atoms as they have three in-plane like
neighbors and three like neighbors in the middle plane. This arrangement can be a segment of
a hd cluster for m ¼ 9.

to some extent. Of these 12, five allow dissolution to proceed and eat out the four
Ag atoms in the lower layer such that dissolution can proceed to the third
layer. Proceeding to three layers and taking the five ways of propagating de-alloying
to the second layer, we find 25 of 60 arrangements that permit de-alloying through to
the fourth layer. Of these 25, only six arrangements have an atom in the central
plane that satisfies the requirement of hdp clusters with m ¼ 9 and two candidate
atoms – one in the bottom and one in the top plane – that will satisfy the m ¼ 9
condition if provided with three Ag atoms in the plane below the bottom one and
above the top one, respectively. The remaining 19 arrangements that do de-alloy
through the third layer lack atoms in the central plane that satisfy the m ¼ 9
condition. Arrangements that satisfy hdp for m ¼ 9 but do not de-alloy also exist
(none of them is of the ‘stacked diamond’ type), but are fewer, and appear –
according to our preliminary analysis – to have lower probability of occurrence than
the exceptions that de-alloy but do not percolate. Figures 15 and 16 show three-layer
arrangements of atoms that satisfy de-alloying requirements and/or hdp with m ¼ 9
requirements.
A simple argument can be advanced to explain why the m ¼ 9 case is special in
that, if we consider any two adjacent Ag atoms in an hd percolation path, these share
four neighboring sites in addition to each other. So, if each only has three Au
neighbors, they will always share at least one Ag neighbor. This provides the
necessary ‘fattening’ of the percolation path to allow dissolution to continue with a
reasonably high probability, and may explain why there is an approximate
correspondence between the hdp threshold for m ¼ 9 and the parting limit, despite
the existence of local counter examples. The percolation backbone undergoes
a fundamental change in configuration at its narrowest points between m ¼ 8
and m ¼ 9.
1688 D.M. Artymowicz et al.

Figure 16. Example of possible arrangements of Ag atoms in a segment of a hd cluster for

m ¼ 9. The atoms in the top, middle and lower planes are black, gray and white, respectively.
For clarity, only the middle plane is drawn. Backbone atom (gray) and two backbone
candidates (white and black) are surrounded by circles. This arrangement can not de-alloy
beyond the top plane as none of the atoms in the central plane has three Ag neighbors in the
plane above.

5. Conclusions
When dissolution of Ag from atomic sites with more than nine total neighbors is
prohibited, the MESOSIM code gives a parting limit close to 55% Ag for de-alloying
of AgAu, in line with historical experimental observations.
When diffusion is quenched, this threshold shifts to 58.4%. It is similar but not
identical to a high-density percolation threshold for Ag atoms with at least nine Ag
neighbors, which is 59.97%. Local configurations can be found that de-alloy but do
not satisfy hdp, and vice versa.
Nevertheless, consideration of the configuration of the percolation backbone
tends to support the idea that there is an underlying relationship between pc(9) and
the parting limit.

Acknowledgements
Research at the Department of Chemical Engineering, University of Toronto, was funded by
NSERC (Canada) and UNENE, the University Network of Excellence in Nuclear
Engineering. The industrial sponsors of R.C. Newman’s Chair within UNENE are AECL,
Ontario Power Generation and Bruce Power. J. Erlebacher’s contribution is funded by the
NSF (USA) under grant DMR-0705525.
 Philosophical Magazine 1689

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1690 D.M. Artymowicz et al.

Appendix 1: Electrochemistry basics

The de-alloying process discussed in this paper is a special case of anodic (oxidative)
dissolution of a metal in an electrolyte – assumed to be an aqueous acid, where no oxides or
other interfering chemical compounds can form. If the acid is strongly oxidizing, such as
concentrated nitric acid, such dissolution may occur spontaneously, without application of
any current or voltage via an external circuit. Immersion in strong nitric acid is often used as a
convenient way to de-alloy noble-metal alloys such as AgAu or CuAu. More generally, the
acid is non-oxidizing, such as dilute aqueous perchloric or sulfuric acid, and de-alloying is
achieved by applying a current or – more usually – a controlled electrode potential versus a
standard reference electrode, using an external circuit. The current gives a direct measure of
the rate of metal dissolution.
The simulation results displayed in this paper show the metal (‘silver’) dissolution rate in
units of current density (i, units A cm2) for easy comparison with electrochemical
experiments. The dissolution flux in mol cm2 s1 is i/nF, where F is Faraday’s constant and
n the dissolution valency. Multiplying this by Avogadro’s number gives the result in atoms
cm2 s1.
For a pure metal with a simple one-electron transfer reaction, such as

Ag ! Agþ ðaqÞ þ e , ð9Þ

the dissolution kinetics are well-behaved and conform to Tafel’s law:

 
i
 ¼ b  log , ð10Þ
i0
i.e. an exponential dependence of current density (i) on , the overpotential, which is the extra
voltage applied across the metal–electrolyte interface over and above that which exists
naturally when the metal and the dissolved metal ion are in equilibrium. i0, the exchange
current density, is the rate of forward and reverse reactions (dissolution and plating) in the
equilibrium condition, and depends on the concentration of metal ions in the electrolyte1. b is
the Tafel coefficient, which is 60–120 mV. In the simulations, a ‘Tafel’-like kinetic law is
applied to individual atoms on a probabilistic basis.
In the simulations, not all surface Ag atoms are equal. The ‘activation energy’ that enters
the expression for the dissolution rate – Equation (2) – depends on the number of near-
neighbors (and their type, although that is not exploited in this paper), as well as the applied
overpotential. Then, the number of Ag atoms that are available for reaction, and the geometry
of the sites in which they are exposed, are affected by the presence and surface diffusion of Au
atoms. Realistic de-alloying kinetics arise naturally from these assumptions.

Appendix 2. Analysis showing that particularly arranged four Ag atoms on (111)

plane are sufficient to sustain dissolution
Here, we analyze stacks of two (111) planes artificially populated with Ag in such a way that
dissolution is possible through the two planes at a minimum volume fraction of Ag. The top
plane is assumed to be the sample’s surface. As all atoms on the surface plane are
9-coordinated, no other conditions need to be satisfied for dissolution of surface Ag.
Each dissolution must start with the removal of three surface Ag atoms – every one of
them a nearest neighbor of the other two. Dissolution of this triplex creates, in a plane below

1
If there are no metal ions present in the electrolyte, there is – formally – no equilibrium to
refer to, but as we are usually dealing with conditions that are far from equilibrium, this rarely
creates complexities. For this case, rather than refer to an actual equilibrium potential, we can
just express Tafel’s Law as (E–E*) ¼ b log(i/i*), where i* is the anodic current density at an
arbitrary electrode potential E*.
 Philosophical Magazine 1691

Figure A1. Coordination of atoms in the plane immediately below the surface: (a) after
dissolution of surface Ag triplex (black), (b) after subsequent dissolution of the common
neighbor to the triplex in the plane below the surface (dark gray). Digits in the circles indicate
number of non-coordinated bonds. If the common neighbor to the back triplex is not Ag, the
dissolution cannot proceed. All other atoms in the plane immediately below the surface remain
12-coordinated.

Figure A2. Coordination of atoms on the plane immediately below the surface after
dissolution of the four surface Ag (black) and the common neighbor to the surface triplex
(dark gray). Digits in the circles indicate number of non-coordinated bonds that atoms have as
a result of that dissolution. Arrangements (a) and (b) are called diamond and flag,
respectively. There are three symmetrically related ‘diamond’ arrangements and six symmet-
rically related ‘flag’ arrangements.

the surface, one atom with three non-coordinated bonds (ncb) (the common neighbor of the
triplex) and six atoms with one ncb each. Assuming the common neighbor to the triplex is Ag
(if not, dissolution stops here), after its dissolution the six atoms gain one more ncb each and,
in the second plane below the surface, three atoms become 11-coordinated. This situation is
shown in Figure A1 (the 12-coordinated atoms are not shown). Even if all the six atoms with
two ncbs were Ag, the dissolution will not progress as there are no atoms with three non-
coordinated bonds. Therefore, at least one of six atoms must be provided with an additional
non-coordinated bond. This can be achieved by planting one more Ag atom (the fourth Ag)
coplanar with the triplex. There are nine possible placements for this fourth atom – three
resulting in a ‘diamond’ arrangement and six in a ‘flag’ arrangement, as exemplified in
Figures A2a and A2b, respectively.
Using the same argument as above, we conclude that four Ag atoms are required on the
plane under the surface for de-alloying to continue into the bulk. Taking into account
coordination information from Figure A2, we now try to identify all possible arrangements of
four Ag atoms on a plane under the surface which can be dissolved after the surface Ag
quadruplex corroded away. There are four such arrangements derived from the configuration
1692 D.M. Artymowicz et al.

Figure A3. Four diamond arrangements of Ag atoms (light gray) in the plane below the
original surface of the sample that can be dissolved after dissolution of a surface Ag diamond
(black circles). Au atoms are white or not shown.

Figure A4. Possible arrangements of four Ag atoms in the plane directly below the surface
(gray), which can be dissolved after dissolution of the surface flag-arranged Ag quadruplex
(black). Au atoms are white or not shown.
 Philosophical Magazine 1693

in Figure A2a and four from the configuration in Figure A2b. These are shown in Figures A3
and A4, respectively. In fact, there are four arrangements of undersurface Ag quadruplex for
every one of nine arrangements of surface Ag quadruplexes. All of these arrangements are of
the diamond type even if surface Ag are arranged in the ‘flag’ configuration. The ‘flag’
arrangement can, therefore, belong to a dissolution cluster only if located on the sample’s
surface. The de-alloying path may therefore be analyzed as a stack of Ag diamonds with some
overlapping between the diamonds.
There is an alternative way of indicating that the ‘flag’ arrangement can partici-
pate in a de-alloying path only at the sample’s surface. It can be shown that it is
impossible to remove all four atoms of the ‘flag’ if there are only four vacancies in
the plane above.