[206.2.3] A general geometric characterization of stochastic media should provide macroscopic geometric observables that allow to distinguish media with different microstructures quantitatively. [206.2.4] In general, a stochastic medium is defined as a probability distribution on a space of geometries or configurations. [206.2.5] Distributions and expectation values of geometric observables are candidates for a general geometric characterization.
[206.3.1] A general geometric characterization should fulfill four criteria to be useful in applications. [206.3.2] These four criteria were advanced in [30]. [206.3.3] First, it must be well defined. [206.3.4] This obvious requirement is sometimes violated. [206.3.5] The so called ‘‘pore size distributions’’ measured in mercury porosimetry are not geometrical observables in the sense that they cannot be determined from knowledge of the geometry alone. [206.3.6] Instead they are capillary pressure curves whose calculation involves physical quantities such as surface tension, viscosity or flooding history [30]. [206.3.7] Second, the geometric characterization should be directly accessible in experiments. [206.3.8] The experiments should be independent of the quantities to be predicted. [206.3.9] Thirdly, the numerical implementation should not require excessive amounts of data. [206.3.10] This means that the amount of data should be manageable by contemporary data processing technology. [206.3.11] Finally, a useful geometric characterization should be helpful in the exact or approximate theoretical calculations.
[206.4.1] For simplicity only two-component media will be considered throughout this paper, but most concepts can be generalized to media with an arbitrary finite number of components.
[206.4.2] Well defined geometric observables are the basis for the geometric characterization of porous media. [206.4.3] A perennial problem in all applications is to identify those [page 207, §0] macroscopic geometric observables that are relevant for distinguishing between classes of microstructures. [207.0.1] One is interested in those properties of the microstructure that influence the macroscopic physical behaviour. [207.0.2] In general this depends on the details of the physical problem, but some general properties of the microstructure such as volume fraction or porosity are known to be relevant in many situations. [207.0.3] Hadwigers theorem [23] is an example of a mathematical result that helps to identify an important class of such general geometric properties of porous media. [207.0.4] It will be seen later, however, that there exist important geometric properties that are not members of this class.
[207.1.1] A two component porous (or heterogenous) sample
consists of two closed subsets
and
called pore space
and matrix
such that
.
[207.1.2] Its internal boundary is denoted as
[207.1.3] The boundary
of a set is defined as the
difference between the closure and the interior of
where the closure is the intersection of all closed
sets containing
and the interior is the union of
all open sets contained in
.
[207.1.4] A geometric observable
is a mapping (functional) that
assigns to each admissible
a real number
that can be calculated from
without solving a physical
boundary value problem.
[207.1.5] A functional whose evaluation requires the solution of a physical
boundary value problem will be called a physical observable.
[207.2.1] Before discussing examples for geometric observables
it is necessary to specify the admissible geometries .
[207.2.2] The set
of admissible
is defined as
the set of all finite unions of compact convex sets
[23, 61, 58, 57, 44](see also the
papers by M. Kerscher and K. Mecke in this volume).
[207.2.3] Because
is closed under unions and
intersections it is called the convex ring.
[207.2.4] The choice of
is convenient for applications
because digitized porous media can be considered as
elements from
and because continuous observables defined for
convex compact sets can be continued to all of
.
[207.2.5] The set of all compact and convex subsets of
is denoted as
.
[207.2.6] For subsequent discussions the
Minkowski addition of two sets
is defined as
![]() |
(8) |
[207.2.7] Multiplication of with a scalar is defined by
for
.
[207.3.1] Examples of geometric observables are the volume of
or the surface area of its boundary
.
[207.3.2] Let
![]() |
(9) |
denote the -dimensional Lebesgue volume
of the compact convex set
.
[207.3.3] The volume is hence a functional
on
.
[207.3.4] An example of a compact convex set is the unit ball
centered at the origin
whose volume is
![]() |
(10) |
[207.3.5] Other functionals on can be constructed from the volume
by virtue of the following fact.
[207.3.6] For every compact convex
and every
there are
[page 208, §0]
numbers
depending only on
such that
![]() |
(11) |
is a polynomial in .
[208.0.1] This result is known as Steiners formula [23, 61].
[208.0.2] The numbers
define functionals on
similar to the volume
.
[208.0.3] The quantities
![]() |
(12) |
are called quermassintegrals [57]. [208.0.4] From (11) one sees that
![]() |
(13) |
and from (10) that .
[208.0.5] Hence
may be viewed as half the surface area.
[208.0.6] The functional
is related to the mean width
defined as the mean value of the distance between a pair of
parallel support planes of
.
[208.0.7]
The relation is
![]() |
(14) |
which reduces to for
.
[208.0.8] Finally the functional
is evaluated from
(11) by dividing with
and taking
the limit
.
[208.0.9] It follows that
for all
.
[208.0.10] One extends
to all of
by defining
.
[208.0.11] The geometric observable
is called Euler characteristic.
[208.1.1] The geometric observables have several important properties.
[208.1.2] They are Euclidean invariant (i.e. invariant under rigid motions),
additive and monotone.
[208.1.3] Let
denote the group of translations with
vector addition as group operation and let
be
the matrix group of rotations in
dimensions [5].
[208.1.4] The semidirect product
is the Euclidean
group of rigid motions in
.
[208.1.5] It is defined as the set of pairs
with
and
and group operation
![]() |
(15) |
[208.1.6] An observable is called euclidean invariant
or invariant under rigid motions
if
![]() |
(16) |
holds for all and all
.
[208.1.7] Here
denotes the rotation
of
and
its translation.
[208.1.8] A geometric observable
is called additive
if
![]() |
![]() |
(17a) | |
![]() |
![]() |
(17b) |
holds for all with
.
[208.1.9] Finally a functional is called monotone if for
with
follows
.
[page 209, §1]
[209.1.1] The special importance of the functionals arises from
the following theorem of Hadwiger [23].
[209.1.2] A functional
is euclidean invariant,
additive and monotone if and only if it is a linear
combination
![]() |
(18) |
with nonnegative constants .
[209.1.3] The condition of monotonicity can be replaced with
continuity and the theorem remains valid [23].
[209.1.4] If
is continuous on
, additive and euclidean invariant
it can be additively extended to the convex ring
[58].
[209.1.5] The additive extension is unique and given by the
inclusion-exclusion formula
![]() |
(19) |
where denotes the family of nonempty subsets
of
and
is the number of elements
of
.
[209.1.6] In particular, the functionals
have a unique additive extension
to the convex ring
[58], which is again be denoted by
.
[209.2.1] For a threedimensional porous sample with the extended
functionals
lead to two frequently used geometric observables.
[209.2.2] The first is the porosity of a porous sample
defined as
![]() |
(20) |
and the second its specific internal surface area which may be defined in view of (13) as
![]() |
(21) |
[209.2.3] The two remaining observables and
have received less attention
in the porous media literature.
[209.2.4] The Euler characteristic
on
coincides with
the identically named topological invariant.
[209.2.5] For
and
one has
where
is the number
of connectedness components of
, and
denotes
the number of holes (i.e. bounded connectedness components
of the complement).
[209.2.6] For theoretical purposes the pore space is frequently
viewed as a random set [61, 30].
[209.2.7] In practical applications the pore space is usually discretized
because of measurement limitations and finite resolution.
[209.2.8] For the data discussed below the set
is a
rectangular parallelepiped whose sidelengths are
and
in units of the lattice constant
(resolution)
of a simple cubic lattice.
[209.2.9] The position vectors
with integers
are
[page 210, §0]
used to
label the lattice points, and
is a shorthand notation for
.
[210.0.1] Let
denote a cubic volume element (voxel)
centered at the lattice site
.
[210.0.2] Then the discretized sample may be represented
as
.
[210.0.3] The discretized pore space
defined as
![]() |
(22) |
is an approximation to the true pore space .
[210.0.4] For simplicity it will be assumed that the
discretization does not introduce errors,
i.e. that
, and that
each voxel is either fully pore or fully matrix.
[210.0.5] This assumption may be relaxed to allow
voxel attributes such as internal surface or
other quermassintegral densities.
[210.0.6] The discretization into voxels reflects the limitations arising
from the experimental resolution of the porous structure.
[210.0.7] A discretized pore space for a bounded sample belongs
to the convex ring
if the voxels are convex and
compact.
[210.0.8] Hence, for a simple cubic discretization the pore
space belongs to the convex ring.
[210.0.9] A configuration (or microstructure)
of a
-component medium may then be represented
in the simplest case by a sequence
![]() |
(23) |
where runs through the lattice points and
.
[210.0.10] This representation corresponds to the simplest discretization
in which there are only two states for each voxel indicating
whether it belongs to pore space or not.
[210.0.11] In general a voxel could be characterized
by more states reflecting the microsctructure within
the region
.
[210.0.12] In the simplest case there is a one-to-one correspondence
between
and
given by (23).
[210.0.13] Geometric observables
then correspond to functions
.
[210.1.1] As a convenient theoretical idealization it is frequently assumed that porous media are random realizations drawn from an underlying statistical ensemble. [210.1.2] A discretized stochastic porous medium is defined through the discrete probability density
![]() |
(24) |
where in the simplest case.
[210.1.3] It should be emphasized that the probability density
is mainly of theoretical interest.
[210.1.4] In practice it is usually not known.
[210.1.5] An infinitely extended medium or microstructure
is called stationary or
statistically homogeneous if
is invariant under
spatial translations.
[210.1.6] It is called isotropic if
is invariant under rotations.
[210.1.7] A stochastic medium was defined through
its probability distribution .
[210.1.8] In practice
will be even less accessible than the
microstructure
itself.
[210.1.9] Partial information about
can be obtained
by measuring or calculating expectation values
of a geometric observable
.
[210.1.10] These are defined as
![]() |
(25) |
[page 211, §0]
where the summations indicate a summation over all configurations.
[211.0.1] Consider for example the porosity defined in (20).
[211.0.2] For a stochastic medium
becomes a random variable.
[211.0.3] Its expectation is
![]() |
![]() |
||
![]() |
|||
![]() |
(26) |
If the medium is statistically homogeneous then
![]() |
(27) |
independent of .
[211.0.4] It happens frequently that one is given only a single
sample, not an ensemble of samples.
[211.0.5] It is then necessary to invoke an ergodic hypothesis
that allows to equate spatial averages with ensemble
averages.
[211.1.1] The porosity is the first member in a hierarchy of
moment functions.
[211.1.2] The -th order moment function is defined generally as
![]() |
(28) |
for .
b (This is a footnote:) b
If a voxel has other attributes besides
being pore or matrix one may define also mixed moment functions
where
for
are the quermassintegral densities for the voxel at site
.
[211.1.3] For stationary media
where the function
depends only on
variables.
[211.1.4] Another frequently used expectation value is the correlation function
which is related to
.
[211.1.5] For a homogeneous medium it is defined as
![]() |
(29) |
where is an arbitrary reference point, and
.
[211.1.6] If the medium is isotropic then
.
[211.1.7] Note that
is normalized such that
and
.
[211.2.1] The hierarchy of moment functions , similar to
,
is mainly of theoretical interest.
[211.2.2] For a homogeneous medium
is a function of
variables.
[211.2.3] To specify
numerically becomes impractical
as
increases.
[211.2.4] If only
points are required along each coordinate axis
then giving
would require
numbers.
[211.2.5] For
this implies that already at
it becomes economical
to specify the microstructure
directly rather than
incompletely through moment or correlation functions.
[page 212, §1]
[212.1.1] An interesting geometric characteristic introduced and
discussed in the field of stochastic geometry are
contact distributions [18, 61, p. 206].
[212.1.2] Certain special cases of contact distributions have appeared
also in the porous media literature [20].
[212.1.3] Let be a compact test set containing the origin
.
[212.1.4] Then the contact distribution is defined as the conditional
probability
![]() |
(30) |
If one defines the random variable
then
[61].
[212.2.1] For the unit ball in three dimensions
is called spherical contact distribution.
[212.2.2] The quantity
is then the distribution
function of the random distance from a randomly chosen
point in
to its nearest neighbour in
.
[212.2.3] The probability density
![]() |
(31) |
was discussed in [56] as a well defined alternative to the frequently used pore size distrubution from mercury porosimetry.
[212.3.1] For an oriented unit interval
where
is the a unit vector one obtains the linear
contact distribution.
[212.3.2] The linear contact distribution written as
is sometimes called lineal path function [70].
[212.3.3] It is related to the chord length distribution
defined as the probability that an interval in the intersection
of
with a straight line containing
has length smaller than
[30, 61, p. 208].
[212.3.4] The idea of local porosity distributions is to measure
geometric observables inside compact convex subsets
, and to collect the results into empirical
histograms [27].
[212.3.5] Let
denote a cube of side length
centered at the
lattice vector
.
[212.3.6] The set
is called a measurement cell.
[212.3.7] A geometric observable
, when measured inside a measurement
cell
, is denoted as
and called a local
observable.
[212.3.8] An example are local Hadwiger functional densities
with coefficients
as in Hadwigers theorem (18).
[212.3.9] Here the local quermassintegrals are defined using
(12) as
![]() |
(32) |
for .
[212.3.10] In the following mainly the special case
will be of interest.
[212.3.11] For
the local porosity is defined by setting
,
![]() |
(33) |
[page 213, §0] [213.0.1] Local densities of surface area, mean curvature and Euler characteristic may be defined analogously. [213.0.2] The local porosity distribution, defined as
![]() |
(34) |
gives the probability density to find a local porosity
in the measurement cell
.
[213.0.3] Here
denotes the Dirac
-distribution.
[213.0.4] The support of
is the unit interval.
[213.0.5] For noncubic measurement cells
one defines
analogously
where
is the local observable in cell
.
[213.1.1] The concept of local porosity distributions
c (This is a footnote:) cor more generally ‘‘local geometry distributions’’ [28, 30]
was introduced in [27] and
has been generalized in two directions [30].
[213.1.2] Firstly by admitting more than one measurement cell,
and secondly by admitting more than one geometric observable.
[213.1.3] The general -cell distribution function is defined as [30]
![]() |
|||
![]() |
(35) |
for general measurement cells
and
observables
.
[213.1.4] The
-cell distribution is the probability density to find
the values
of the local observable
in cell
and
in cell
and so on until
of local observable
in
.
[213.1.5] Definition (35) is a broad generalization
of (34).
[213.1.6] This generalization is not purely academic, but was
motivated by problems of fluid flow in porous media
where not only
but also
becomes
important [28].
[213.1.7] Local quermassintegrals, defined in (32),
and their linear combinations (Hadwiger functionals)
furnish important examples for local observables
in (35), and they have recently been measured
[40].
[213.2.1] The general -cell distribution is very general indeed.
[213.2.2] It even contains
from
(24) as the special case
and
with
.
[213.2.3] More precisely one has
![]() |
(36) |
because in that case if
and
for
.
[213.2.4] In this way it is seen that the very definition of a stochastic
geometry is related to local porosity distributions
(or more generally local geometry distributions).
[213.2.5] As a consequence the general
-cell distribution
is again mainly of theoretical
interest, and usually unavailable for practical computations.
[213.3.1] Expectation values with respect to
have generalizations to averages with respect to
.
[213.3.2] Averaging with respect to
will be denoted by an overline.
[213.3.3] In the
[page 214, §0]
special case and
with
one finds [30]
![]() |
|||
![]() |
|||
![]() |
|||
![]() |
|||
![]() |
|||
![]() |
|||
![]() |
(37) |
thereby identifying the moment functions of order
as averages with respect to an
-cell distribution.
[214.1.1] For practical applications the -cell local porosity
distributions
and their analogues for other
quermassintegrals are of greatest interest.
[214.1.2] For a homogeneous medium the local porosity distribution obeys
![]() |
(38) |
for all lattice vectors , i.e. it is independent of
the placement of the measurement cell.
[214.1.3] A disordered medium with substitutional disorder [71]
may be viewed as a stochastic geometry obtained by placing
random elements at the cells or sites of a fixed regular
substitution lattice.
[214.1.4] For a substitutionally disordered medium
the local porosity distribution
is a periodic function of
whose
period is the lattice constant of the substitution
lattice.
[214.1.5] For stereological issues in the measurement of
from thin sections see [64].
[214.2.1] Averages with respect to are denoted by an overline.
[214.2.2] For a homogeneous medium the average local porosity is found as
![]() |
(39) |
[page 215, §0]
independent of and
.
[215.0.1] The variance of local porosities for a homogeneous medium
defined in the first equality
![]() |
(40) |
is related to the correlation function as given in the second equality [30]. [215.0.2] The skewness of the local porosity distribution is defined as the average
![]() |
(41) |
[215.1.1] The limits and
of small resp. large
measurement cells are of special interest.
[215.1.2] In the first case one reaches the limiting resolution
at
and finds for a homogeneous medium [27, 30]
![]() |
(42) |
[215.1.3] The limit is more intricate because it requires
also the limit
.
[215.1.4] For a homogeneous medium (40)
shows
for
and this suggests
![]() |
(43) |
[215.1.5] For macroscopically heterogeneous media, however,
the limiting distribution may deviate from this result
[30].
[215.1.6] If (43) holds then in both limits the geometrical
information contained in reduces to the single number
.
[215.1.7] If (42) and (43) hold there exists a special
length scale
defined as
![]() |
(44) |
at which the -components at
and
vanish.
[215.1.8] In the examples below the length
is a measure for
the size of pores.
[215.2.1] The ensemble picture underlying the definition of a stochastic medium is an idealization. [215.2.2] In practice one is given only a single realization and has to resort to an ergodic hypothesis for obtaining an estimate of the local porosity distributions. [215.2.3] In the examples below the local porosity distribution is estimated by
![]() |
(45) |
where is the number of placements of the measurement
cell
.
[215.2.4] Ideally the measurement cells should be far apart or at
least nonoverlapping, but in
[page 216, §0]
practice this restriction
cannot be observed because the samples are not large enough.
[216.0.1] In the results presented below is placed on
all lattice sites which are at least a distance
from
the boundary of
.
[216.0.2] This allows for
![]() |
(46) |
placements of in a sample with side lengths
.
[216.0.3] The use of
instead of
can lead to deviations due to
violations of the ergodic hypothesis or simply due to oversampling
the central regions of
[10, 11].
[216.0.4] Transport and propagation in porous media are controlled by the connectivity of the pore space. [216.0.5] Local percolation probabilities characterize the connectivity [27]. [216.0.6] Their calculation requires a threedimensional pore space representation, and early results were restricted to samples reconstructed laboriously from sequential thin sectioning [32].
[216.1.1] Consider the functional
defined by
![]() |
(47) |
where are two compact
convex sets with
and
,
and ‘‘
in
’’ means that
there is a path connecting
and
that lies
completely in
.
[216.1.2] In the examples below the sets
and
correspond to
opposite faces of the sample, but in general other choices
are allowed.
[216.1.3] Analogous to
defined for the whole sample one defines
for a measurement cell
![]() |
(48) |
where and
denote those two faces of
that are normal to the
direction.
[216.1.4] Similarly
denote the faces of
normal to the
- and
-directions.
[216.1.5] Two additional percolation observables
and
are introduced by
![]() |
![]() |
(49) | |
![]() |
![]() |
(50) |
[216.1.6] indicates that the cell is percolating in
all three directions while
indicates
percolation in
- or
-
-direction.
[216.1.7] The local percolation probabilities are defined as
![]() |
(51) |
[page 217, §0] where
![]() |
(52) |
[217.0.1] The local percolation probability gives
the fraction of measurement cells of sidelength
with
local porosity
that are percolating in the ‘‘
’’-direction.
[217.0.2] The total fraction of cells percolating along the ‘‘
’’-direction
is then obtained by integration
![]() |
(53) |
[217.0.3] This geometric observable is a quantitative measure for the number
of elements that have to be percolating if the pore
space geometry is approximated by a substitutionally
disordered lattice or network model.
[217.0.4] Note that neither nor
are additive
functionals, and hence local percolation probabilities
have nothing to do with Hadwigers theorem.
[217.1.1] It is interesting that there is a relation between
the local percolation probabilities and the local Euler
characteristic .
[217.1.2] The relation arises from the observation that the voxels
are closed, convex sets, and hence for any two voxels
the Euler characteristic of their intersection
![]() |
(54) |
indicates whether two voxels are nearest neighbours.
[217.1.3] A measurement cell contains
voxels.
[217.1.4] It is then possible to construct a
-matrix
with matrix elements
![]() |
![]() |
(55) | |
![]() |
![]() |
(56) |
where and the
sets
and
are two opposite
faces of the measurement cell.
[217.1.5] The rows in the matrix
correspond to voxels while
the columns correspond to voxel pairs.
[217.1.6] Define the matrix
where
is the transpose of
.
[217.1.7] The diagonal elements
give the number of
voxels to which the voxel
is connected.
[217.1.8] A matrix element
differs from zero
if and only if
and
are connected.
[217.1.9] Hence the matrix
reflects the local
connectedness of the pore space around a single voxel.
[217.1.10] Sufficiently high powers of
provide information about the global
connectedness of
.
[217.1.11] One finds
![]() |
(57) |
where is the matrix element in the upper right
hand corner and
is arbitrary subject to the condition
.
[217.1.12] The set
can always be decomposed uniquely
into pairwise disjoint connectedness components (clusters)
[page 218, §0]
whose number is given by the rank of
.
[218.0.1] Hence
![]() |
(58) |
provides an indirect connection between the local
Euler characteristic and the local percolation probabilities
mediated by the matrix .
d (This is a footnote:) dFor percolation systems it has been conjectured that
the zero of the Euler characteristic as a function of
the occupation probability is an approximation
to the percolation threshold [45])