Module B:

aggregates of grains
-formation and simulation LECTURE 6 :
physics of aggregates

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OUTLINE - LECTURE 6

VI. Details about the numerical algorithms

VII. Fractal structure

VII.1 fundamentals
VI I.2 the mass-radius relation
VII.3 the pair-correlation function
VII.4 values of the fractal dimension

VIII. Fractal aggregates

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VI.1 the hierarchical model

VI.2 hierarchical BaCCA
VI.3 hierarchical DLCCA
VI.4 hierarchical RCCA

VIII.1 fundamentals
VIII.2 definitions of the aggregate radius
VIII.3 physical properties depending only on the fractal dimension
VIII.4 definitions of the porosity

VI.1 DETAILS ABOUT THE NUMERICAL

ALGORITHMS
- the hierarchical model aggregation models are based on the double process : diffusion + sticking
full-system simulations are possible but the codes are a bit difficult to write because
of the (generally : periodic) boundary conditions, and the simulations are slow in
the usual dilute regime
in the following pages, some remarks about :
how to model diffusion (Brownian, ballistic or reaction-limited)
how to manage the sticking event

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VI.2 DETAILS ABOUT THE NUMERICAL ALGORITHMS

- Hierarchical Ballistic Cluster-Cluster Aggregation model along the simulation, the most demanding part is the diffusion, that is :
consider two clusters moving along random linear trajectories, when do they
collide?
the full-system problem is tricky because of the periodic boundary conditions
(and kind of billiard if hard boundaries)

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VI.2 DETAILS ABOUT THE NUMERICAL ALGORITHMS

- Hierarchical Ballistic Cluster-Cluster Aggregation model the hierarchical algorithm is much simpler

(because only 2 clusters in free space)

in principle, one should take the initial distance, Do, between the two clusters to be
1/n1/3, with n the number of clusters per unit of volume
generally, one does not know the value of Do,
but it was proved that the resulting clusters
do not depend on the choice of Do if
Do > 1.2(Rmax,1+Rmax,2)

Do
Rmax,2

Rmax,1

computing time is Do2

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take Do as small as possible

VI.2 DETAILS ABOUT THE NUMERICAL ALGORITHMS

- Hierarchical Ballistic Cluster-Cluster Aggregation model consider two clusters moving along random linear trajectories, when do they
collide?
lu
j

for each couple of grains (i,j) with i cluster1 and j cluster2,

is there a positive solution in l to the quadratic equation :

(ri lu r j ) 2 (2a) 2

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VI.2 DETAILS ABOUT THE NUMERICAL ALGORITHMS

- Hierarchical Ballistic Cluster-Cluster Aggregation model consider two clusters moving along random linear trajectories, when do they
collide?
lu
rj

much faster
than N2 process

rj-ri

for each couple of grains (i,j) with i cluster1 and j cluster2,

is there a positive solution in l to the quadratic equation :

(ri lu r j ) 2 (2a) 2
yes if :

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ri

u(r j ri ) 0

u(r

2
2

r
)

(
r

r
)

4
a
j
i
j
i
2

(and starting from the circumscribed spheres)

positive solution
real solution

VI.3 DETAILS ABOUT THE NUMERICAL ALGORITHMS

- Hierarchical Brownian Cluster-Cluster Aggregation model same idea as for BaCCA, but diffusion = random walk

at each step :
dl u
rj

rj-ri

ri

for each couple of grains (i,j) with i cluster1 and j cluster2,

is there a positive solution in l < dl to the quadratic equation :

(ri lu r j ) 2 (2a) 2
yes if :

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u(r j ri ) 0

u(r

2
2

r
)

(
r

r
)

4
a
j
i
j
i
2

(and starting from the circumscribed spheres)

positive solution
real solution

VI.3 DETAILS ABOUT THE NUMERICAL ALGORITHMS

- Hierarchical Brownian Cluster-Cluster Aggregation model one can take the initial distance, Do, between the two clusters as small as possible
(for example : Rmax,1 + Rmax,2 + dl)

select a large sphere (radius Dmax) : if the diffusing cluster crosses the limit of
this large sphere : it is removed and replaced on the small sphere of radius Do

Dmax

Do

computing time is Dmax2

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take Dmax as small as possible

it was proved that the resulting clusters do not depend on the choice of Dmax if Dmax > 5Do

VI.4 DETAILS ABOUT THE NUMERICAL ALGORITHMS

- Hierarchical Reaction-Limited Cluster-Cluster Aggregation Meakins algorithm = no diffusion
the full-system simulations are impracticable (sticking probability very small)
at each step :

find a random couple of grains (i,j) with i cluster1 and j cluster2,

and a random tangent position between them, such that :

(ri ' r j ' ) 2 (2a) 2

for all the other couples (i,j) of grains
(we do not know tricks to make it faster)

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OUTLINE - LECTURE 6

VI. Details about the numerical algorithms

VII. Fractal structure

VII.1 fundamentals
VI I.2 the mass-radius relation
VII.3 the pair-correlation function
VII.4 values of the fractal dimension

VIII. Fractal aggregates

R. Botet 04/2016

VI.1 the hierarchical model

VI.2 hierarchical BaCCA
VI.3 hierarchical DLCCA
VI.4 hierarchical RCCA

VIII.1 fundamentals
VIII.2 definitions of the aggregate radius
VIII.3 physical properties depending only on the fractal dimension
VIII.4 definitions of the porosity

VII.1 FRACTAL STRUCTURE

- FUNDAMENTALS Witten and Sander proved in 1981 that natural aerosol aggregates have fractal structure

what is a fractal?

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VII.1 FRACTAL STRUCTURE

- FUNDAMENTALS FRACTAL IS CHARACTERIZED BY SELF-SIMILARITY
that is : part is similar to the whole, just after changing the length-scale

example : Vicsek fractal

grain

5 grains
length-scale divided by 3
25 grains
length-scale divided by 9

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5n grains
length-scale divided by 3n

VII.2 FRACTAL STRUCTURE

- THE MASS-RADIUS RELATION FRACTAL IS CHARACTERIZED BY SCALING-LAW
in particular : between mass and diameter (or : number of grains and radius)

example : finite-size Vicsek fractals

N = 5 grains
diameter = 3

NR

df
N = 25 grains
diameter = 9

in this example df = log(5)/log(3) = 1.46

(5n = (3n)df)
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N = 5n grains
diameter = 3n

VII.2 FRACTAL STRUCTURE

- THE MASS-RADIUS RELATION FRACTAL IS CHARACTERIZED BY SCALING-LAW
in particular : between mass and diameter (or : number of grains and radius)

check and measurement of the fractal dimension

is straightforward if we can measure both mass and radius

log N

NR

df

log R
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Au colloids, Weitz et al 1984

VII.2 FRACTAL STRUCTURE

- THE MASS-RADIUS RELATION FRACTAL IS CHARACTERIZED BY SCALING-LAW
in particular : between mass and diameter (or : number of grains and radius)

a real experiment :

NR

df

in this example df 1.7

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carbon black smoke, Xiong and Frielander 2001

VII.3 FRACTAL STRUCTURE

- THE PAIR-CORRELATION FUNCTION FRACTAL IS CHARACTERIZED BY SCALING-LAW
g(r) = probability to find grain at the distance r from a given grain

g (r )

log g(r)

rdr

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Ag
grains04/2016
in ait-waterinterface, Yongdong et al 2002

1
r

3 d f

hr / R g

log r

with h a cutoff function

h(0) = 1 ; h() = 0

VII.3 FRACTAL STRUCTURE

- THE PAIR-CORRELATION FUNCTION FRACTAL IS CHARACTERIZED BY SCALING-LAW
g(r) = probability to find grain at the distance r from a given grain

g (r )

NR

df

1
r

3 d f

with h a cutoff function

h(0) = 1 ; h() = 0

number of grains inside a sphere of radius r centered on the

center of mass

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hr / R g

g (r ' )4r '2 dr ' r

df

RAYLEIGH-GANS-DEBYE THEORY
- THE POWER-LAW REGIMEF ( , )

sin qr
g (r )4r 2 dr
qr

for a fractal particle (definition) :

g (r )

hr / R g

1
r

3 d f

with h a cutoff function

h(0) = 1 ; h() = 0

Menger sponge (df = 2.57)

then :

F ( , )

1
df
q

d f 2

sin(u ) h(u / qRg )du

such that if qRg >> 1 :

power-law regime
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F ( , )

1
df
q

direct measurement of the

fractal dimension of the particles

RAYLEIGH-GANS-DEBYE THEORY
- THE POWER-LAW REGIMEGuinier regime ( Rg)

Isca(q)

power-law regime ( df )

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F ( , )

1
df
q

VII.4 FRACTAL STRUCTURE

- VALUES OF THE FRACTAL DIMENSION FOR AGGREGATES 1 df 3
linear aggregate

homogeneous aggregate

NR

N R3

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VII.4 FRACTAL STRUCTURE

- VALUES OF THE FRACTAL DIMENSION FOR AGGREGATES 1 df 3
linear aggregate

homogeneous aggregate

NR
but : fractal dimension is related to correlations
not to porosity
porous df 3 polymeric sphere (Lapierre, 2014)

N (1 p) R3
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volume fraction

N R3

OUTLINE - LECTURE 6

VI. Details about the numerical algorithms

VII. Fractal structure

VII.1 fundamentals
VI I.2 the mass-radius relation
VII.3 the pair-correlation function
VII.4 values of the fractal dimension

VIII. Fractal aggregates

R. Botet 04/2016

VI.1 the hierarchical model

VI.2 hierarchical BaCCA
VI.3 hierarchical DLCCA
VI.4 hierarchical RCCA

VIII.1 fundamentals
VIII.2 definitions of the aggregate radius
VIII.3 physical properties depending only on the fractal dimension
VIII.4 definitions of the porosity

VIII.1 FRACTAL AGGREGATES

- FUNDAMENTALS Witten and Sander proved in 1981 that natural aerosol aggregates have fractal structure
of fractal dimension df = 1.8
this result agrees with numerical results on the aggregate models that we know:

fractal dimensions
Brownian

Ballistic

Reaction-Limited

Cluster-Cluster

1.8

1.9

2.0

Particle-Cluster

2.5

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PARTICLE-CLUSTER

CLUSTER-CLUSTER

BROWNIAN

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df = 1.8

df = 2.5

BALLISTIC

REACTION-LIMITED

df = 1.9

df = 2.0

df = 3

df = 3

VIII.2 FRACTAL AGGREGATES

- DEFINITIONS OF THE AGGREGATE RADIUS 1) the relevant definition of the radius for dust particle is the radius of gyration :

NR

df

1
R
N
2
g

2
(
r

r
)
i cm
i 1

1
where rcm is the location of the center of mass : rcm
N

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r
i 1

VIII.2 FRACTAL AGGREGATES

- DEFINITIONS OF THE AGGREGATE RADIUS 1) the relevant definition of the radius for dust particle is the radius of gyration :

NR

df

1
R
N
2
g

2
(
r

r
)
i cm
i 1

1
where rcm is the location of the center of mass : rcm
N
2) maximum radius (= half diameter of the particle):

NR

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df

2
R max

1
max i , j (ri r j ) 2
4

r
i 1

VIII.2 FRACTAL AGGREGATES

- DEFINITIONS OF THE AGGREGATE RADIUS 1) the relevant definition of the radius for dust particle is the radius of gyration :

NR

df

1
R
N
2
g

2
(
r

r
)
i cm
i 1

1
where rcm is the location of the center of mass : rcm
N

r
i 1

2) maximum radius (= half diameter of the particle):

NR

df

2
R max

1
max i , j (ri r j ) 2
4

3) effective radius ( = radius of the sphere of same volume) :

NR

df
eff

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3
Reff

3V
4

VIII.2 FRACTAL AGGREGATES

- DEFINITIONS OF THE AGGREGATE RADIUS for optical properties of fractal dust, it is important to know if the fractal dimension of the
scattering particles is < 2 or > 2

df 1.9
no shadowing
all the grains feel directly the incident light

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df 2.5
shadowing
most of the grains are hidden behind others

VIII.2 FRACTAL AGGREGATES

- DEFINITIONS OF THE AGGREGATE RADIUS for optical properties of fractal dust, it is important to know if the fractal dimension of the
scattering particles is < 2 or > 2

df 2.5

df 1.9

4) the projected radius (= radius of the circle of same area as projection)

NR

df
pro

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2
pro

VIII.2 FRACTAL AGGREGATES

- DEFINITIONS OF THE AGGREGATE RADIUS -

Particle-Cluster aggregates are isotropic in average

aggregate radius is well-defined

df = 2.5
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df = 3

df = 3

VIII.2 FRACTAL AGGREGATES

- DEFINITIONS OF THE AGGREGATE RADIUS Cluster-Cluster aggregates are essentially anisotropic
one can define three aggregate radius

2
2
they are the eigenvalues of the inertia matrix: ( yi zi )
i
yi xi

i
zi xi

df = 2.0

for the RCCA model:

Rg1/Rg3 = 1.75
Rg2/Rg3 = 1.63

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xi zi
i
i

2
2
i ( xi zi ) i yi zi
z i yi
( xi2 yi2 )

i
i

xi yi

VIII.3 FRACTAL AGGREGATES

- PHYSICAL PROPERTIES DEPENDING ONLY ON df 1. electromagnetic wave scattering
in the domain : 1/R < q 4sin( /2)/l < 1/a , we have seen that there exists the power-law
behavior of the X-ray scattering (when Rayleigh-Gans-Debye theory is valid) :

I (q) 1 / q

df

because I(q) is essentially the Fourier transform of the pair-correlation function g(r)

it is robust power-law as it remains true even if the conditions are beyond the RGD theory

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VIII.3 FRACTAL AGGREGATES

- PHYSICAL PROPERTIES DEPENDING ONLY ON df 2. orbits of dust particles
in the solar system, orbits of dust particles around the Sun are essentially ruled by the ratio,
b , between the force due to radiative pressure and the gravitational force :

S
b Q pr
M

surface of the particle

mass of the particle

if the particle is compact : b 1/L (L = typical size of the particle), hence big difference
between small and large particles
it the particle is fractal of fractal dimension df < 2, the system is so fluffy that almost all
the grains are in surface, then the surface facing the sun is just N, similarly to the mass.
Then:

b Qpr

and no big difference between small and large particles is expected in the fractal df < 2 case

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VIII.4 FRACTAL AGGREGATES

- DEFINITIONS OF THE POROSITY the porosity, p, of a material is generally defined as the void fraction, that is :

p 1f
where f is the volume fraction (proportion of matter = N(4a3/3)/(4R3/3))
For a fractal aggregate of size N and radius R for which : N ko (R/a)df, porosity is :

a
p 1 k
R
1
o

3 d f

which depends on the size, R, of the aggregate if df < 3

p 1 for the large aggregates df < 3

p constant < 1 for the large aggregates df 3

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VIII.4 FRACTAL AGGREGATES

- DEFINITIONS OF THE POROSITY precise definition of the porosity depends on the context
(it may depend on the physical features)
a few contexts :

light scattering using the Effective-Medium theory (aggregate = sphere + inclusions)

stocking chemical compounds (aggregate = high specific surface)
chemical reactor (aggregate = catalyst)
transport of fluid throughout the aggregate (aggregate = permeable material)

a
p 1 ko1
R

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3 d f

is only related to the inertia of the aggregate

(how fluffy it is)

VIII.4 FRACTAL AGGREGATES

- DEFINITIONS OF THE POROSITY example : the Effective-Medium Theory

ms

good choice for the effective refractive index:

mm

Maxwell-Garnett formula

m 2 mm2
ms2 mm2
p 2
2
2
m 2mm
ms 2mm2
volume fraction of the inclusions

Ag inclusions in C grains, Tang et al, 2010

here : refractive index ms for the inclusions

and mm for the matrix
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VIII.4 FRACTAL AGGREGATES

- DEFINITIONS OF THE POROSITY example : the Effective-Medium Theory

mg

inclusions = grains (df < 2) :

1

mg2 1

m 1
(1 p) 2
2
m 2
mg 2
2

Maxwell-Garnett formula

volume fraction of the grains

aggregate df < 2

refractive index mg for the grains

and 1 for the voids
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VIII.4 FRACTAL AGGREGATES

- DEFINITIONS OF THE POROSITY example : the Effective-Medium Theory

mg

inclusions = voids (df > 2) :

1

Maxwell-Garnett formula

m 2 mg2
m 2m
2

2
g

1 mg2
1 2mg2

volume fraction of the voids

aggregate df > 2

refractive index mg for the grains

and 1 for the voids
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VIII.4 FRACTAL AGGREGATES

- DEFINITIONS OF THE POROSITY example : the Effective-Medium Theory

another possible definition of the porosity in

this context :
determine the best value of the refractive index m for
which the Mie sphere theory reproduces the results from
T-Matrix or DDA
warning 1 : the resulting porosity depends on the size R
of the aggregate
warning 2 : the resulting porosity should be close to
(but a bit different from) the Maxwell-Garnett formula

the corresponding porous sphere scatters the same as

the aggregate
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better formula

Summary of the Lecture 6

Cluster-Cluster aggregates are fractal

fractal dimension depends on the diffusion process
df for Particle-Cluster > df for Cluster-Cluster

physical properties of fractal clusters depend on df

df can be measured through scattering experiments
some geometric features, such as porosity, are not well defined

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