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Module B

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

R. Botet 04/2016

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

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

R. Botet 04/2016

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)

R. Botet 04/2016

2 Rmax. one does not know the value of Do. between the two clusters to be 1/n1/3.VI.1 computing time is  Do2 R.1+Rmax.2 DETAILS ABOUT THE NUMERICAL ALGORITHMS . but it was proved that the resulting clusters do not depend on the choice of Do if Do > 1. Do. one should take the initial distance. Botet 04/2016  take Do as small as possible .2(Rmax. with n the number of clusters per unit of volume generally.Hierarchical Ballistic Cluster-Cluster Aggregation model the hierarchical algorithm is much simpler (because only 2 clusters in free space) in principle.2) Do Rmax.

j) with i  cluster1 and j  cluster2. when do they collide? lu j i for each couple of grains (i. is there a positive solution in l to the quadratic equation : (ri  lu  r j ) 2  (2a) 2 R. Botet 04/2016 ? .2 DETAILS ABOUT THE NUMERICAL ALGORITHMS .Hierarchical Ballistic Cluster-Cluster Aggregation model consider two clusters moving along random linear trajectories.VI.

VI. 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 : R. Botet 04/2016 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 .2 DETAILS ABOUT THE NUMERICAL ALGORITHMS .Hierarchical Ballistic Cluster-Cluster Aggregation model consider two clusters moving along random linear trajectories.

3 DETAILS ABOUT THE NUMERICAL ALGORITHMS . Botet 04/2016 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. 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 : R.Hierarchical Brownian Cluster-Cluster Aggregation model same idea as for BaCCA.

between the two clusters as small as possible (for example : Rmax.1 + Rmax.Hierarchical Brownian Cluster-Cluster Aggregation model one can take the initial distance. Do.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 R.VI.3 DETAILS ABOUT THE NUMERICAL ALGORITHMS . Botet 04/2016  take Dmax as small as possible it was proved that the resulting clusters do not depend on the choice of Dmax if Dmax > 5Do .

and a random tangent position between them. Botet 04/2016 .VI.4 DETAILS ABOUT THE NUMERICAL ALGORITHMS .Hierarchical Reaction-Limited Cluster-Cluster Aggregation Meakin’s algorithm = no diffusion the full-system simulations are impracticable (sticking probability very small) at each step : find a random couple of grains (i.j’) of grains (we do not know tricks to make it faster) R.j) with i  cluster1 and j  cluster2. such that : (ri '  r j ' ) 2  (2a) 2 for all the other couples (i’.

3 hierarchical DLCCA VI. Details about the numerical algorithms      VII.2 the mass-radius relation VII.1 fundamentals VIII.LECTURE 6  VI.1 the hierarchical model VI. Botet 04/2016 VI.4 hierarchical RCCA VIII.4 values of the fractal dimension VIII. Fractal structure      VII.OUTLINE .2 definitions of the aggregate radius VIII.2 hierarchical BaCCA VI.3 physical properties depending only on the fractal dimension VIII.1 fundamentals VI I. Fractal aggregates     R.3 the pair-correlation function VII.4 definitions of the porosity .

1 FRACTAL STRUCTURE . Botet 04/2016 .VII.FUNDAMENTALS Witten and Sander proved in 1981 that natural aerosol aggregates have fractal structure… what is a fractal? R.

1 FRACTAL STRUCTURE .VII. just after changing the length-scale example : Vicsek fractal grain 5 grains length-scale divided by 3 25 grains length-scale divided by 9 R. Botet 04/2016 … 5n grains length-scale divided by 3n .FUNDAMENTALS FRACTAL IS CHARACTERIZED BY SELF-SIMILARITY that is : part is similar to the whole.

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 NR df N = 25 grains diameter = 9 in this example  df = log(5)/log(3) = 1.46… (5n = (3n)df) R.VII. Botet 04/2016 N = 5n grains diameter = 3n .2 FRACTAL STRUCTURE .

2 FRACTAL STRUCTURE . Weitz et al 1984 . Botet 04/2016 Au colloids.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 NR df          log R R.VII.

Botet 04/2016 carbon black smoke.VII.7 R. Xiong and Frielander 2001 .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 : NR df in this example  df  1.2 FRACTAL STRUCTURE .

VII. Yongdong et al 2002 1 r 3 d f    hr / R g        log r with h a cutoff function h(0) = 1 .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) r rdr R. h() = 0 . Botet Ag grains04/2016 in ait-waterinterface.

VII. h() = 0 number of grains inside a sphere of radius r centered on the center of mass   r 0 R. Botet 04/2016 hr / R g  g (r ' )4r '2 dr '  r df .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 )  NR df 1 r 3 d f with h a cutoff function h(0) = 1 .3 FRACTAL STRUCTURE .

 ) 2 1  df q direct measurement of the fractal dimension of the particles .THE POWER-LAW REGIMEF ( .  ) 2   0 sin qr g (r )4r 2 dr qr for a fractal particle (definition) : g (r )  hr / R g  1 r 3 d f with h a cutoff function h(0) = 1 . Botet 04/2016 F ( . h() = 0 Menger sponge (df = 2.57) then : F ( .RAYLEIGH-GANS-DEBYE THEORY .  ) 2 1  df q   0 u d f 2 sin(u ) h(u / qRg )du such that if qRg >> 1 : power-law regime  R.

Botet 04/2016 F ( .RAYLEIGH-GANS-DEBYE THEORY .THE POWER-LAW REGIMEGuinier regime ( Rg) Isca(q) power-law regime ( df ) q R.  ) 2 1  df q .

4 FRACTAL STRUCTURE .VII.VALUES OF THE FRACTAL DIMENSION FOR AGGREGATES  1  df  3 linear aggregate homogeneous aggregate NR N  R3 R. Botet 04/2016 .

4 FRACTAL STRUCTURE .VII. Botet 04/2016 volume fraction N  R3 . 2014)  N  (1  p) R3 R.VALUES OF THE FRACTAL DIMENSION FOR AGGREGATES  1  df  3 linear aggregate homogeneous aggregate NR but : fractal dimension is related to correlations not to porosity porous df  3 polymeric sphere (Lapierre.

LECTURE 6  VI.OUTLINE .3 the pair-correlation function VII.2 the mass-radius relation VII. Fractal aggregates     R.4 definitions of the porosity .4 values of the fractal dimension VIII.2 definitions of the aggregate radius VIII. Botet 04/2016 VI.4 hierarchical RCCA VIII. Details about the numerical algorithms      VII.2 hierarchical BaCCA VI.1 the hierarchical model VI.3 physical properties depending only on the fractal dimension VIII.1 fundamentals VIII. Fractal structure      VII.3 hierarchical DLCCA VI.1 fundamentals VI I.

Botet 04/2016 .0 Particle-Cluster 2.5 3 3 R.VIII.1 FRACTAL AGGREGATES .9 2.8 1.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 df = 2.PARTICLE-CLUSTER CLUSTER-CLUSTER BROWNIAN R.0 df = 3 df = 3 .5 BALLISTIC REACTION-LIMITED df = 1.9 df = 2. Botet 04/2016 df = 1.

2 FRACTAL AGGREGATES .DEFINITIONS OF THE AGGREGATE RADIUS 1) the relevant definition of the radius for dust particle is the radius of gyration : NR df 1 R  N 2 g N 2 ( r  r )  i cm i 1 1 where rcm is the location of the center of mass : rcm  N R.VIII. Botet 04/2016 N r i 1 i .

VIII.2 FRACTAL AGGREGATES . j (ri  r j ) 2 4  N r i 1 i . Botet 04/2016 df 2 R max   1 max i .DEFINITIONS OF THE AGGREGATE RADIUS 1) the relevant definition of the radius for dust particle is the radius of gyration : NR df 1 R  N 2 g N 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): NR R.

Botet 04/2016 3 Reff  3V 4 i .DEFINITIONS OF THE AGGREGATE RADIUS 1) the relevant definition of the radius for dust particle is the radius of gyration : NR df 1 R  N 2 g N 2 ( r  r )  i cm i 1 1 where rcm is the location of the center of mass : rcm  N N r i 1 2) maximum radius (= half diameter of the particle): NR df 2 R max   1 max i . j (ri  r j ) 2 4  3) effective radius ( = radius of the sphere of same volume) : NR df eff R.2 FRACTAL AGGREGATES .VIII.

5 shadowing most of the grains are hidden behind others .2 FRACTAL AGGREGATES .DEFINITIONS OF THE AGGREGATE RADIUS for optical properties of fractal dust.VIII. Botet 04/2016 df  2.9 no shadowing all the grains feel directly the incident light R. it is important to know if the fractal dimension of the scattering particles is < 2 or > 2 df  1.

Botet 04/2016 R 2 pro  S  .2 FRACTAL AGGREGATES . it is important to know if the fractal dimension of the scattering particles is < 2 or > 2 df  2.VIII.9 4) the projected radius (= radius of the circle of same area as projection) NR df pro R.DEFINITIONS OF THE AGGREGATE RADIUS for optical properties of fractal dust.5 df  1.

2 FRACTAL AGGREGATES . Botet 04/2016 df = 3 df = 3 .5 R.VIII.DEFINITIONS OF THE AGGREGATE RADIUS - Particle-Cluster aggregates are isotropic in average  aggregate radius is well-defined df = 2.

75 Rg2/Rg3 = 1.63 R.VIII. Botet 04/2016    xi zi  i i  2 2 i ( xi  zi )  i yi zi    z i yi ( xi2  yi2 )   i i    xi yi .0 for the RCCA model: Rg1/Rg3 = 1.2 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  i  df = 2.

Botet 04/2016 . electromagnetic wave scattering • in the domain : 1/R < q  4sin( /2)/l < 1/a .PHYSICAL PROPERTIES DEPENDING ONLY ON df 1.VIII. 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 R.3 FRACTAL AGGREGATES .

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).3 FRACTAL AGGREGATES .VIII. hence big difference between small and large particles  it the particle is fractal of fractal dimension df < 2.PHYSICAL PROPERTIES DEPENDING ONLY ON df 2. orbits of dust particles around the Sun are essentially ruled by the ratio. similarly to the mass. orbits of dust particles • in the solar system. Botet 04/2016 . Then: b  Qpr and no big difference between small and large particles is expected in the fractal df < 2 case R. then the surface facing the sun is just  N. b . the system is so fluffy that almost all the grains are in surface.

of a material is generally defined as the void fraction. p. porosity is : a p  1 k   R 1 o 3 d f which depends on the size.DEFINITIONS OF THE POROSITY • the porosity.VIII. Botet 04/2016 .4 FRACTAL AGGREGATES . of the aggregate if df < 3 p  1 for the large aggregates df < 3 p  constant < 1 for the large aggregates df  3 R. that is : p  1f where f is the volume fraction (proportion of matter = N(4a3/3)/(4R3/3)) For a fractal aggregate of size N and radius R for which : N  ko (R/a)df. R.

VIII. Botet 04/2016 3 d f is only related to the inertia of the aggregate (how fluffy it is) .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  ko1   R R.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.4 FRACTAL AGGREGATES . Botet 04/2016 .VIII. Tang et al. 2010 here : refractive index  ms for the inclusions and  mm for the matrix R.

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 R.VIII.4 FRACTAL AGGREGATES . Botet 04/2016 .

VIII.4 FRACTAL AGGREGATES . Botet 04/2016 .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 p 1  mg2 1  2mg2 volume fraction of the voids aggregate df > 2 refractive index  mg for the grains and  1 for the voids R.

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 R.4 FRACTAL AGGREGATES . Botet 04/2016 better formula .VIII.

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. are not well defined R. such as porosity. Botet 04/2016 .