Modeling of Plume Dynamics and Shock Wave

in Laser Ablation with Application to
Nano{Technology
Diomar Cesar Lob~ao12 and Alex Povitsky12
1

2

Concordia University, Montreal H3G 1M8, Quebec, Canada,
lobao@cerca.umontreal.ca,
WWW home page: http://www.cerca.umontreal.ca/~lobao
Centre de recherche en calcul applique{CERCA, 5160, boul. Decarie, bureau 400
H3X 2H9 Montreal, Quebec, Canada

The aim of this study is to nd optimal conditions for the
formation of carbon nanotubes in a laser furnace. This paper will describe our mathematical model and numerical algorithm, and discuss
some of the uid physics underlying this crucial technology. An axisymmetric unsteady computational gas dynamic model of plume expansion
into ambiance has been developed. In the present work the vapor gas
phase is modeled using the Relaxing TVD scheme in generalized coordinates. A numerical model of pulsed ablated gas is proposed based
on the mass, momentum, and energy conservation laws. The proposed
model implements a multi-species formulation for concentration of chemical components combined with the compressible Euler equations. To advance the solution in time, this set of equations is integrated numerically
by second-order Runge-Kutta scheme.
Abstract.

1

Introduction

Known processes of production of carbon nanotubes-tubes include laser ablation
(LA), chemical vapor deposition (CVD), and decomposition of high-pressure
carbon oxide (HiPco). The practical choice of the process is a trade-o between
product quality and quantity. All processes are controlled by metal catalyst
particles that initialize synthesis of carbon nanotubes from feed-stock gas or
ejected plume. Similar to the HiPco modeling [7], the LA CFD model is based
on the combined Eulerian and Lagrangian approach applied to the tracking of the
trajectories of catalyst particles. The Lagrangian approach to track temperature
of the catalyst particles in the plume is implemented to evaluate the eÆciency of
the process. In the laser vaporization process, the feedstock plume loaded with
catalyst particles expands explosively into the background gas. The thermal
behavior of catalyst particles is critical for nanotubes synthesis.
Available experimental data [1],[2] include average plume temperature at a
given time moment and the plume geometric shape. Our computational results
are in good agreement with these computational and experimental results. There

is no available experimental data about temperature of individual catalyst particles. The present code perform very well in very low ambient pressure, pressure
of order of 10 6 atm as well as up to 1:0 atm has been tested.
Shock waves were formed in the ambient gas in the case of the explosive ablation. The propagation of incident and re ected shock waves a ects the plume
behind it. The plume mixing is caused by the Raleigh{Taylor instability at the
plume{to{gas interface and the baroclinic deposition of vorticity while the re ected shock wave interacts with the plume [7]. For the assessment of the proposed mathematical model and numerical method, numerical results are compared with those obtained in the experiments found in [1],[2] where the ambient
gas was the inert Argon and the substrate target material was the Carbon Trimmer C3.

2

Governing Equations

The compressible Euler equations written in general curvilinear coordinates ; 
for unsteady ows take the following form:

@ Q~ + @ F~
@ t~ @

@ G~
@

+

= S~

(1)

For generality all variables will be non{dimensionalized. Although the parameters used in the non{dimensionalization process are arbitrary, freestream quantities are usually used. Applying a non-dimensionalization to the Euler equations
leaves all equations in the same form as before, so they can be viewed as equations in the new non{dimensional variables. The conserved variable vector and
uxes are given as,

Q

2 
3
66  u 7
Æ 6  v 777
= 6
J 66 E 77
4  C1 5

F 

C

2 
U 3
6 
uU + xp 77
6
6
Æ  vU + y p 77
= 6
J 66 (E + p)U 77
4  C1 U 5 

C U

2

G

(2)

2

2 
V 3
66  uV + x p 7
7
6  vV + y p 7
Æ
7
= 6
6
J 6 (E + p)V 77
4  C1 V 5

S

2 3
0
6
607
7
16
p 77
= 6
J 66 0 77
405

(3) 

C V
0
T
Where  is the density, m = (U; V; C ; C ) is mass, E is total energy
per unit volume, p pressure, and C ; C are mass fraction of two species being
considered respectively. U; V are the contravariant velocities [8] which are in directions normal to constant ;  surfaces respectively, and J = 1 = [x y x y ]
is the Jacobian of transformation. Æ is the radial axisymmetrical coordinate in
2

1

1

2

2 

direction, for 2D full geometry Æ = 1 and S = 0. The quantities x and x
are the metrics of the transformation (x; y ) ! (;  ). In the numerical scheme,
the metrics are approximated by second{order nite di erences where the indices i; j are related to the ;  directions respectively. Second order three{point
backward nite di erence are used for the boundary points.
The total energy is de ned by
E

p +  (u 2+ v )
2

=

2

+ 

h

(4)

where h = h(hi ) is the enthalpy per unit mass for each species. The equation of
state for multi-species ow can be written as,

p=

2
X

i=1

pi =

2
X

i=1

2
X 

Ci Ri T = ( CiRi )T = RT
i=1

where T is temperature and R is de ned as, R =

3

(5)

P2
i=1 Ci Ri [9].

Numerical Scheme

The relaxing TVD scheme as described in [22] and [6] provides high order accuracy to approximate solutions of compressible Euler equations (Eq.(1)) written
in conservation form. Relaxation methods make use of the characteristic variables of the system and nite speed of propagation and do not need Riemann
solvers. Using the same idea the relaxing TVD is very similar to central schemes
as those described in [23] and [11]. The method used to solve Euler equations
is the monotone upwind scheme for conservation laws (MUSCL). The MUSCL
alone when applied to Euler equations meets diÆculties by the fact that the
momentum and energy uxes depend on the pressure. In order to determine the
ow upwind direction it is needed to calculate the ux Jacobian eigenvectors
matrices at each cell at each time step. This is straight for advection equation
since that the velocity can be used to de ne the ow upwind direction, however
it is not for the Euler equations. The relaxing TVD scheme o ers an alternative
to circumvent the need for calculating the ux Jacobian eigenvectors matrices
the for Euler equations, which for multi{species and or reactive chemical systems
is extremely economical and eÆcient. The MUSCL method is completed with a
second order explicit Runge{Kutta time integrator.
3.1

Relaxing TVD Scheme

Let us consider a 1D system of conservation laws and illustrate the relaxing TVD
scheme, since the generalization to multi{dimensional cases is straightforward.

@q
@t

+

@F [q]
@x

=0

(6)

This system is replaced by the relaxing system as,

@q + @cv = 0
@t @cq
@x
@v
@t + @x = 0

(7)

where c(x; t) is a free parameter called freezing speed [6]. The essence of the
method is to apply Strang [12] splitting on these two equations. A TVD ux
slope limiter is applied to the linear advection equation, also called relaxation
system with v = F [q ]=c and it is used to calculate uxes, while an explicit time
integration is implemented using second order Runge{Kutta method. In [6] is
shown that this scheme is TVD under the constraint that c is grater than the
characteristic speed u given by @F
@q . One way to satisfy this condition is to de ne
c as: c = j u j + a, where a is the local speedq+ofv sound. To solve
the relaxed
system, it is decoupled using variables w1 = 2 and w2 = q 2 v . The linear
system of equations

@w
@t

+

@cw
@x

=0

(8)

is discretized in space using MUSCL scheme as described in [6].
The conserved averaged quantities w are de ned at integer grid cells xi .
It is needed to de ne the uxes at cell boundaries, F = cw where F =
F (w1 ) F (w2 ) at xi+1=2 . Then, @x cw = F (xi+1=2 ) F (xi 1=2 ). The remaining
step is to de ne the ux F at the half cells. The rst{order upwind de nition
is F (xi+1=2 ) = cw(xi ), assuming ow is to right. There are two second{order
choices: 1) (cw(xi ) + cw(xi+1 ))=2 and 2) (3=2)cw(xi (1=2)cw(xi 1 )). Generalizing these choices is possible to write F (xi+1=2 ) = cw(xi ) + w, where 
w+ = cw(xi+12) cw(xi) and w = cw(xi) 2cw(xi 1) . De ne the limiter minmod
as minmod(a; b) = (sign(a) + sign(b))Min(j a j; j b j)=2. It chooses the argument with smaller absolute magnitude if the magnitudes have the same sign, and
returns zero otherwise. The w = minmod(w+ ; w ) limiter is the simplest
TVD MUSCL choice. At the extrema, minmod=0, and the second order scheme
reverts to a rst order upwind scheme. The mathematical justi cation for this
can be found in [13]. The time step is determined by satisfying the CFL condit
tion, cmax 
x  1. Note that a new freezing speed is computed for each partial
time step in the Runge-Kutta scheme.
For more than one spatial dimension, the simplest generalization is to apply
the freezing advection to each dimension. In two dimensions, the system( 1) can
be split using Strang technique [12] into two separate 1D equations which are
solved in sequential way. Consider that the operator Li represent the updating
of q t to q t+t making use of the ux in the i direction. The sweep has to be
symmetrical, rst the forward sweep is carried out as, q t+t = L L q t and them
the reverse sweep is carried out as, q t+2t = L L q t+t . Note that the same
time step t has to be used in order to keep the second order accuracy in time.

4

Experimental Setup and Computational Model

Radiation of a laser beam is focused on Carbon C3 solid target. The diameter of
the focusing spot is 5mm, placed inside a chamber containing Argon at pressure
of 1atm and temperature of 1500K [1],[2]. The pulse ring duration is 20ns. Under these conditions, the laser delivers 100atm pressure at 5000K for the gaseous
plume. The axisymmetrical chamber is 5:0cm of diameter and 25cm long. The
physical domain is discretized in a computational domain using a structured
grid, having 250  50 nodes in the axial and radial directions, respectively. The
initial conditions at the grid points corresponding to the 5mm diameter laser
beam spot was kept on for approximately 20:0ns. At the end of this time, the
carbon mass fraction boundary conditions are turned o and replaced by a non{
penetrating solid wall boundary condition. Then, the numerical code solves this
ow eld as the time progress. The out ow is set as adjustable sub/supersonic
boundary. The solid boundary is treated imposing the tangential velocity satisfying n  V = 0, n is the normal surface unit vector. On the axisymmetrical
boundary, simple extrapolation boundary condition is adopted.

5

Modeling of plume dynamics

In all simulations, a sequence of CFL numbers was used in order to integrate the
equations with the maximum time step and to avoid the blow up of the solution
due to the large pressure gradients, which may cause non-linear instability. For
the rst 180 steps CFL of 0:0001 is used and the time step is of the order of
10 11 sec. The CFL increases after any 180 of 0:001, and is respectively equal to:
0:01; 0:1; 0:3 and 0:5, which is the maximum CFL. The time step t is computed
at the beginning of each step and is given by the maximum ow eld characteristic
velocity ; as t = maxCFL
. The most severe test case for the present code
( + )
is when the ambient pressure is close to the vacuum, in such situation some codes
doesn't work well or even doesn't work at all for such low pressure. In recent
years, material science community expresses strong interest to carry out laser
ablation based synthesis of nanotubes with very low chamber gas pressure since
the higher ambient gas pressure may halt the production of carbon nanotubes
(see [18] for more details). As the Argon pressure had decreased to near to
vacuum conditions, the plume expansion tends to process in much higher rate
than that for standard ambient pressure conditions.
The following computational results are obtained for the ambient pressure of
Argon equal to 10 6 atm. The plume shape is depicted in Fig. 1 left at 2:6s. At
this time moment, the plume has not hit the wall and the plume expansion is
similar to that for Sedov{Taylor blast. At a later time moment, as for example,
at 10s as depicted in Fig. 1 right the plume reaches the wall of the chamber tube
and its shape substantially deviates from the original semi{spherical surface.

Plume Mass Fraction Carbon C3 - Vacuum
Time= 2.6 microsec

0.1

0

0.1

0

0

0.1

Symmetrical axis

Fig. 1.

5.1

0.939867
0.877209
0.814551
0.751893
0.689236
0.626578
0.56392
0.501262
0.438605
0.375947
0.313289
0.250631
0.187973
0.125316
0.0626578

0.2

Radial axis

Radial axis

0.934721
0.869007
0.803293
0.737579
0.671865
0.606152
0.540438
0.474724
0.40901
0.343296
0.277582
0.211868
0.146155
0.0804407
0.0147268

Plume Mass Fraction Carbon C3 - Vacuum
Time= 10.0 microsec

0.3

0.2

0.2

0

0.1

0.2

0.3

Symmetrical axis

Plume Expansion Carbon C3. Left, vacuum at 2:6s. Right, vacuum at 10:0s.

Lagrangian Approach to Model the Temperature of Catalyst
Particles

The 10 uniformly{distributed initial positions for the streaklines are chosen at
the laser spot. The streakline is a line connecting particles released from the
same location. Since the catalyst particles are of sub{micron size, they follow
the streaklines and do not have their own inertia. A Runge{Kutta second order
explicit scheme is used to integrate in time the streaklines. The Langrange's
approach has an advantage over the Euler's approach since it gives the temperature of each catalyst particle as a function of time. Having the temperature of
catalyst particles as a function of time, it will be possible to model kinetics of
formation of carbon nanotubes.
The temperature along streaklines for the above mentioned 10 particles is
shown in Fig. 2 left. The smooth temperature drop is clearly observed for the
initial phase of plume expansion into the vacuum. In Fig. 2 right the instantaneous plume temperature distribution and velocity vector eld are shown. The
stagnation points in the ow eld appear as a result of interaction of plume with
the wall. The particles move upstream passing through regions of higher temperature. In the case of laser ablation into vacuum, the velocity eld is a quite
complex vector eld, that includes the contact lines, boundary curves dividing
vortices, and critical points.
For the laser ablation into vacuum, the temperature of catalyst particles is
quite di erent from the maximum temperature of the plume. While the latter
temperature tends to increase up to  28 second, the temperature of catalyst
particles increases until the particles become a ected by the backward velocity.
The re ected shock waves caused by the wall are relatively weak and do not
cause visible temperature jumps along trajectories of catalyst particles. In the
case of low ambient pressure, the major reason for particle temperature jumps
is a backward motion of particles upstream of the stagnation point.

16

Temperature of Catalyst Particles
Moving along Streaklines

15

Temperature, T/300 K

14
13
12
11
10
9
8
7
6
5
0.00E+00

1.00E-05

2.00E-05

3.00E-05

Time, microsecond

Fig. 2. Temperature Streaklines - Vacuum, Left. Right, Temperature Contour/Velocity
Field - Vacuum.

5.2

Injection Velocity

All our previous simulations used a zero carbon injection velocity (iv ). Carbon
injection velocity simulates the rate of carbon mass ablation as it is injected into
the ow eld by the laser ring process [1]. To nd carbon injection velocity, one
should model melting and vaporization processes, that is out of scope of this
paper. In this paper, we consider the range of carbon injection velocities and
nd the features of temperature dynamics of catalyst particles as a function of
injection velocity. Gaseous carbon is released with a velocity rate that is non{
dimensionalized by the freestream sound speed. The carbon injection velocity
is kept on during the plume injection process. After the 20 ns plume injection
period, the injection velocity is turned o and replaced by the chamber boundary
condition.
For iv = 15:0, the carbon plume concentration is depicted in Fig. 3 left, the
temperature along streaklines is shown in Fig. 3 right, and the peak temperature
pro le as a function of time is shown in Fig. 4 left. To show that temperature
oscillations of catalyst particles are caused by crossing the shock waves, the pressure along the streaklines is shown in Fig. 4 right. To summarize, the temperature
of particles substantially increases with the increase of injection velocity. However, the amplitude of temperature oscillations increases as well that may cause
problems of performance of particles as good catalysts.

6

Conclusion

In the current research, the investigation has been carried out by numerical
simulation of the carbon plume expansion after the laser had red at the target.
The numerical modeling is based on unsteady multi{species formulation for Euler

Fig. 3. Carbon C3 Plume for iv = 15:0, Left. Right, Temperature Streaklines for
iv = 15:0.

equations using the TVD{based numerical discretization. The presented model
qualitatively ts the available experimental results for plume dynamics in carbon
nanotubes synthesis. Relaxing TVD scheme appears to have important numerical
features suitable for modeling of plume dynamics in laser ablation. In this work
we have discovered that:
{

{
{

{

The high pressure initial conditions are similar to that of explosions. The
very strong shock and large gradients of conserved variables are correctly
presented by this numerical scheme.
The used relaxing TVD scheme does not show a problem to model low
ambiance pressure conditions close to vacuum.
The Lagrangian approach reveals important structures of shock interaction
with plume that are not explicitly observed in Eulerian pressure and concentration isolines.
Using dimensional splitting, it is a straightforward task to implement the
code in parallel environment of the Silicon Graphics F90 system.

The proposed mathematical model gives a physical insight into the plume
dynamics in laser ablation:
{

{

The reasons for non{monotonic behavior of temperature of catalyst particles
are interaction of particles with re ected shock waves and circular motion of
the particles caused by formation of vortical zones, stagnation points, and
sliplines. While the former reason is important for higher{pressure of the
ambient gas, the latter reason plays its role for near{vacuum condition.
The position of the front of the plume shows some discrepancies with experiments [2]. The position of the front of the plume primarily depends on the
injection velocity, which may be used as a tuning parameter to correspond

Peak Temperature Pro le for iv = 15:0, Left. Right, Pressure Streaklines for
iv = 15:0.
Fig. 4.

{

numerical modeling with experiments. The plume propagation reveals to be
much slower than that of the leading shock wave especially for low injection
rate.
The self{similar solution for plume expansion revealed good agreement with
t4=5 power scale law rather than with Sedov{Taylor solution t2=5. This holds
even for very short duration of plume ejection.

Acknowledgments Authors were supported by the NSERC grant and by Con-

cordia University Start{up Funds of Dr. Povitsky. The authors wish to thank
the Centre de Recherche en Calcul Applique{CERCA (Montreal) for the logistic
and computational facilities available during this work time. The rst author
thanks Dr. Ian Stewart, University of Bristol U.K., for his comments.

References
1. Greendyke, R., Scott, C. and Swain, J., CFD Simulation of Laser Ablation Carbon
Nanotube Production. 8Th AIAA/ASME Joint Thermophysics and Heat Transfer
Conference. Paper AIAA 2002{3026, June 24-26, St. Louis, Missouri, U.S.A., 2002.
2. Puretzky, A.A., Chittenhelm, H., Fan, X., et al., Investigations of Single-Wall Carbon Nanotube Growth by Time{Restricted Laser Vaporization. Physical Review B,
Vol. 65, 245425, 2002.
3. Zeldovich, Y.B., Raizer, Y.P., Physics of Shock Waves and High-Temperature Hydrodynamic Phenomena. Ed. by W.D. Hayes, R.F. Probstein, Academic Press, London, 1966.
4. Anisimov, S.I., Baverle, D. and Lukyanchuk, B.B., Physical Review B., Vol. 48,
12076, 1993.
5. Sedov, L.I., Similarity and Dimensional Methods in Mechanics, Academics Press,
London, 1959.

6. Jin, S. and Xin, Z., The Relaxation Schemes for Systems of Conservation Laws in
Arbitrary Space Dimensions", Comm. Pure Appl. Math. 48, pp. 235-276, 1995.
7. Povitsky, A. and Salas, M., Trajectory{based Approach to Jet Mixing and Optimization of the Reactor for Production of Carbon Nanotubes, accepted for publication
in AIAA Journal, September 2002.
8. Lob~ao, D.C., An Implicit Time Marching Procedure for High Speed Flow, AIAA
Paper 93-3315-CP, presented at the 11th AIAA Computational Fluids Dynamics
Conference, Orlando, FL, 1993.
9. Stall, D.R. and Prohet, H., JANAF Thermochemical Tables, National Standard
References Data Series, 1971.
10. Anderson, J.D., Hypersonic and High Temperature Gas Dynamics, McGraw-Hill,
1989.
11. Kurganov, A., Tadmor, E., New High-Resolution Central Scheme for Conservative
Laws of Convection{Di usion Equations, J. Comp. Phys. 160, pp.241-282, 2000.
12. Strang, G., SIAM J. Num. Anal., 5, 506, 1968.
13. Yee, H.C., NASA TM 101088, 1989.
14. Yee, H.C. and Harten, A., Implicit TVD Schemes for Hyperbolic Conservation
Laws in Curvilinear Coordinates, AIAA Paper n. 85-1513, 1985.
15. Harten, A., On a Class of High Resolution Total Variation Stable Finite Di erence
Schemes, SIAM Journal Numerical Analysis, Vol.21, pp.1-23, 1984.
16. Aregba-Driollet, D., and Natalini, R., Discrete Kinetic Schemes for Multidimensional Systems of Conservation Laws. SIAM J. Numer. Anal. 37, pp. 1973-2004,
2000.
17. Valery, B., Rivie, K., and Israel, S., Converting Spatial to Pseudotempral Resolution in Laser Plasma Analysis by Simultaneous Multi ber Spectroscopy, Anal.
Chem., 72, No. 13, pp. 2987-2994, 2000.
18. Chen, K.R., Leboeuf, J.N, and et al., Mechanisms A ecting Kinetic Energies of
Laser-Ablated Materials, J. VaC. Sci. Technol. A14(3), pp.1111-1114, 1996.
19. Kim, J.U., Clemens, N.T., and Varghese, P.L., Experimental Study of an Underexpanded Pulsed Laser-Jet, AIAA-99-0452, 37th Aerospace Sciences Meeting, Reno,
Jan., 1999.
20. Kim, K.J., and Wilson, D.E., Theoretical Analysis of a Plasma Jet impinging on a
Nonreacting Surface, AIAA-99-0455, 37th Aerospace Sciences Meeting, Reno, Jan.,
1999.
21. Dabora, E.K., Variable Energy Blast Waves, AIAA J., vol. 10, no. 10, pp.13841386, 1972.
22. Liu, T.P., Hyperbolic Conservation Laws With Relaxation. Comm. Math. Phys.
108, pp.153-175, 1987.
23. Nessyahu, H., and Tadmor, E., The Convergence Rate for Approximate Solutions
for Nonlinear Scalar Conservation Laws. SIAM J. Numer. Anal., 29, pp.1505-1519,
1992.
24. Krasniker, R., Bulatov, V. and Israel, S., Study of Matrix E ects in Laser Plasma
Spectroscopy by Shock Wave Propagation. Spectrochimica Acta Part B 56, pp.609{
618, 2001.

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