Home Search Collections Journals About Contact us My IOPscience

Cataphoresis in electric arcs

This content has been downloaded from IOPscience. Please scroll down to see the full text.

1998 J. Phys. D: Appl. Phys. 31 3383

(http://iopscience.iop.org/0022-3727/31/23/012)

View the table of contents for this issue, or go to the journal homepage for more

Download details:

IP Address: 138.73.1.36
This content was downloaded on 03/10/2015 at 05:06

Please note that terms and conditions apply.

J. Phys. D: Appl. Phys. 31 (1998) 3383–3390. Printed in the UK PII: S0022-3727(98)94907-5

Cataphoresis in electric arcs

A B Murphy
CSIRO Telecommunications and Industrial Physics, PO Box 218, Lindfield,
NSW 2070, Australia

Received 5 June 1998, in final form 21 August 1998

Abstract. A two-dimensional numerical model is used to investigate cataphoresis

(demixing driven by electrical fields) in free-burning arcs in mixtures of argon with
helium, hydrogen, nitrogen and oxygen at atmospheric pressure. The method of
inclusion of electrical field effects in the combined diffusion coefficient treatment of
diffusion and demixing is presented. Cataphoresis is found to lead to large
increases in helium concentration near the anode in argon–helium arcs and smaller
decreases in hydrogen concentration near the axis in argon–hydrogen arcs. There
is no significant effect in argon–nitrogen and argon–oxygen arcs. The effects of
cataphoresis on other arc properties are generally small and are significant only in
argon–helium arcs.

1. Introduction concept of combined diffusion coefficients, which allowed

Cataphoresis is the partial separation of different chemical
elements in a plasma due to the transport of ions in an
externally applied electrical field. It is a special case of
demixing, which refers to all diffusion-driven processes that
lead to such separation. These processes include demixing
due to partial pressure gradients, frictional forces and
thermal diffusion. Murphy [1–3] has shown that demixing
can lead to large changes in the composition of free-
burning arcs in mixtures of argon with hydrogen, helium,
nitrogen and oxygen. It can also alter properties such as
the temperature, convective flow, and thermal fluxes.
Observations of cataphoresis in thermal plasmas date
back to the start of the 20th century. For example, Lenard
[4] recorded the observation that spectral emissions from
metal vapours introduced into arcs in air between carbon
electrodes were greatest in the region near the cathode.
Mannkopf [5] was the first to demonstrate that this increase
in emission from metallic elements near the cathode was
due to an increase in partial pressure of these elements,
rather than being due to an enhancement of excitation.
He showed further that the partial pressure of a metallic
element was greater the larger its degree of ionization.
Frie [6] presented a simplified theoretical discussion of
the effect. Cataphoresis is also observed in low-pressure
discharges, in which strong separation of different noble
gases [7], of metallic vapours from noble gases [8, 9], and
of isotopes of hydrogen [10] has been demonstrated.
Calculation of the effects of cataphoresis (and demixing
in general) in thermal plasmas has been restricted by the
need to treat the diffusion of the many species present in
plasmas produced from gas mixtures. The conservation
of mass of each of the species has to be considered
and diffusion coefficients describing the diffusion of each
species with respect to every other species have to
be calculated. Murphy [11, 12] recently introduced the
the treatment of diffusion to be greatly simplified for
many mixed-gas plasmas. The concept was applied to
a two-dimensional model of a free-burning arc in a gas
mixture [1], allowing demixing processes in the arc to be
investigated.
In this paper, an extension of the combined diffusion
coefficient formulation to allow calculation of diffusion
driven by an externally applied electrical field is presented.
The incorporation of this extension into the two-
dimensional free-burning arc model allows the effect
of cataphoresis to be investigated. Some industrially
relevant gas mixtures are considered. Both the changes
in composition caused by demixing and the consequent
changes in arc properties such as the temperature, flow
velocity and thermal transport are calculated. The
contributions of cataphoresis to the changes are assessed
and compared with those of other demixing processes.
In section 2, the extension of the combined diffusion
coefficient formulation to allow treatment of the effects
of applied electrical fields is discussed. The equations
and methods used in the computational model are also
presented. In section 3, the results of the model for free-
burning arcs in various mixtures of argon with helium,
hydrogen, nitrogen and oxygen are given. The results are
discussed in section 4 and conclusions are presented in
section 5.
2. Theory
2.1. The combined diffusion coefficient formulation
The combined diffusion coefficient formulation [11, 12]
greatly simplifies the treatment of diffusion in many
mixtures of gases, through treating the diffusion of gases,
rather than of species. Here a gas is defined to consist of all
species derived from that gas; hence nitrogen gas includes

0022-3727/98/233383+08$19.50
c 1998 IOP Publishing Ltd 3383
A B Murphy

nitrogen molecules, atoms, ions and electrons derived from Note that the ambipolar terms do not appear in the term in
ionization of these species. In this section, the basis of the E. Also note that, when there is no ionization, ambipolar
formulation is outlined for a gas mixture under the influence effects do not occur, so we write Dija = Dij and DiT a = DiT .
of an externally applied electrical field. The combined diffusion coefficient formulation may be
In a gas mixture containing q species, the equation applied to mixtures of homonuclear gases that do not react
describing the mass flux of species i relative to the mass- with each other, under the assumption of local chemical
average velocity is [13, 14] equilibrium. As will be shown, in the case of a mixture of
two such gases in the presence of a temperature gradient and
n2 X
q
an applied electrical field, it allows the q 2 ordinary diffusion
Ji ≡ ni mi vi = mi mj Dij dj − DiT ∇ ln T (1)
ρ coefficients (of which q(q − 1)/2 are linearly independent)
j =1
and the q thermal diffusion coefficients (of which q − 1 are
where vi is the diffusion velocity of species i relative to linearly independent) to be replaced by just three combined
the mass-average velocity, T is the temperature and diffusion coefficients.
If we consider a mixture of two gases A and B, with
   Xq 
ρj ρj ρ species 1 being the electron, species 2 to p belonging to
dj = ∇xj + xj − ∇ ln P − Fj − nl Fl (2) gas A, and species p + 1 to q belonging to gas B, we can
ρ Pρ mj l=1
define the mass flux of gas A as
describes the diffusion forces due to gradients in mole
X
p
fraction xj and pressure P and due to external forces Fj . n JA = si J i (9)
and ρ are respectively the number density and mass density; i=1
ρj , nj and mj are respectively the mass density, number
density and mass of the j th species. Dij and DiT are where the si are stoichiometric coefficients, given by
respectively the ordinary and thermal diffusion coefficients.
X
p
Here we neglect gradients in the pressure and assume si = (me /mA ) Zk xk /xe (i = 1) (10)
the only external field to be a dc electrical field E. Note k=2
that gravitational fields have no direct effect on diffusion,
X
p X
p
so there is no loss of generality through their omission. If
we also include the ambipolar electrical field E a caused si = bi xk bk xk (2 ≤ i ≤ p). (11)
k=2 k=2
by the separation of electrons and ions resulting from the
tendency for electrons to diffuse more rapidly, the force on Here bi is the number of atoms in a molecule of species i;
a particle of species j is Fj = Zj e(E + E a ), where e is thus bi = 2 for a diatomic molecule or ion and bi = 1 for
the elementary charge and Zj is the charge number of the an atom or monatomic ion. Also, me is the electron mass
j th species. Then (2) becomes and xe is the mole fraction of electrons.
For the calculation of combined diffusion coefficients
exj Zj other than the combined electrical field diffusion coefficient,
dj = ∇xj − (E + E a ) (3)
kB T the J1 term can be neglected, since me  mi for i 6= 1
and since ambipolar effects ensure that ve ' vi for i 6= 1.
where kB is Boltzmann’s constant. As shown previously However, since ambipolar effects do not influence electrical
[11], the mass flux of species i then becomes field diffusion, the last relation does not hold in this case
q   and the J1 term is significant in calculating the combined
n2 X exj Zj Dij
Ji = mi mj Dija ∇xj − E − DiT a ∇ ln T electrical field diffusion coefficient. Note that neglecting
ρ j =1
kB T the J1 term is equivalent to setting s1 = 0, as was done
(4) in previous papers on the combined diffusion coefficient
where formulation [11, 12].
αi X
q
By writing an expression for JA in a form analogous
Dija = Dij + Zl Dlj (5)
β l=1 to (4), namely

αi mi X Zl DlT n2
q
DiT a = DiT + (6) JA = x
mA mB (DAB ∇xB + DAB
E
E) − DAB
T
∇ ln T (12)
β l=1 ml ρ

are respectively the ordinary and thermal diffusion where mB is the average mass of the heavy species of gas B
coefficients, modified to take into account ambipolar and xB is the sum of mole fractions of all species of gas B,
effects. In (5) and (6) and equating this to (9), we can then derive expressions for
x T E
the combined diffusion coefficients DAB , DAB , and DAB ,
X
q
using the relation
αi = nj mj Zj Dij (7)
j =1
∇xj = (∂xj /∂xB ) + (∂xj /∂T )∇T (13)
X
q
β=− Zi Zj nj mj Dij . (8) which is valid since the assumption of local chemical
i,j =1 equilibrium means that the composition can be defined as a

3384
 Cataphoresis in electric arcs

2.2. Demixing and cataphoresis

0.0006 50% Ar, 50% He
combined electric field diffusion coefficient (m2V–1s–1) 50% Ar, 50% H2
Murphy [1] has shown that the terms in DAB x
, DABT1
and
50% Ar, 50% N2
50% Ar, 50% O2 T
DA in (12) each correspond to a distinct demixing process;
demixing due to mole-fraction gradients, frictional forces
0.0004
and thermal diffusion, respectively. Demixing due to mole-
fraction gradients acts to keep the total mole fraction of
each gas uniform throughout the arc, giving rise to mass-
0.0002 fraction gradients in regions where a gas dissociates or
ionizes; demixing due to frictional forces is driven by the
nett effect of the collisional interactions between the species
of the different gases; and thermal diffusion also leads to
0 demixing whenever a temperature gradient is present.
E
The term in DAB in (12) corresponds to cataphoresis, or
demixing due to electrical field gradients. The one-to-one
–0.0002 correspondences between the various combined diffusion
0 10000 20000 coefficients and demixing processes permit the effect of
temperature (K) each process to be calculated separately, thereby allowing
the physical causes of demixing to be examined. In this
paper, this property will be used to examine the effects
Figure 1. The dependence of the combined electrical field
E
of cataphoresis relative to those of the other demixing
diffusion coefficient DAr ,X on the temperature for mixtures of processes.
equal parts argon and helium, hydrogen, nitrogen and
oxygen by mole fraction.
2.3. The numerical model
function of the temperature and the relative concentrations
A two-dimensional axisymmetrical model of a free-burning
of the two gases. We obtain [11]
arc in a mixture of two gases has been developed [1]. It
1 X X
p q
∂xi is based on the model of Lowke et al [15], which treated
x
DAB = si mj Dija (14) an arc in a single gas. It is assumed that the arc is in
mB i=1 j =1 ∂xB
local thermodynamic equilibrium and that the plasma flow
T
DAB = DAB
T1
+ DAT (15) is laminar.
The coupled partial differential equations describing
where mass continuity, radial and axial momentum conservation,
n2 Xp X q
∂xj energy conservation, conservation of mass of one of the
T1
DAB =− mA si mj Dija T (16) gases, electrical current continuity and one of Maxwell’s
ρ i=1 j =1
∂T
equations are solved numerically. The full set of equations
and is given in [1]; here we give only the two equations
X
p
si D T a involving the mass flux JA ; the energy conservation
DAT = mA i
(17)
i=1
mi equation
 
e 1 X
p X
q j2 κ 5kB
E
DAB =− si mj xj Zj Dij . (18) ∇ · (ρvh) = −U +∇· ∇h + j · ∇h
kB T mB  σ  cp  2ecp
i=1 j =1
κ
+∇ · (hA − hB ) JA + ∇YA (19)
These satisfy the relations DAB x
= DBAx T
, DAB = −DBA T
and cp
DAB = −DBA .
E E
and the equation of mass conservation of one of the gases:
Figure 1 shows the combined electrical field diffusion
coefficients for mixtures of argon and other gases. It ∇ · (ρvYA ) = −∇ · JA . (20)
can be seen that the coefficient is largest for the argon–
helium mixture, followed by the argon–hydrogen mixture. Note that there was a sign error in the energy-conservation
Argon, nitrogen, oxygen and hydrogen all have similar first equation as it appeared in [1].
ionization energies, while that of helium is much higher. In the above equations, v is the mass-average velocity
Generally, the coefficient is larger the greater the difference of the gas, j is the current density, h is the plasma enthalpy
in the level of ionization in the gases; the electrical field acts and YA is the sum of the mass fractions of the species
preferentially on the more strongly ionized gas, leading to of gas A. The material functions are the mass density ρ,
more rapid diffusive separation of the gases. The relatively viscosity η, nett radiative emission coefficient U , thermal
E
large value of DAB for the argon–hydrogen mixture is conductivity κ and specific heat at constant pressure cp . All
due to the small mass of hydrogen atoms; the diffusion these material functions are functions of the temperature
coefficient Dij is proportional to [(mi + mj )/mi mj ]1/2 . and the respective mass fractions of gases A and B. hA and
At low temperatures for which ionization is insignificant, hB are respectively the enthalpies of gases A and gas B,
E
DAB = 0, as expected. defined as the sum of the enthalpies of the species making

3385
A B Murphy
up the respective gas, and are functions of the temperature
only.
The mass flux JA , which appears in (19) and (20),
is given in (12) in terms of the gradient of the mole
fraction xA . JA may be written in terms of YA by using
xA = (M/MA )YA , where M and MA are respectively the
masses of the gas mixture and of gas A, averaged over all
species including electrons. The effect of cataphoresis is
included through the term in the electrical field E in (12).
The thermodynamic properties h, cp and ρ were
calculated as functions of the temperature and YA for the
gas mixtures considered using the NASA code [16, 17].
x T1
The transport coefficients η, κ, DAB , DAB and DAT
and the electrical conductivity σ , which appears in the
current-continuity equation, were calculated as described by
Murphy and Arundell [18] for argon–nitrogen and argon–
oxygen mixtures, by Snyder et al [19] for argon–hydrogen
mixtures and by Murphy [20] for argon–helium mixtures.
Nett radiative emission coefficients U for argon, helium,
oxygen and hydrogen were calculated using the method of
Cram [21]. Those for nitrogen were calculated by taking
the values of Ernst et al [22] for a plasma radius of 1.5 mm
and multiplying these by a factor of 1.5. The adjustment
is necessary since the radius of the radiating central region
of the arc is less than 1.5 mm [23], hence the absorption of
radiation will be smaller than that calculated for a radius of
1.5 mm.
The coupled partial differential equations describing
the arc were solved numerically using the control-volume
approach of Patankar [24], incorporating the modifications
recommended by Van Doormal and Raithby [25]. A
rectangular grid of 82 axial by 48 radial control cells was
used, with the grid more closely spaced near the electrodes.
Comparison with results obtained with a 41 by 24 grid
showed that there was a maximum change of 8% in the
mass fraction of the minority gas and generally much less.
Boundary conditions for YA were given by Murphy [1].
Those for all other variables were given by Lowke et al
[15].
In section 2.2, it was noted that the various demixing
processes, including cataphoresis, correspond to different
combined diffusion coefficients. By setting the appropriate
coefficients to zero in (12), it is possible to isolate
the influences of the various demixing processes on the
properties of the arc. For instance, the effect of cataphoresis
can be excluded by setting DAB E
= 0 in (12). The effect of
all demixing processes can be excluded by removing (20)
from the model and setting the final term in (19) to zero.
3. Results
3.1. Effects of cataphoresis on the arc’s composition
An arc typical of those used in gas–tungsten arc welding
was modelled. The tungsten cathode had a diameter of
3.2 mm and a conical tip of 60◦ included angle. It
was situated 5 mm above a flat anode. The arc current
was 200 A and the total gas flow was 10 l min−1 .
The gas mixture was introduced through a nozzle placed
concentrically around the cathode, with a radius 2.35 mm
3386
greater than that of the cathode. Calculations were
performed for input gas mixtures of argon with helium,
hydrogen, nitrogen and oxygen.
Figure 2 shows the calculated distribution of helium
and the temperature distribution for an arc in a mixture
of 10% helium and 90% argon by mass (corresponding
to 52.6% helium by moles). Results are given for
calculations performed including and neglecting the effects
of cataphoresis. In both cases the other demixing processes
are included. Figure 2 shows that demixing causes a strong
concentration of helium towards the axis of the arc, with
the mass fraction of helium increasing from 0.10 in the
arc’s fringes to 0.26 on the axis. Cataphoresis is found to
have a significant additional effect on the arc’s composition,
leading to an increase in helium concentration in regions
close to the anode. Its effect is much smaller closer to the
cathode. Cataphoresis does not significantly alter the arc’s
temperature distribution.
Figure 3 shows the radial dependence of the mass
fraction of helium for three different mixtures of argon and
helium: 1, 5 and 10% helium by mass, corresponding to
9.2, 35.5 and 52.6% by moles. Results are again given for
calculations performed including and neglecting the effects
of cataphoresis. In all cases, cataphoresis leads to a large
increase in the mass fraction of helium at z = 4 mm (4 mm
below the cathode tip) and progressively smaller increases
as z decreases.
Figure 4 shows the radial dependence of the mass
fraction of hydrogen for a mixture of 1% hydrogen in
argon by mass, corresponding to 16.7% hydrogen by
moles. Demixing has a large effect on argon–hydrogen
arcs, leading to a strong concentration of hydrogen near the
axis. However, the effect of cataphoresis is relatively small;
it leads to a small decrease in the hydrogen concentration
at radii less than 1 mm.
Figure 5 shows the radial dependence of the mass
fraction of nitrogen for a mixture of 20% nitrogen in
argon by mass, corresponding to 26.2% nitrogen by
moles. Although demixing considerably alters the arc’s
composition, increasing the mass fraction of nitrogen on
the axis to almost 0.26, cataphoresis has a negligible effect.
Argon–oxygen arcs exhibit similar behaviour; demixing
leads to a considerable change in mass fraction of oxygen,
but the effect of cataphoresis is negligible.
In figures 4 and 5, decreases in the mass fractions of
hydrogen and nitrogen respectively are apparent at radii
less than 1 mm for z ≤ 2 mm. These decreases appear
in calculations performed both including and neglecting
the effect of cataphoresis. This is a consequence of the
large axial flow velocity close to the axis that is driven by
the j × B force associated with the large current density
near the cathode’s tip; this is known as the Maecker
effect. Diffusion is not sufficiently rapid to allow complete
demixing of the input gas mixture in this region, due to the
rapid convective influx of the input gas mixture. This effect
is not nearly so marked in the argon–helium arc, since the
flow velocity is smaller [1].
 Cataphoresis in electric arcs

-2 -2

2
(a) (b)

2
01
0.00.0186

8
0 0

0.

16
18
0.0
14
1
z (mm)

6
2 2

4
0.0

10

2
10
0.0

12
12 8
4 4
4 16

14
0 01
0.02 0.
0 2 4 6 0 2 4 6
r (mm) r (mm)

Figure 2. (a) Isopleths of the mass fraction of helium and (b) isotherms, labelled in units of 1000 K, calculated for a 200 A,
5 mm arc with a 10 l min−1 input flow composed of 10% helium and 90% argon by mass. Results of calculations performed
(——) including and (– – –) neglecting the effects of cataphoresis are shown; the other demixing effects are included in both
cases.

3.2. Effects of cataphoresis on other arc properties
It has been shown [1] that, in most cases, demixing has
little effect on arc properties such as the temperature, flow
velocity and thermal fluxes, despite there often being large
changes in arc composition. However, there are some
exceptions; in argon–hydrogen arcs, demixing can lead to
temperature decreases of up to around 6%, and in argon–
helium arcs demixing can increase the axial flow velocity
by more than 20%. Furthermore, large increases in the
distribution of the thermal flux to the anode can be caused
by demixing; the thermal flux on the axis increases by up
to around 50% in argon–hydrogen arcs and 10% in argon–
nitrogen arcs. These changes can be explained in terms of
the changes in transport properties caused by the altered
gas composition [1].
In general, cataphoresis has little further effect on the
arc temperature and velocity. The temperature is altered
by less than 1% at any position for the gas compositions
studied. There is some effect on the axial flow velocity in
argon–helium arcs. Figure 6 shows the radial dependence
of the axial velocity in an arc in a mixture of 5% helium in
argon by mass, for the case in which all demixing processes
are neglected (that is, assuming that the fraction of helium
mass is uniform throughout the arc), the case in which
cataphoresis is neglected but the other demixing processes
are included and the case in which both cataphoresis and the
other demixing processes are included. Cataphoresis causes
a decrease in the axial velocity on the axis at a position
1 mm above the anode of around 4%, in addition to the
16% decrease caused by other demixing processes. This is
due to the increase in viscosity that is caused by increases
in helium concentrations in argon–helium mixtures [1, 20],
which leads to a greater transfer of momentum from the
central to the fringe regions of the arc, giving a less-peaked
velocity profile.
Demixing has a large effect on the thermal flux to
the anode, particularly in argon–hydrogen arcs, for which
increases in the thermal flux on the axis of almost 50% were
calculated [1]. Figure 7 shows the effects of cataphoresis
and other demixing processes on the thermal flux to the
anode in an arc in a mixture of 1% hydrogen in argon by
mass. It is clear that cataphoresis has only a very small
effect on the thermal flux. This is consistent with the small
change in the mass fraction of hydrogen adjacent to the
anode; the mass fraction of hydrogen at the anode on the
axis is calculated to be 0.0284 if cataphoresis is included
and 0.0283 if it is neglected.
The effect of cataphoresis on the thermal flux to the
anode is more significant in argon–helium arcs, although it
is still small. As shown in figure 8, cataphoresis leads to a
flattening of the thermal flux profile; the magnitude of the
effect is similar to that of the other demixing processes.
4. Discussion
The observations of cataphoresis in arcs that were noted
in section 1 showed that metallic elements tended to
concentrate near the cathode. This is easily explained in
terms of the relative ionization energies of the metallic
elements and the elements present in air. Metals ionize
more easily than do oxygen or nitrogen, hence the
concentration of metal ions at a given temperature is higher
than that of oxygen and nitrogen ions. Hence the electrical
field has a greater effect on the metals, concentrating them
near the cathode.
In this paper, arcs containing metal vapour have not
been treated, since the assumption of a fully mixed input gas
would not be valid in the case of metal vapours, which are
typically derived from the vaporization of an electrode or of
particles injected into the arc. Very low quantities of metal

3387
A B Murphy

0.025 0.035
(a)
with cataphoresis
without cataphoresis
0.03 with cataphoresis
0.02 without cataphoresis
helium mass fraction

hydrogen mass fraction

0.025
0.015 z = 4 mm
0.02
3 mm
z = 4 mm
0.01 0.015
1 mm
2 mm 3 mm
0.01
0.005
0 2 4 6 1 mm 2 mm
radius (mm) 0.005
0 2 4 6
0.15
radius (mm)
(b)

0.125 Figure 4. The radial dependence of the mass fraction of

hydrogen gas at four axial distances below the cathode, for
a 200 A, 5 mm arc with a 10 l min−1 input flow composed
helium mass fraction

of 1% hydrogen and 99% argon by mass. Results of

0.1 calculations performed (——) including and
(· · · · · ·) neglecting the effects of cataphoresis are shown;
z = 4 mm the other demixing effects are included in both cases. The
0.075 horizontal line shows the input mass fraction.
3 mm

0.05 0.26
1 mm
2 mm with cataphoresis
without cataphoresis
0.025
0 2 4 6
0.24
radius (mm)
nitrogen mass fraction

z = 4 mm
0.3 0.22
(c)

0.25
0.2
3 mm
helium mass fraction

0.2
0.18 2 mm
z = 4 mm 1 mm
0.15
3 mm 0.16
0 2 4 6
0.1 radius (mm)
1 mm
2 mm
Figure 5. The radial dependence of the mass fraction of
0.05 nitrogen gas at four axial distances below the cathode, for
0 2 4 6 a 200 A, 5 mm arc with a 10 l min−1 input flow composed
radius (mm) of 20% nitrogen and 80% argon by mass. Results of
calculations performed (——) including and
Figure 3. The radial dependence of the mass fraction of (· · · · · ·) neglecting the effects of cataphoresis are shown;
helium gas at four axial distances below the cathode, for a the other demixing effects are included in both cases. The
200 A, 5 mm arc with a 10 l min−1 input flow composed of horizontal line shows the input mass fraction.
(a) 1% helium and 99% argon; (b) 5% helium and 95%
argon; and (c) 10% helium and 90% argon by mass.
Results of calculations performed (——) including and vapours are typically present in free-burning arcs of the type
(· · · · · ·) neglecting the effects of cataphoresis are shown; considered here with tungsten cathodes and strongly water-
the other demixing effects are included in both cases. The cooled copper anodes [26], so it is reasonable to neglect the
horizontal line shows the input mass fraction.
3388
 Cataphoresis in electric arcs

400 150
with cataphoresis
no cataphoresis with cataphoresis
no demixing no cataphoresis
no demixing

anode heat flux (W mm–2)

300
z = 2 mm
100
axial velocity (m s–1)

200
z = 4 mm
50
100

0 0
0 0.5 1 1.5 2 0 1 2 3 4
radius (mm) radius (mm)

Figure 6. The radial dependence of the axial velocity at
two axial distances below the cathode for a 200 A, 5 mm
arc with a 10 l min−1 input flow composed of 5% helium
and 95% argon by mass. Results of calculations performed
(——) including cataphoresis and the other demixing
effects, (· · · · · ·) neglecting cataphoresis but including the
other demixing effects and (– – –) neglecting both
cataphoresis and the other demixing effects are shown.
Figure 8. The radial dependence of the heat flux to the
anode in a 200 A, 5 mm arc with a 10 l min−1 input flow
composed of 5% helium and 95% argon by mass. Results
of calculations performed (——) including cataphoresis and
the other demixing effects, (· · · · · ·) neglecting cataphoresis
but including the other demixing effects and
(– – –) neglecting both cataphoresis and the other
demixing effects are shown.

have similar ionization energies, hence the relative degree

400 of ionization will be similar for both gases present in the
with cataphoresis argon–hydrogen, argon–nitrogen and argon–oxygen arcs.
no cataphoresis Helium, however, has a much higher ionization energy than
no demixing that of argon.
anode heat flux (W mm–2)

300 Many of the results presented in section 3 can be

200
100
0 E
0 1 2 3
radius (mm)
Figure 7. The radial dependence of the heat flux to the
anode in a 200 A, 5 mm arc with a 10 l min−1 input flow
composed of 1% hydrogen and 99% argon by mass.
Results of calculations performed (——) including
cataphoresis and the other demixing effects,
(· · · · · ·) neglecting cataphoresis but including the other
demixing effects, and (– – –) neglecting both cataphoresis
and the other demixing effects are shown.
influence of metal vapours on the arc’s properties. Of the
gases considered, hydrogen, nitrogen, oxygen and argon all
explained on this basis. Cataphoresis was found to a have
negligible effect on the argon–nitrogen and argon–oxygen
arcs, which is expected since the electrical field will have
a similar effect on each gas present, owing to their similar
levels of ionization. This is reflected in the small values of
E
DAB for the respective gas mixtures shown in figure 1.
Cataphoresis has a larger effect on the argon–hydrogen
arcs, despite the fact that argon and hydrogen have similar
ionization energies. This is because hydrogen diffuses more
rapidly than do nitrogen and oxygen, owing to its much
smaller mass. This is reflected in the relatively large value
of DAB for the argon–hydrogen mixture shown in figure 1.
4 The effect of cataphoresis on the argon–hydrogen arc is
to decrease the concentration of hydrogen near the arc’s
E
axis. This occurs because DAB is large at relatively low
temperatures, peaking at 11 000 K, and thus cataphoresis
is important at relatively large radii, around 2–3 mm. At
these radii, the electrical field is directed inwards and
E
upwards towards the cathode; since DAr,H is positive, (12)
2
shows that the flux of argon relative to the mass-average
velocity will also be inwards and upwards; hence the flux
of hydrogen will be outwards and downwards.
The argon–helium arc is the most strongly affected
by cataphoresis; figure 3 shows a strong increase in the
helium concentration near the anode at all radii. Figure 1

3389
A B Murphy
E near the anode are strongly increased, and hydrogen
shows that DAB is larger for the argon–helium mixture
than it is for the other mixtures and that it peaks at a
relatively high temperature, around 18 000 K. This indicates
that cataphoresis should be important in the central region
of the arc. Since DAr,HeE
is positive, the flux of helium
will be outwards and downwards. This leads to the
concentration of helium near the anode and ensures that
helium concentrations away from as well as close to the
axis are increased.
Frie [6] has presented a simple quantitative calculation
of the effect of cataphoresis on arcs. He treated the case of
a mixture of a non-ionized ‘fill gas’ and a partially ionized
gas. He further assumed that the collision cross section for
interactions between atoms and ions of the partly ionized
gas was the same as that for interactions between atoms of
that gas. This led to the result that the the partial pressure
pF of the fill gas varied according to ∇pF /pF ∝ −(1/T )j.
This shows that the partial pressure of the fill gas will
tend to increase away from the cathode and the arc’s
axis, which is in accord with the results presented here.
Frie qualitatively explained this effect by noting that the
ions will travel towards the cathode in the electrical field,
where they are discharged and then diffuse, because of
the resulting concentration, away from the cathode. The
collisional forces that the ions and atoms exert on the fill
gas cancel each other out and the current-carrying electrons
carry the fill-gas atoms towards the anode.
Frie’s assumption that the atom–ion collision cross
section is equal to the atom–atom cross section is
inaccurate; charge-exchange effects ensure that the atom–
ion cross section is much larger [18, 27]. Frie’s qualitative
explanation is predicated on this assumption; in any case
it is unnecessarily complicated. It is sufficient to say that
the gas that is more strongly ionized will be more affected
by the electrical field; hence there will be a nett flux of
this gas, relative to the mass-average velocity, towards the
cathode.
5. Conclusions
Cataphoresis, demixing driven by an applied electrical field,
has been included in a numerical model of a free-burning
arc in a gas mixture. This has been done by including an
additional term, proportional to the electrical field strength,
in the expression for the diffusive mass flux. This term is
easily incorporated into the combined diffusion coefficient
formulation.
Cataphoresis is driven by the different levels of
ionization of the gases present. The more-strongly ionized
gas is more greatly affected by the electrical field than is
the other gas, leading to concentration of this gas towards
the cathode and the axis of the arc and of the less-strongly
ionized gas towards the anode and away from the axis. Use
of the combined diffusion coefficient formulation allowed
the effect of cataphoresis to be easily separated from that
of other demixing processes.
Cataphoresis is found to cause significant separation
of gases, in addition to those changes caused by other
demixing effects, in argon–helium arcs and has a smaller
effect in argon–hydrogen arcs. Helium concentrations
3390
concentrations near the arc’s axis are decreased. In argon–
nitrogen and argon–oxygen arcs, cataphoresis does not have
a significant effect.
Cataphoresis generally does not cause significant
changes in other arc properties. The only cases in which
changes of greater than 1% were calculated were for
the axial velocity distribution and thermal flux to the
anode in argon–helium arcs; no significant changes in arc-
temperature distributions were calculated for any of the gas
mixtures considered.
Mixtures of gases are used in arc and plasma processes
for two main reasons: first, to provide the species required
to drive chemical reactions in the arc or at the electrodes;
and second, to increase thermal transport to the electrodes
or to particles injected into the plasma. The results
of this study have shown that cataphoresis can cause
significant changes in the arc’s composition, but little
change in thermal transport, at least in the mixtures of
gases considered. Hence, it may be reasonable to neglect
cataphoresis in modelling the heat-transfer aspects of arc
and plasma processes. However, particularly in mixtures of
gases with different ionization energies, it may be important
to take account of cataphoresis when considering chemical
processes in arcs.
References
[1] Murphy A B 1997 Phys. Rev. E 55 7473
[2] Murphy A B 1996 Appl. Phys. Lett. 69 328
[3] Murphy A B 1994 Phys. Rev. Lett. 73 1797
[4] Lenard P 1903 Ann. Phys., Lpz. 11 636
[5] Mannkopf R 1932 Z. Phys. 76 396
[6] Frie W 1963 Z. Phys. 172 99
[7] Riesz R and Dieke G H 1954 J. Appl. Phys. 25 196
[8] Druyvesteyn M J 1935 Physica 2 255
[9] Loeb L B 1958 J. Appl. Phys. 29 1369
[10] Beckey H D, Groth W E and Welge K H 1953 Z. Natur. a
8 556
[11] Murphy A B 1993 Phys. Rev. E 48 3594
Murphy A B 1994 Phys. Rev. E 50 5145
[12] Murphy A B 1996 J. Phys. D: Appl. Phys. 29 1996
[13] Hirschfelder J O, Curtiss C F and Bird R B 1964
Molecular Theory of Gases and Liquids 2nd edn (New
York: Wiley)
[14] Devoto R S 1966 Phys. Fluids 9 1230
[15] Lowke J J, Kovitya P and Schmidt H P 1992 J. Phys. D:
Appl. Phys. 25 1600
[16] Kovitya P 1984 IEEE Trans. Plasma Sci. 12 38
[17] Gordon S and McBride B J 1971 NASA Report SP-273
[18] Murphy A B and Arundell C J 1994 Plasma Chem. Plasma
Process. 14 451
[19] Snyder S C, Murphy A B, Hofeldt D L and Reynolds L D
1995 Phys. Rev. E 52 2999
[20] Murphy A B 1997 IEEE Trans. Plasma Sci. 25 809
[21] Cram L E 1985 J. Phys. D: Appl. Phys. 18 401
[22] Ernst K A, Kopainsky J G and Maecker H H 1973 IEEE
Trans. Plasma Sci. 1 (4) 3
[23] Aubrecht V and Lowke J J 1994 J. Phys. D: Appl. Phys. 27
2066
[24] Patankar S V 1980 Numerical Heat Transfer and Fluid
Flow (Washington: Hemisphere)
[25] Van Doormaal J P and Raithby G D 1984 Numer. Heat
Transfer 7 147
[26] Gleizes A, Bouaziz M, Gonzalez J-J and Razafinimanana
M 1997 IEEE Trans. Plasma Sci. 25 891
[27] Capitelli M 1977 J. Physique Colloq. 38 C3-227