HOT ELECTRON PI-ENOMENA IN LIQUID AND GASEOUS ARGON AND NITROGEN IN

DIVERGENT ELECTRIC FIELDS.

J. L. Hernandez-Avila, N. Bonifaci and A. Denat

CNRS. Laboratoire dElectrostatique et de Matkriaux DiBlectriques
BP 166 38042 GRENOBLE cedex 9 (France)

ABmCT

A comparative study of electrical conduction and emitted light in an atomic (Ar) and a
molecular liquid (N2) is presented as a function of various parameters. From the
spectroscopic analysis of emitted light (in the range 200-850 nm), the energy of the hot
electrons in these liquids may be measured. A simultaneous study was carried out on dense
gases as a function of the applied pressure. We discuss the electron swarm parameters
deduced from these results, in an attempt to explain the behavior of electrons in the gas-
liquid phase transition.

INTRODUCTION

Previous studies [1,2] of the electrical conduction of gaseous and liquid hydrocarbons,
using point-plane electrodes, has shown that corona discharges occur in the liquid phase as
well as in the gas phase. For example, with a point cathode, above a threshold voltage Us, a
current instability connected with a regular regime of current pulses was observed. For a
given gas density, the discharge characteristics of this pulse regime, as a function of
applied voltage and tip radius, show the same variation laws in both liquids and gases.
However, in liquids, contrary to results in gases, the characteristics of this Trichel-like
pulse regime displayed no pressure dependence, at least in the range of our experimental
values (0.1-12 MPa).
Pulses of emitted light are correlated to current pulses and the mean light intensity
varies proportionally to the mean current I,. The spectral analysis of the emitted light
should help in the understanding of the mechanisms of corona discharges. Unfortunately,
the light emitted by hydrocarbons in such experiments is mainly due to complex processes
of fragmentation and recombination of the molecules (CH, C2, etc). This effectively mask
the phenomena we wish to examine and makes it impossible to deduce discharge parameters
from the spectral data.
Consequently, we have chosen to investigate the processes of corona discharge in
simpler liquids: i.e. argon and nitrogen, where we will not encounter problems of
fragmentation, etc, in the hope of clarifying the corona discharge processes in superdense
fluids. The conclusions of this study will hopefully be transferable to other liquids
(hydrocarbons).

57lA4
 EXF'ERIh4ENTALSETUP

The gases (99.99990 8 purity) were further purified by passage over two oxygen and
moisture traps. The gas was then transferred into a stainless-steel coaxial cell (50 Cl)
mounted in a cryostat. This cell could withstand pressures up to 6 MPa and its temperature
could be adjusted to the desired value between 83 to 150 OK.
The cell used at room temperature (300 OK) could be pressurized up to 10 MPa. These
cells were previously pumped to about Pa before filling at a flow rate of 3 Ymn. The
tungsten needles had point radii between 0.1 to 6 pm, and the point plane distance was
varied between 0.5 and 10 mm.

The spectral analysis of emitted light is camed out with a Jarrel-Ash spectrograph
(focal lengh 275 mm) and an optical multichannel analyser (OMA 111). In order to reduce the
dark current, the photo-detector (model 1420R, spectral range 180-900 nm) was cooled to a
temperature of -4OOC. The spectrograph is equipped with a turrel of three gratings: 150, 600
and 1200 grooves per mm (maximum resolution 0.3 nm). The image of the point is focused
on the entrance slit (width 25 pm) of the spectrograph using a spectrosil B lens . The slit
can be used to select any section of the light region localized at, say, X pm from the tip.
The spectral range was limited between 200 and 850 nm by the characteristics of the set up.
Simultaneously, we measured the total intensity of the emitted light using a
photomultiplier (RCA C3 1034/02) cooled to -20°C. This, with an oscilloscope (Tektronix
7834) and a frequency meter (connected to the oscilloscope out gate) or a charge storage
device [3], allows us to make time-resolved measurements of the conduction current and of
the light intensity, as well as their pulse frequencies and their correlation. The high
voltage, from a stabilized DC power supply, is connected to the point electrode. An
oscilloscope and/or a current meter (Keithley 61OC) are connected to the plane electrode.
Electric field and mobilities calculations were made via the hyperboloidal
approximation of the point-plane electrode configuration [4].

RESULTS

GasCS
As breakdown occurs in these gases at low pressure (P < 0.1 MPa) at the corona
threshold voltage U, (unless an external limiting resistor prevents it), gaseous Argon and
Nitrogen were studied, therefore, at room temperature, between 0.1 to 10.MPa. Above U,,
similar regimes of corona discharge pulses were detected whatever the point polarity and,
the mean current was space charge limited. The onset field E,, deduced from U,, increases as a
function of the gas density in both compounds (fig. l a and lb). We noticed that in Ar gas,
E,(N) seems to saturate at about a density of lgl~ m - ~ .
The charge carrier mobilities (K.for a negative point and K+ for a positive point) are
calculated from the slopes of the 1112(U) plots (fig. 2a and 2b). When the gas density
increases, the mobilities decrease. In N2 gas, our K+(N) is in good agreement with the data
of Gee and Freeman [5]. Moreover, the extrapolation at 2.5.1019 cm-3 (atmospheric
pressure) of the K+(N) dependence gives a value for K+ close to the value measured in low
pressure N, gas by Brown [ 6 ] .For the Ar gas at 2.5.10' ~ m - the
~ , same extrapolation gives
a value for K+ near the value of K(Ar+) found by Hornbeck [7]. This suggests that for
positive corona, the charge carriers in each case are N2+ and Ar+ (or Arz+) ions.

58
 In these gases, the values of K., though generally higher than the values of K, at the
same density, are much too small to be attributed to electronic carriers. However, in N2 gas
we supposed that the negative carriers are Nz- or N-ions. The negative carriers in Ar gas are
unknown though it is always possible to attribute this role to impurities.
10
..... .. ............................................ loo

...................... 4
...................... .....................
...................... ................ ...................
...A ...............
.............. .....
GI i qlia Liquid

...................... :........................ ;.....................

A

mn" i i NislmIun?
1
a
ldO 10'' 1022 1

Figure 1%: Negative corona onset figure 1b: Negative corona onset
electric field E , vs Argon density N. electric field E, vs Nitrogen density N.

1 ~ . " " " I ""'

............

........

..................................

............... i................................... i...u . . . . . d

1 U' I
N ~ ~ o I / o ~ ?
104 1. &Em%UCblIQ
*...,-a1 . .......I ........i N l ? t m / y n l
10'~ iozo I02' ioz2 ICP 10'0 1020 18' 1022 lo23

Fiuure 2a: E:, and K. mobilities vs Fiuure 2h: K, and K. mobilities vs

Nitrogen density N. Argon density N.

The electrical characteristics of the current pulse regime (e.g.charge per pulse, pulse
form and frequency, etc) are functions of the point polarity, tip radius and gas density.
For negative polarity, the charge (Qi) per pulse decreases as a function of the gas
density (Fig. 3a and 3b). When the density is varied from 2.1020 to 2.1021 ~ m - the ~ , Qi
values fall by one order of magnitude. We also noted the strong tip radius influence on the
charge measurements (fig. 3b).
For positive polarity, there is also a regime of current pulses. In gaseous Nitrogen, the
amplitude of these pulses is, however, barely within the limits of our detection system and
do not appear in the fig. 3b. In the two gases, Q, increases with the density (pressure) (Fig.
3a).
For a given denriity and point radius, whatever the point polarity, the pulse frequency F
is proportional to the mean current I,, i.e. I, =QF. Q is a mean charge per pulse and the ratio

59
Qi/Q is between 0.2 and 0.4 depending on gas density. Both Q and Qi are proportional to
the point radius.
Measurements of Qi and of the delay time At between two successive pulses show that
there is a correlation between Qi and the At preceding the pulse Qi, and that the histograms
of Qi and At follow a normal distribution.

. . . . . . . !. . . . . . . . . I ..... a,wi I
ai[Pcl i 14 0 -1p111m 0 Tipmdi-4pm .
o o+rl"lmm
..................... toe El Tip rsdii 1Spm . -
I j l : 1 # i ....Q ................j ..................... ~

................. ............. .....................

.....................$.............................................
: T Liquid

10'1 . .......I
i
. .'
. . . . . . IO" N[atm/cm'] i t .
N Nq.ar. Pblarity
2. . . . . . . . . . . . . . . ./ t. ....
10'0 1021 1 oz0 1 d' N[mol/cm3]
Id'

Figure: Charge Qi for a negative Figure 3b: Charge Qi for a negative

and a positive corona vs Argon corona vs Nitrogen density N.
density N.

Liauids
With a negative voltage applied to the point, below the critical temperature,
phenomena similar to those described in gases are observed. A regular regime of current
pulses abruptly appears above a corona onset voltage U,. Es calculated from the values of U,
is about 4 MV/cm in argon and around 10 MV/cm in N2 (fig. l a and lb). All the different
characteristics (Im(U), Im(F), Qi(U), etc) are independent of the hydrostatic pressure applied
to the liquid (P I 6 MPa).
In li uids, the mobilities deduced from the space charge limited current are in the range
1
0.7-4 10- cm2/Vs. This corresponds to values of the electrohydrodynamic mobility KEH>
(- cm2/Vs) and shows that charge carriers are mainly ions and that liquid motion
occurs. However, no stable ions of the form Ar,- are known to exist and, consequently,
impurities like 0 2 must be postulated to exist to form negative ions [8]. In N2, the negative
ions may be Nz-.

For positive points, in liquid N2 in the same range of voltage, no current could be
detected. In liquid Argon the positive ion mobility is approximately 5 - 6 ~ 1 0 cm2/Vs
-~ (fig.
2a and 2b) in close agreement with Henson 191.
. .
LjPht e m ~ o ~henomena
n
In liquid Ar, each emitted light pulse is correlated to a current pulse. The emission
spectrum is constituted by the ArI 4s-4p line array between 695.5 and 842 nm (excited
states of 13-13.5 eV) and sometimes, we observe a forbidden line of atomic oxygen at
557.7 nm (lSo-lQ, excited state of 4.17 eV). At relatively high electronic densities (e.g. Qi
> 50pC) a continuum extending from 400 to 850 nm, in addition to a many-line spectrum is
observed and its intensity grows with Qi. The intensity distribution, once corrected for the

60
various instrumental responses (photocathode response, grating efficiency, etc), seems to
correspond to that of a free-bound recombination spectrum (e.g. recombination with
positive ions Ar+ +. e- --> Ar* + hv ) [10,11]. The absolute emission coefficient of the
continuous radiation. E(V)at frequency V, predicted by the Kramer-Unsold theory allows a
determination of electron temperature and electron density. For example, for Qi = 100 pC,
we deduce Te= 3000 .. 4000 OK and ne-3 10' ~ m - ~ .
In liquid nitrogen, we observe the second positive band emission system of N2 (C3nu --
> B3ng excited states of 11-12 ev) in the region 330-400 nm. We sometimes also observe
the forbidden line of oxygen at 557.7 nm.

CONCLUSION

All the electrical characteristics of this corona regime in liquid and gaseous argon and
nitrogen demonstrate! the existence of a self-sustained (Qi/Q<0.5, Q and Qi are proportional
to rp, etc) and self-stabilized (Qi(n) is a function of At(n-l), 1/F is a small fraction of the ion
transit time, etc) discharge. In liquids these characteristics are independent of the applied
hydrostatic pressure and indicate that the discharge occurs in the liquid phase.
Our light emission analysis reveals the formation of excited states of energy above 10
eV in the liquid phase. This indicates that very hot electrons, capable of ionizing, are
produced near the point electrode. In conclusion, this study of corona discharges in argon
and nitrogen (gas and liquid) demonstrated that avalanches can be produced in the liquid
phase. An estimation of the multiplication coefficient, a, can be made, using the
assumption that, for the same values of E,, the avalanche in liquid and gaseous phases
spreads out in the same manner [1,2]. From this, we found that hot electrons in the liquid
~ i nand NL=1.7.1022cm-3 in N2) avalanche as in the gas at
phase ( N ~ = 2 . 1 . 1 0 ~ % c m -Ar
N*=1.3.1021cm-3 in argon and N*=:3.4.1021cm-3 in nitrogen. Consequently, the ratio
NL/N* is equal to 16 in argon and to 5 in nitrogen. This must be compared to xenon, where
NL/N*=27 [12] which indicates that NL/N* is a function of the electronic properties of the
liquids.
REFERENCES

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201-204, 1988.
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[4] R. Coehlo and J. Debeau, J. Phys D.Vol4. pp 1266-1280 1971.
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York, p 4-161, 1958.
[7] J.A. Hombeck, Phys. Rev.,Vol 84, pp 615-620, 1951.
[8] H.T. Davis, A.R. Stuart and L. Meyer, J. Chem. Phys., Vol 37, pp 2470-2472, 1962.
[9] B.L.Henson, Phys. Rev. Vol 135, pp 1002-1008, 1964
[IO] A. Unsold, Ann. Physik, Vol 33, pp 607-616, 1938.
[ l l ] H.N. Olsen, Phys. Rev., Vol 124, pp 1703-1708, 1961.
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2591, 1974.

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