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A Dielectric Barrier Discharge (DBD) Plasma Reactor: An Efficient Tool

to Measure the Sustainability of Non-Thermal Plasmas through the
Electrical Breakdown of Gases
To cite this article: S. P. Das et al 2018 IOP Conf. Ser.: Mater. Sci. Eng. 410 012004

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ICAEFM IOP Publishing
IOP Conf. Series: Materials Science and Engineering 410 (2018) 012004 doi:10.1088/1757-899X/410/1/012004
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A Dielectric Barrier Discharge (DBD) Plasma Reactor: An Efficient Tool to Measure

the Sustainability of Non-Thermal Plasmas through the Electrical Breakdown of Gases

S. P. Das*, G. Dalei and A. Barik

Department of Chemistry, Ravenshaw University, Cuttack-753003, Odisha

Email:[email protected]

Abstract

Gas discharges in plasma atmosphere are known to consist of a collection of different particles,
mainly electrons, ions, neutral atoms and molecules. In this piece of research work we aim for the
complete decomposition of volatile organic pollutants in NTP system. So the formation of plasmas in
DBD systems and its sustainability are the main goal. The present need is to characterize the plasmas
and optimization of the designed and fabricated plasma system under variable conditions. One of most
important issue is the electrical breakdown of gases and to find the point of electrical breakdown.
The volatile organic pollutants taken are Benzene, toluene, xylene, chlorobenzene,
dichlorobenzene, nitrobenzene, methylene chloride etc. Self-sustainability of DBD-plasmas is
explained for different VOCs under different experimental conditions taking helium and argon as
carrier gases in terms of Paschen’s curves. It explains the breakdown voltage as a function of the
electrode spacing or gas gap (d), operating pressure (p), and gas composition [1]. The breakdown
voltage is a function of the product of the pressure (p) and the inter-electrode distance (pd) also. It is
verified that as the nature of substituent group changes, it varies the breakdown voltage and glow
discharge zone following Townsend breakdown curve and eventually depends upon electron density
of the system.

Keywords: Gas discharges, VOCs, DBD systems, Paschen’s curves, Townsend breakdown curve,
self-sustainable plasma.

1. INTRODUCTION
In 1889 Friedrich Paschen developed a law which is known as Paschen’s law and the curve
obtained from it is called the Paschen’s curve, it explained the breakdown voltage as a function of the
electrode spacing or gap (d), operating pressure (p), and gas composition [1]. The breakdown voltage
is a function of the product of the pressure (p) and the inter-electrode distance (pd).

 = () (1)

Vb= is the breakdown voltage.

The mathematical formulation of Paschen’s curve is derived from Townsend’s assumption

[2]. Description of the basic charge generation processes including electron impact ionization (α
process) and secondary electron emission from the cathode due to primarily ion bombardment (the γ
process), though other bombardment processes may play a vital role in this theory [3]. Historically,
Paschen’s curve has proved to be accurate for large gaps and at low pressures [4-5], but it is often
acknowledged that it fails to explain the behaviour of curve at extremely low or high pd values [6-7].

1.1Conditions for self sustained discharge

Sustainability of plasma depends upon the applied voltage which must exceed the breakdown
voltage of the gases. When this voltage is attained, the gases lose their dielectric properties and turn
into conductors. It must satisfy the following relations:

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1−
 − 1 =0

1

 = 1 + 


Paschen derived breakdown voltage from the above relationship as:


 =  (2)
 


Finally expressing:

 = () (3)

A and B are the constants and can also be calculated as:

!
A=
"#!
, $% is electron-neutral collisional cross-section, Tn is temperature of neutral atom, k is the
Boltzmann constant.

B = &' where Vi is the ionization potential and γ is secondary electron emission coefficient.

From equation (1) it is clear that breakdown voltage depends on the product of p and d for a
given gas. From the Paschen curve (figure 1), it is understood that breakdown voltage is minimum for
a certain pd product. But it is large for both small and large values of pd. This can be explained as
there are too few collisions/ too large collisions at low and high values of pd respectively [8-19]. In
order to optimize the newly designed DBD reactor, Paschen law and Townsend Theory were verified
and the results were discussed in this piece of work.

Figure 1. Paschen curves obtained for helium, neon, argon, hydrogen using the expression for the
breakdown voltage as a function of the parameters A, B [20].

2. MATERIALS AND METHODS

In this work to optimize the DBD plasma system, we have performed a simple
investigation on the electrical breakdown of Ar and He gas molecules between two parallel electrode
plates separated by variable distance and voltage. The current is kept low so that the temperature is
below the critical value beyond which thermionic emission occurs. In order to avoid emission of
excess free electrons from the electrode, the low electric field is maintained. The parallel electrode

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plates are used to avoid corona discharge due to accumulation of charges on cornered surfaces that
can cause high potential gradients around them.

The experimental arrangement used to study DBD discharge at atmospheric pressure

condition is sketched in Figure 2.

Figure 2 . Parallel Plate Plasma Reactor

The discharge is generated between two plane electrodes that is covered by 3mm thick pyrex
dielectric plates. The normal AC power supply is connected (frequency 50Hz) to a step-up
transformer for generation of potential from 0-30kV. Two mass flow controller of the range 0-5
lit/min is connected to measure the gas flow to the reactor. The breakdown voltage for different VOCs
with carrier gases like He and Argon are studied here.

Two MFCs are connected to the carrier gases Argon and Helium. The other end is attached to
the reactor chamber. When high voltage is applied to the system, plasma is generated. Varying
different voltages as well as gas gap the system is optimized. The gas gap distance can be varied from
3mm to 15mm. preliminarily break down voltages at different gaps are noted. By plotting a graph
between break down voltage verses pd (pressure (p) X distance (d)), Paschen Curves for different
gases are obtained.

In the second case we changed the flow rate of the gases, and then measured the discharge
current. Pressure exerted was calculated from the flow rate. Then by plotting graphs between break
down voltages and (P X d), we get Paschen’s Curve.

3. RESULTS AND DISCUSSION

3.1. Optimization of the reactor in presence of Ar at a fixed gap.

The optimization parameters for different gases (argon and He) varying voltage and
distance were analyzed. Townsend breakdown and Paschen Curve were analyzed for different
pressure and distance [6]. Impedance matching resistor was installed between HV power supply and
DBD reactor for maximum power transfer at optimized operating condition.

The curve (figure 3) for Ar is obtained when gas-gap is kept fixed at 11mm and mass flow
rate is varied from 0.5-5.0 lit/min. It is observed from the figure 4 that when P X d value is 24.75
(Torr X mm) the minimum value of Vb corresponds to 2.1 KV and at this condition the system is
optimized.

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14

12

10
Voltage in kV

0 50 100 150 200 250 300

p*d (au)

Figure 3. Paschen Curve for Ar

3.2 Optimization of the system in Ar with volatile organic compound.

In presence of Ar, different volatile organic compounds ionize in different voltage (figure 4,
5, and 6). Benzene, xylene and toluene and in Ar plasma ionize at 2.8 kV, 4.5 kV and 2.6 kV.
Between benzene and toluene, due to branching, toluene reacts first. In spite of presence of two
substituted methyl groups in xylene its breakdown voltage is higher than others. This may be
explained in terms of steric effect. During the course of experiment we also found that xylene
decomposes at higher voltages than benzene and toluene indicating presence of some stabilizing
energy in xylene between methyl substituent.
Vb

2.90

2.88
Breakdown voltage Vb(kV)

2.86

2.84

2.82

2.80

-10 0 10 20 30 40 50 60 70 80
P x d (a.u)

Figure 4. Paschen Curve for Ar + Benzene

7.5

7.0
Breakdown voltage Vb(kV)

6.5

6.0

5.5

5.0

4.5
-10 0 10 20 30 40 50 60 70 80

P x d (a.u)

Figure 5. Paschen Curve for Ar + Xylene

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B
3.6

3.4
Breakdown voltage Vb(kV)

3.2

3.0

2.8

2.6

2.4
0 10 20 30 40 50 60 70

P x d (a.u)

Figure 6. Paschen Curve for Ar + Toluene

3.3 Optimization of the plasma reactor depending upon the two different gap distances between the
electrodes for He plasma

From the figures 7 and 8 it is clear that He plasma is best explained when its mass flow rate is
1.0lit/min. but the breakdown voltage is higher (6.5 KV) when the gas gap is 7mm (figure 7) as
compared to 4mm distance (i.e 3.9 KV) (figure 8). The system can work efficiently for formation of
sustainable helium plasma at a gas gap distance 4- 7mm and the applied voltage in the range of 3.9-
6.5 kV. So the formation and existence of He plasma in this system can be understood in following
ways:

i. It depends upon the distance between the electrodes.

ii. Also on the flow rate of the gas i.e. concentration of the gas present in the reactor volume
iii. Volume of the chamber as its volume depends upon the inter electrode distance

Vb
12

11
Breakdown voltageVb(kV)

10

5
-2 0 2 4 6 8 10 12 14 16 18
P x d x 10 (a.u)

Figure 7. Paschen Curve for He (d=7mm fixed and mass flow is varied)

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Vb
4.4

4.3
Breakdown voltage Vb(kV)

4.2

4.1

4.0

3.9

-10 0 10 20 30 40 50 60 70 80
P x d (a.u)

Figure 8. Paschen Curve for He (d=4mm fixed and mass flow is varied).

3.4 . Optimization of He plasma in presence of volatile organic compounds in different flow rates
From the figure 9, 10 and 11, it is clear that all the above system is optimized in the gas gap
of 4mm for the formation of He plasma. In three cases mass flow rate is 1lit/min. The gas gap distance
is 5mm and 4mm in figure 10 and 11 respectively. For figure 10 the breakdown voltage is 3.2kV and
it is slightly greater than in figure-11 i.e 3.0 kV. The deviation may be due to the atmospheric
humidity (condition) and gas gap. But in case of figure 9 as the gas gap (pd) is 8mm the minima
broadened the Paschen curve and we get higher breakdown voltage at 5.5KV.

Figure 9. Paschen Curve for He + Benzene (d=8mm )

Vb
4.6

4.4

4.2
Breakdown voltage Vb(kV)

4.0

3.8

3.6

3.4

3.2

2 4 6 8(Torr.10 12 14 16
P x d (a.u)

Figure 10. Paschen Curve for He + Benzene (MFC= 1lit/min ) (d=5mm )

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Vb

3.6

3.5
breakdown voltage Vb(kV)

3.4

3.3

3.2

3.1

3.0

-10 0 10 20 30 40 50 60 70 80
P x d (a.u)

Figure 11. Paschen Curve for He + Benzene

Vb
3.5

3.4
break down voltage (Vb)in kV

3.3

3.2

3.1

3.0

-10 0 10 20 30 40 50 60 70 80
P x d (a.u)

Figure 12. Paschen Curve for He + Toluene

3.5 Optimization of He plasma in reactor in the presence of different volatile compounds

Comparing the figures 11, 12, 13 and 14, the breakdown voltages of the volatile organic
compounds like benzene, toluene, xylene and chlorobenzene are found to be 3.0kV, 3.0kV, 3.8kV and
2.7kV respectively. Which shows for a particular mass flow rate (1lit/min), the breakdown voltages
differs for different compound. In case of nitrobenzene (in figure 15) the breakdown voltage is about
4.0kV which is much greater than chlorobenzene i.e.2.7kV. As the gap distance is more (6mm).So it
required more voltage to break the compound at higher gas gap. It indicate breakdown voltage (i)
depends upon the nature of the VOC compound and bond energies of the compounds.
B

4.6

4.5
Breakdown voltage Vb (kV)

4.4

4.3

4.2

4.1

4.0

-10 0 10 20 30 40 50 60 70 80

P x d (a.u)

Figure13. Paschen Curve for He + Xylene

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B
3.6

3.4
Breakdown voltage Vb(kV)

3.2

3.0

2.8

2.6
-10 0 10 20 30 40 50 60 70 80

P x d (a.u)

Figure 14. Paschen Curve for He + Chlorobenzene

Vb
12

11

10
breakdown voltageVb(kV)

3
-20 0 20 40 60 80 100 120 140 160
P x d (a.u)

Figure 15. Paschen Curve for He + Nitrobenzene

3.6 .Verification of Townsend breakdown curve.

Plasma breakdown as an important fundamental process in plasma science has been a subject
of enormous studies from the early days of gaseous electronics. Due to its relevance in a wide range
of applications, it is used for a deeper understanding of fundamental plasma behaviour [21-24].
Renewed interest in breakdown phenomena, especially breakdown in small gaps, emerged from the
possibility of lower facility and process costs for a variety of plasma processing and micro-
manufacturing techniques. At the same time, direct current (DC), pulsed DC and radio-frequency
(RF) discharges are widely used in the microelectronics industry, in plasma display panels, for
depositing thin films, for semiconductor processing, surface modification, analytical chemistry,
biotechnological and environmental applications, waste treatment etc. [25-31]. As already pointed out,
a better understanding of voltage breakdown, besides being scientifically interesting, will aid progress
in many fields and technologies, which generally fall into two categories: those that require high
electric fields, and those that require high electric currents. On the other hand, unwanted voltage
breakdown limits many technologies involving high electric fields [32]. Electric breakdown is
referred to as a process that transforms a non-conducting material to a conducting one when a
sufficient strong electric field is applied comprising an involved set of transient processes such as
collision of electrons, ions and photons with gas molecules and electrode processes which take place
at or near the electrode surface. Other possible gas processes include ion-atom collisions, excited
atom-molecule collisions, and atom-atom collisions. In 1928, Langmuir [33] introduced the word
plasma to describe the ionized gas that is created in a gas discharge.

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From above facts here we conclude that

Mechanism: mechanism of Townsend theory involves three steps which is represented as below
Let A is a gas molecules or atoms undergo ionization involving following steps:
Step-1 photo ionization:
A + hν → A+ + e
Step-2 ionization by excited atoms or molecule
A + A* → A+ + e + A
Or
Associative ionization
A + A* → A2+ + e
Step-3 Dissociative Recombination
A2+ + e → A + A*
Or Associative recombination
A+ + e → A + γ

Figure 16. Electron avalanche on the basis of Townsend’s theory

Following the Townsend theory (shown in figure 16) in this work, Voltage-current
characteristic of low temperature discharge between electrodes for a wide range of currents is plotted
in figure 17, plasmas become self-sustaining, i.e. the breakdown occurs. The simplest breakdown
condition can be expressed as: each primary electron generated in the initial avalanche and lost at the
anode is replaced by another electron generated by secondary emission at the cathode. This represents
a steady self-sustained current in the homogeneous field:

Et = Vb/d
(Point B in Figure 17), where Vb is the breakdown voltage and is determined from Equation (3) as a
function of d, γ and the known function α (EA: region of non- self-sustaining discharge, (BC)
Townsend discharge, (CD) subnormal glow discharge, (DE) normal glow discharge EF) abnormal
glow discharge. All these data shows the existence and sustainability of the plasma in the designed
reactor.

Figure 17. I-V curve of He + Benzene

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Figure 18. Breakdown voltage curve for different volatile compounds

3.7. Comparison of breakdown voltages for different substrates (VOCs) from current-voltage curve.

Influenced by Townsend experiment we have calculated the breakdown voltages (in figure 18
& 19). Breakdown voltage starts at 3.0kV, 2.7kV, 3.0kV and 3.8kV for benzene, chlorobenzene,
toluene, xylene respectively in figure 18. But it is 3.2kV, 6.0kVfor ortho-dichlorobenzene and
methylene chloride in figure 19. Here all these vocs are taken in combined with He as carrier gas. The
bond dissociation energy of C-H bond in benzene is ~390kCal/mole [8], in toluene is ~77.5kCal/mol
and in xylene ~77.5Kcal/mole [9], and that for C-Cl bond in chlorobenzene is ~399.19kCal/mole, for
ortho- dichlorobenzene it is 385.4 kCal/mole and that for methylene chloride is 310.0 kCal/mole[10].
It is observed that C-Cl bond energy is highest, but its breakdown voltage is 2.7kV and 3.2kv in case
of chloro and dichlorobenzene. For benzene bond energy is ~390kCal/mole, but dissociates at 3.0kV.
Similarly, the glow region also starts at 11.5kV for chlorobenzene and 5.0kV for di-chlorobenzene
where as that of benzene is 14.0kV. Since the electron affinity of Cl is appreciable, as soon as the
chamber is filled with He plasma , Chlorine atom gets detached from chlorobenzene and
dichiorobenzene quickly becoming neutral recombining with free electron in the plasma. Again for
benzene the maximum current is drawn i.e. 0.67mA and for chlorobenzene it is lower than benzene
i.e. 0.41mA whereas for dichlorobenzene it is much less i.e. 0.1mA justifying chlorine as a strong
electron scavenger. In both the cases the chlorine ions get detached from chlorobenzene and
dichlorobenzene in plasma medium by using DBD reactor at low breakdown voltage and current
producing sustainable plasma.

Figure 19. Breakdown voltage curve for different volatile compounds

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But it is found that in case of aliphatic dichloro compound i.e. methylene chloride, bond
dissociation energy is comparatively less i.e. 310.0kV whereas breakdown voltage starts at 6.0kV
and glow region starts immediately at6.5kv. It may be due to low molecular mass, high volatile nature
(B.P.-39.5) of the compound which gets dissociated completely in plasma medium due to electron
induced reaction.

4. CONCLUSION

Dielectric barrier discharge assisted plasma technique is a novel green technique with high
energy evolution. The developed DBD assisted plasma reactor is optimized using various diagnostic
methods. Optimization of a plasma reactor depends on size, gap between the electrodes, gas flow rate
as well as applied potentials and stability of carrier gases. It also depends upon the nature of the
compounds and type of bond which has been verified taking different volatile organic compounds like
benzene, toluene, nitrobenzene, chlorobenzene, dichlorobenzene, methylene chloride etc. Different
aspects discussed above give the reliability of the Paschen curve and Townsend breakdown theory
verified from our DBD plasma system operating in room temperature and atmospheric pressure.

ACKNOWLEDGMENT: Authors are thankful to BRNS India for funding and Ravenshaw
University for providing all facilities.

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