non-thermal atmospheric pressure plasmas: applications

50
Non-Thermal Atmospheric Pressure Plasmas: Applications Alexander Fridman, Applications Alexander Fridman, Nyheim Chair Professor, Drexel University, Philadelphia, USA NON-THERMAL ATMOSPHERIC PRESSURE DISCHARGES APPLICATIONS IN FUEL CONVERSION AND HYDROGEN PRODUCTION APPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGY APPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGY APPLICATIONS IN MATERIAL TREATMENT PLASMA MEDICINE Applications of Non-Thermal Atmospheric Pressure Plasmas APPLICATIONS IN FUEL CONVERSION AND HYDROGEN PRODUCTION •Plasma Conversion of Natural Gas, Liquid and Solid Hydrocarbons, Production of H2 and SynGas •Plasma Decomposition of H2S, Production of Hydrogen and Elemental Sulfur APPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGY •Plasma Decontamination of Air and Water Streams from Chemical Pollutants •Plasma Disinfection and Sterilization of Surfaces, Air and Water Streams APPLICATIONS IN MATERIAL TREATMENT •Plasma Polymerization and Processing of Polymers: Low Pressure vs. Atmospheric Pressure •Plasma Processing of Electronic Materials •Plasma in Tissue Engineering 1mm PLASMA MEDICINE •Plasma Sterilization of Living Tissue •Plasma-Stimulated Blood Coagulation Pl T t t fW d d Ski Di Plasma Treatment of Wounds and Skin Diseases. NON-THERMAL ATMOSPHERIC PRESSURE DISCHARGES: How to Keep them Cool? •Cold Plasmas vs. Transitional (Warm) Plasmas: Specifics of Applications Examples of Cold and Warm Plasma Sources Examples of Cold and Warm Plasma Sources •Gliding Arc Tornado and FE-DBD as Examples of the Cold and Transitional (Warm) Plasma Sources

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Non-Thermal Atmospheric Pressure Plasmas: Applications

Alexander Fridman,

Applications

Alexander Fridman,

Nyheim Chair Professor, Drexel University, Philadelphia, USA

•NON-THERMAL ATMOSPHERIC PRESSURE DISCHARGES

•APPLICATIONS IN FUEL CONVERSION AND HYDROGEN PRODUCTION

•APPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGYAPPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGY

•APPLICATIONS IN MATERIAL TREATMENT

•PLASMA MEDICINE

Applications of Non-Thermal Atmospheric Pressure Plasmas

•APPLICATIONS IN FUEL CONVERSION AND HYDROGEN PRODUCTION

•Plasma Conversion of Natural Gas, Liquid and Solid Hydrocarbons, Production of H2 and SynGas

•Plasma Decomposition of H2S, Production of Hydrogen and Elemental Sulfur

•APPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGY

•Plasma Decontamination of Air and Water Streams from Chemical Pollutants

•Plasma Disinfection and Sterilization of Surfaces, Air and Water Streams

•APPLICATIONS IN MATERIAL TREATMENT

•Plasma Polymerization and Processing of Polymers: Low Pressure vs. Atmospheric Pressure

•Plasma Processing of Electronic Materials

•Plasma in Tissue Engineering1mm

•PLASMA MEDICINE

•Plasma Sterilization of Living Tissue

•Plasma-Stimulated Blood Coagulation

Pl T t t f W d d Ski Di•Plasma Treatment of Wounds and Skin Diseases.

•NON-THERMAL ATMOSPHERIC PRESSURE DISCHARGES: How to Keep them Cool?•Cold Plasmas vs. Transitional (Warm) Plasmas: Specifics of Applications•Examples of Cold and Warm Plasma Sources•Examples of Cold and Warm Plasma Sources•Gliding Arc Tornado and FE-DBD as Examples of the Cold and Transitional (Warm) Plasma Sources

辻野貴志
タイプライターテキスト
Copyright remains with the author(s).

Thermal Plasma Non-Thermal Cold Plasma

Cold Plasmas vs. Transitional (Warm) Plasmas: Specifics of ApplicationsNon-Thermal

thermal ionization

Non Thermal Cold Plasmadirect electron impact ionization

Transitional (Warm) Plasmastepwise electron impact ionization

Aurora

X-ray view of the sun

Aurora

TORNADO

Corona DischargeICP Torch

TORNADO

Gliding Arc

Co o a sc a geICP Torch• High power density

and productivity.

•High selectivity

•High plasma power and density.

•High gas temperature.

•Low gas temperature and very high electron temperature.

•High selectivity

• Relatively low temperature.

•Low selectivity of chemical processes .

•Low power density

•High chemical selectivity.

NonNon--Thermal Thermal Atmospheric Pressure Atmospheric Pressure Cold PlasmasCold Plasmas

APG in He mix.APG in He mix.

Cold PlasmasCold Plasmas

Electron BeamElectron BeamDielectric Barrier DischargeDielectric Barrier Discharge

APG in He mix.APG in He mix.

Floating Electrode (p/np) DBDFloating Electrode (p/np) DBD

Packed Bed DBDPacked Bed DBD10kW Pulsed Corona10kW Pulsed Corona Pulsed CoronaPulsed Corona

Non-Thermal Atmospheric Pressure pTransitional (Warm) Plasmas

Micro APG

TORNADO

Gliding ArcModerate

Pressure MW

NonNon--Thermal Transitional (Warm) Thermal Transitional (Warm) At h i P PlAt h i P Pl

“GLIDING ARC in Flat Geometry”“GLIDING ARC in Flat Geometry”“GLIDING ARC in Flat Geometry”

Atmospheric Pressure PlasmasAtmospheric Pressure Plasmas

GLIDING ARC in Flat GeometryGLIDING ARC in Flat GeometryGLIDING ARC in Flat Geometry

N E ilib i R i

Electron Temperature

~ 1 - 1.5 eV

Maximum ElectronNon-Equilibrium Region Maximum Electron Density (1/cm3)

1012 - 1014

Maximum Gas Temperature

300 - 3000KTemperature

Average Power Density

10 - 300 W/cm3

Fast Equilibrium to Non-Equilibrium Transition

Q i E ilib i R i (1 5 kV)

Ionization Mechanism

Stepwise / Direct

Quasi-Equilibrium Region (1- 5 kV) Discharge Cycle 2 - 10 mSec.

Current (A) 0.01 - 10

Power (kW) 0.1 - 100

“GLIDING ARC in Flat Geometry”“GLIDING ARC in Flat Geometry”“GLIDING ARC in Flat Geometry”

Extinction

Non-Equilibrium Region

Elongation

Fast Equilibrium to Non-Equilibrium Transition

Initial BreakdownQuasi-Equilibrium RegionQuasi Equilibrium Region

Gliding Arc Rotating inGliding Arc Rotating in Magnetic FieldMagnetic Field

4

4.5

4

4.5

4

4.5 7

Magnetic Field: 0.1TCurrent: 10-100 mA

1.5

2

2.5

3

3.5

1.5

2

2.5

3

3.5

1 5

2

2.5

3

3.5

6

Voltage: 2 – 5 kVFrequency: 50 – 200 Hz.

50

0.5

1

-4 -3 -2 -1 0 1 2 3 4

0

0.5

1

-4 -3 -2 -1 0 1 2 3 40

0.5

1

1.5

-4 -3 -2 -1 0 1 2 3 4

44

5

BB 1/60th of a sec

3

1 2

3BB

1/60th of a sec

(+)

Fuel & Oxidizer

1 2

(-)

Power Supply & Regulator

Plasma Enhanced Plasma Enhanced CombustionCombustion

1/1000th of a sec

“THE GLIDING ARC IN TORNADO”“THE GLIDING ARC IN TORNADO”“THE GLIDING ARC IN TORNADO”

Flat circularElectrode 2Electrode 2

Gas out

Free end of spiral electrode

Plasma reactorSpiral shape

Electrode 1-A

Circular ringElectrode 1-B

Connection wireto power supply

Flow Visualization Camera Speed: 1.normal, 2. 1 msec.

“It Melts a Metal Rod But You Can Touch It”

Applications of Non-Thermal Atmospheric Pressure Plasmas

•APPLICATIONS IN FUEL CONVERSION AND HYDROGEN PRODUCTION

•Plasma Conversion of Natural Gas, Liquid and Solid Hydrocarbons, Production of H2 and SynGas

•Plasma Decomposition of H2S, Production of Hydrogen and Elemental Sulfur

•APPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGY

•Plasma Decontamination of Air and Water Streams from Chemical Pollutants

•Plasma Disinfection and Sterilization of Surfaces, Air and Water Streams

•APPLICATIONS IN MATERIAL TREATMENT

•Plasma Polymerization and Processing of Polymers: Low Pressure vs. Atmospheric Pressure

•Plasma Processing of Electronic Materials

•Plasma in Tissue Engineering1mm

•PLASMA MEDICINE

•Plasma Sterilization of Living Tissue

•Plasma-Stimulated Blood Coagulation

Pl T t t f W d d Ski Di•Plasma Treatment of Wounds and Skin Diseases.

•NON-THERMAL ATMOSPHERIC PRESSURE DISCHARGES: How to Keep them Cool?•Cold Plasmas vs. Transitional (Warm) Plasmas: Specifics of Applications•Examples of Cold and Warm Plasma Sources•Examples of Cold and Warm Plasma Sources•Gliding Arc Tornado and FE-DBD as Examples of the Cold and Transitional (Warm) Plasma Sources

Plasma-Chemical Hydrogen Production

Plasma PO optimal parameters:gas

chromatography

Production

Plasma PO optimal parameters:

CH4+0.5O2 = CO + 2 H2

optimal equivalence ratio = 3.3,

chromatography

p q ,[O2]/ [CH4]=0.6

Preheating temperature = Internal, 750KC i 92%

GLIDING ARC REACTOR

gas sampling

resistor box

Conversion = 92%Electric energy cost :

experimental = 0.06 kWh/m3

modeling EQ = 0.11 kWh/m3

powersupply

g Qmodeling NE = 0.07 kWh/m3

Output Syn-Gas energy = 3.00 kWh/m3

power for 100,000 barrel/day of Liquid Fuel:i t l 4 5 MW

Quartzheater

mixing chamber

experimental = 4.5 MWmodeling EQ = 8.2 MWmodeling NE= 5.2 MW

Oscilloscope & data acquisition

Temperature controller

Flowcontrollers

Gliding Arc Tornado for Fuel Conversion into SynGas

Gas Chromatography GlidingGas Chromatography

resistorbox

Gliding Arc

ReactorGas

Samplingbox

powersupplysupply

Heat Exchanger

Oscilloscope &

Flow Controllers

Exchanger

& data acquisition

Gliding-Arc-Tornado Plasma-Catalytic Methane Partial Oxidation

THE EXPERIMENTAL SETUP

FIRED ATFIRED AT EQUIVALENCE RATIO

4.

Syn-gas Burner

Plasma-Catalytic Reactor

Simulation Vs Experiments The conversion degree: α = ([H2] + [CO]) / 3[CH4]

1

The conversion degree: α = ([H2] + [CO]) / 3[CH4]

0.8

0.9

0.6

0.7

rsio

n D

egre

e

0 4

0.5

0.6

Co

nve

r

0.3

0.4

2.8 3.2 3.6 4 4.4 4.8Equivalence Ratio

Modeling results With plasma

Modeling results without plasmaWith plasma

Experimental results with plasma

without plasma

Experimental results without plasma

Simulation Vs Experiments Electric Energy Cost = W (KW-hr)/ meter cube of

0.18

Electric Energy Cost = Wel(KW-hr)/ meter cube of Syn-Gas (Output Syn-Gas Energy = 3.00 kWh/m3)

0.15

)

0.09

0.12

En

erg

y C

ost

^3

of

syn

gas

)

0 03

0.06

Ele

ctri

c

(KW

hr/

m

0

0.03

2.8 3.2 3.6 4 4.4 4.8Equivalence Ratio

Modeling results

E i t l ltExperimental results

Simulation Vs Experiments Total Energy Cost = (Electric Energy Cost +

10

gy ( gyMethane Energy Cost) per meter Cube of Syn-Gas

8

9

as)

6

7

En

erg

y C

ost

r/m

^3

of

syn

ga

4

5

E

(KW

hr

3

4

2.8 3.2 3.6 4 4.4 4.8Equivalence RatioEquivalence Ratio

Modeling results With plasma

Modeling results without plasmaWith plasma

Experimental results with plasma

without plasma

Experimental results without plasma

Gliding Arc Tornado Plasma Catalysis Highlights:

•Only 2.0% of Total Energy Consumption Required for

Plasma Catalysis Highlights:

Plasma Power

•Electric Energy Cost 0.06 kWh/m3 of syn-gas (energy from gy y g ( gySyn-Gas = 3.0 KW-hr/m3).

•92% conversion at Equivalence Ratio of 3 392% conversion at Equivalence Ratio of 3.3.

•Internal Heat Recuperation (Preheating) at 750 K.

•No soot Deposition.

•Large Specific Production Rates due to Low Residence g pTimes.

•Effective for Higher Hydrocarbon Conversion to Syn-Gas.Effective for Higher Hydrocarbon Conversion to Syn Gas.

•Not Sensitive to Sulfur and Other Impurities.

GAT for on board liquid fuel conversion

H2S Dissociation

with production of H2 and Sulfur

H2S → H2 +S(s), 0.2eV/molWhat has been done 20 years ago…

The most successful project on hydrogen production with the help of plasma (Russia Kurchatov Inst 1980-s (Major

( )

help of plasma (Russia, Kurchatov Inst., 1980-s (Major problem – Microwave, Power, PhDs)

The best results obtained in microwave plasma of moderate pressure: high Te, low T0,

The industrial scale H2S plasma-chemical plant with the power of about 1 MW has been built on the basis of microwave plasma generators near the city of Orenburg (also refinery near Lviv, Ukraine). ( y , )

Similar project started in 1990-s in the USA by the Argon National Laboratory (Harkness & Doctor 1993), was stopped because of the use of MW plasma generators (UOP Mobile)(UOP, Mobile)

The economic estimations of the hydrogen production using this method and taking into account pure sulfur productions were promising.

Conversion Degree and Energy Cost of H2 ProductionConversion Degree and Energy Cost of H2 Production by H2S Dissociation in Non-Equilibrium Plasma

What’s new in the H2S plasma technology?(after 20 years…)

• New discharges: gliding “arc” (Mimicking Microwave)

• New gas-dynamic solutions: reverse-New gas dynamic solutions: reversevortex or “tornado” flow

h f l d i l• GAT – cheaper, powerful and simple alternative to microwave plasma

• New generation of power supplies

H2S dissociation in 8

HH S

GAT2

H2H2S

Heat2

36

Dielectric reactor with

H2

H2S

Sulfur1

7

Dielectric reactor with discharge ignition at the reduced pressure.

H2S

5

7

Problem: quartz-metal sealing

A th ibl l tiAnother possible solution –discharge elongation over the metal reactor wall

Sulfur Sulfur

metal reactor wall

Sulfur

4

Sulfur

Laboratory System for H2S dissociation in the Gliding Arc Tornado

H2, H2O, S

43

6

H2S, H23

5H2, H2O

7

7

H2S

H2S, H2, S

1

H2

8

Scheme of the experimental system: (1) Plasma reactor, (2) Sulfur receiver; (3) Sulfur filter (4) Iron

5S

2

receiver; (3) Sulfur filter, (4) Iron sponge, (5) Water container, (6) Gas chromatograph, (7) Flow meter; (8) Heat exchanger. g

H2S Dissociation

in Gliding Arc Tornadoin Gliding Arc Tornado

(treatment of phosphogypsum)11

H2H2S Process Characteristics:•Gas Temperature 200-400C

Heat2

36

•Electron Temperature 15,000K•H2S Conversion Degree: 95% •Products: Hydrogen Sulfur

H2S

Sulfur

H2

3

4

•Products: Hydrogen, Sulfur•Energy Cost: 0.8 kWh/m3 H2

Sulfur

5

7 •5000 t/day phosphogypsum:•1, 142 t/day of H2S

H2

1

•1,076 t/day S; 67 t/day H2•Power requirement 6.6 MW (min)•Maximum unit power today 1 2 MW

Sulfur•Maximum unit power today 1.2 MW

Plasma Ignitiongand Flame Stabilization

Applications of Non-Thermal Atmospheric Pressure Plasmas

•APPLICATIONS IN FUEL CONVERSION AND HYDROGEN PRODUCTION

•Plasma Conversion of Natural Gas, Liquid and Solid Hydrocarbons, Production of H2 and SynGas

•Plasma Decomposition of H2S, Production of Hydrogen and Elemental Sulfur

•APPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGY

•Plasma Decontamination of Air and Water Streams from Chemical Pollutants

•Plasma Disinfection and Sterilization of Surfaces, Air and Water Streams

•APPLICATIONS IN MATERIAL TREATMENT

•Plasma Polymerization and Processing of Polymers: Low Pressure vs. Atmospheric Pressure

•Plasma Processing of Electronic Materials

•Plasma in Tissue Engineering1mm

•PLASMA MEDICINE

•Plasma Sterilization of Living Tissue

•Plasma-Stimulated Blood Coagulation

Pl T t t f W d d Ski Di•Plasma Treatment of Wounds and Skin Diseases.

•NON-THERMAL ATMOSPHERIC PRESSURE DISCHARGES: How to Keep them Cool?•Cold Plasmas vs. Transitional (Warm) Plasmas: Specifics of Applications•Examples of Cold and Warm Plasma Sources•Examples of Cold and Warm Plasma Sources•Gliding Arc Tornado and FE-DBD as Examples of the Cold and Transitional (Warm) Plasma Sources

VOC Destruction inVOC Destruction in Non-Thermal Plasma

“Non-thermal Plasma Oxidation” = “Thermal Oxidation” – “Heat Energy”

RTO → 0 1 eV/mol Plasma → 10-30 eV/molRTO → 0.1 eV/mol, Plasma → 10-30 eV/mol

Critical VOC Concentration → 0.3-1 % = 3,000-10,000 ppm

Electric Energy → Plasma Electrons →Active Radicals → Selective Oxidation

e + N2 → N2+ + e + e N2

+ + H2O → N2 + H2O+2 2 2 2 2 2

H2O+ + H2O → H3O+ + OH OH + R-H → R- + H2O

R- + O2 → R-O-O- R-O-O- + R-H → R-O-O-H + R-

R O O → CO + H O R O O H → CO + H O

Slide 32

R-O-O- → CO2 + H2O R-O-O-H → CO2 + H2O

HVLC Brownstock Washer Vent EmissionsHVLC Brownstock Washer Vent Emissions

CAS f i “ h i ”NCASI Information “The worst case scenario”suggested by GP

Dimethyl Disulfide 2 ppm 20 ppmDimethyl Disulfide 2 ppm 20 ppm

Dimethyl Sulfide - 1727 ppm

Methanol 83 ppm 2330 ppm

Acetone 3 ppm -

Terpenes 209 ppm 62 ppm

Conditions

Temperature 103°F 150°F

R l ti H idit 100% 100%Slide 33

Relative Humidity 100% 100%

Pulsed Corona, Philadelphia, Chicago

Electron Beam: Moscow

Slide 34Gliding Arc: PhiladelphiaDBD, Packed Bed: PNNL

Pulsed Corona ReactorVoltage pulses: - up to 20 kV

- duration 100 ns / rise time 10 ns- power 25 W / frequency 2000 Hz

Flow rate: - 2 SLMTemperature: - from 70OC to 220OC

Thyratron-

Multiple streamer

dischargesbased

High Voltage

Power Supply

g

Hazardous Central

Slide 35

gas inByproducts out

Central wire External cylinder

Wet Pulsed Corona Reactor

Gas phase byproducts out

Water input

A layer of absorbing material covers theMultiple streamer

discharges

A layer of absorbing material covers the internal wall of the external cylinder, in order to create a continuos water film.

External cylinder

RH non soluble

+OH

R+H O

Central wire

External cylinder R+H2O

+O2

RO2

Thyratron-based

High Voltage Hazardous

Water output2

RO2H soluble peroxides

Slide 36

Power SupplyHazardous

gas in

Wet Pulsed Corona Reactor

University Operation Conditions:

Water Film Flow: 0.01ml/min - 220 ml/min

Gas Flow Rate: 1 SLM

Kurchatov Institute Operation Conditions:Operation Conditions:

Gas Flow Rate: 30 CFM Power: 1kW

Slide 37

VOC Removal in Corona Discharge

Acetone Methanol

80

100

Acetone

80

100

Methanol

60

80

RE

[%

]

60

80

RE

[%

]

20

405 ppm

20 ppm

200 ppm

1000 ppm

DR

20

40 5 ppm 20 ppm 200 ppm1000 ppm

DR

00.02 0.04 0.06 0.08 0.1 0.12

1000 ppm

SEI [kWh/m3]

00.02 0.04 0.06 0.08 0.1

SEI [kWh/m3]

• no organic compounds are produced as byproducts of the oxidation process;

Slide 38

oxidation process;

VOC Removal in Corona Discharge

Alpha-Pinene Dimethyl Sulfide

80

100

90

100

60

RE

[%

]

80

90

RE

[%

]

20

40 150 ppm400 ppm800 ppm

DR

70< 300 ppm400 ppm1000 ppm

DR

00.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1

SEI [kWh/m3]

60

0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1

SEI [kWh/m3]

• acetone and methanol are the main organic byproducts from destruction of Alpha-Pinene and Dimethyl Sulfide respectively

Slide 39

destruction of Alpha Pinene and Dimethyl Sulfide respectively (about 5-10%);

VOC Removal in Wet Corona

• the presence of the water film allows to

100

Wet Coronaincrease VOC removal by synergetic effect of

80

90

%]

Corona

plasma and water absorption;

70

DR

E [

Methanol = 1000 ppmMethanol = 1000 ppm

Corona

Water flow rates:

60

Acetone = 200 ppm

• 0.4 ml/min for methanol

0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1

SEI [kWh/m3] • 1 ml/min for acetone

Slide 40

Wet Corona is the Championfor Brownstock Washer Vent Emission

Destruction – Removal Efficiency – 98-100%

Treatment

y

Byproducts – No Byproducts in Gas Phase

Energy Price: Regular conditions – 10 W-h/m3

Worst Case Scenario – 20 W-h/m3

For 25,000 SCFM Brownstock Washer stream: Power – 500 kW

W t 25 l/ iWater – 25 gal/min

Advantages: 1. Long Period No-Maintenance, No Catalyst, No Regeneration

2. Low Inertia, Easy Adjustable for Different VOC Concentration

3. No Byproducts, No Emission of Sulfur Compounds

Slide 41

4. Low Cost

Mobile Environmental Laboratory

Slide 42

Control room boundaryPneumatic and hydraulic scheme

ScrubberCorona

discharge volume

Mist Separator

Automatic regulator

BlowerCorona control

itWater pump

Trailer boundary

Corona setup boundary

Treated air flow

unit

Treated air flowCompressed air and pressure control

line Clean and technical water

Waste water

Spray or air atomizing nozzles

Flow metersVacuum-gauge

Slide 43

Waste water

Control lines TapsPressure regulator

8 kW Pilot Pulsed Corona Discharge

Slide 44

Mobile Environmental Laboratory

Slide 45

Air Sterilization Using Non-thermal Plasma

Objective: Sterilize indoor air containing bio-aerosols at standard HVAC conditions (room temperature, pressure, high flow rates) using non thermal plasmaflow rates) using non-thermal plasma

Pathogen Detection & Remediation Facility (PDRF)•Sealed air flow system (250 liters 25 l/sec)Sealed air flow system (250 liters, 25 l/sec)•3 Non-thermal Plasma Reactors

–Dielectric Barrier Discharge (DBD)–Magnetically-rotated Gliding Arc

Influenza A virus cluster

–Pulsed Corona•Air sampling system

Virus size: 80-120 nm

Cyanobacteria – non-pathogenic unicellular bacteria (algae) used for initial tests.

Influenza A virus generally considered more difficult toInfluenza A virus – generally considered more difficult to destroy & requires many safety precautions for experiments

Spores – B. Subtilis B. ThurengiensisCyanobacteriaSize: ~1 micron

Slide 46

p g

Air Sterilization Experiments

Interchangeable Plasma Devices:

p

ev ces:DBD, Gliding Arc

Sealed Air Flow System

Air Sampling Equipment

AIR FLOW

Collison Nebulizer

BioSafety Level 2 Fume HoodCentrifugal

Blower

AIR FLOW

Slide 47

Pathogen Detection and Remediation Facility (PDRF)

Pathogen Detection and Remediation Facility (PDRF)Pathogen Detection and Remediation Facility (PDRF)

Slide 48

Dielectric Barrier Discharge (DBD) for Air SterilizationDielectric Barrier Discharge (DBD) for Air Sterilization

Electron Avalanche

150 cm (6.

Avalanche

.5”)

Viruses pass between wires through plasma

Area of DBD plasma region: ~104cm2

Quartz Capillary covers high voltage wire

Maximum Voltage: 18.4 kV

1.5 mm Discharge Gap

Slide 49

Maximum Voltage: 18.4 kV Operating Frequency: 6.8 kHz

Power Consumption: ~160 WattsReactor Inlet

View

Magnetically Rotated Gliding Arc for Air SterilizationMagnetically-Rotated Gliding Arc for Air Sterilization

Plasma treated air flow

Design PrototypeN N In Operation

Arc starts at the shortest gap and glides along the

spiral to stabilize at

S S

[+[p

constant distance position between electrodes

Outer pipe di t 8”

10 kVDC Power

Supply

[+]

[–]

Slide 50Contaminated air flow

Top View

diameter: 8”Arc Rotation Frequency: 20 Hz

Power ~ 1KW

DBD Air SterilizationPlasma Air Sterilization experiments

DBD Air Sterilizationp

1.00E+06

nit

s r

1 00E+03

1.00E+04

1.00E+05

min

g U

nre

of

Air

Expt 1

Expt 2First Pass Through Plasma

1.00E+01

1.00E+02

1.00E+03

on

y F

or

cfu

)/L

itr p

Expt 3

ControlComplete Inactivation

1.00E+00

0 2 4 6 8 10 12

Co

lo (c

Time (min)

R lt f th i t ili ti i t S l t k b f dResults of the air sterilization experiments. Samples taken before and after plasma exposure. Complete inactivation is observed at the third

sample.

Water Sterilization SystemWate Ste ili ation System

Spark in Water Corona in Water

Comparison of inactivation efficiency of d ff f d hdifferent types of discharges in water

Comparison of inactivation efficiency of different types of discharges in water(in all cases average discharge power was the same)

Plasma Sterilization of WaterLOG REDUCTION VS. ENERGY

FOR DIFFERENT BACTERIAL CONCENTRATION

A low D-value of 125 J/L was obtained for an initial

t ti fconcentration of 104 CFU/ml of bacterial solutionbacterial solution.

The D-value

Log reduction vs Energy for different concentrations in

decreased with a decrease in b t i lLog reduction vs. Energy for different concentrations in

case of spark discharge plasma treatment (distance 0.5 cm, energy in pulse 2J)

bacterial concentration.

Gliding Arc & DBDGliding Arc & DBD for sterilization of fruits/vegetables

Contaminated apples were treated with Gliding Arc and Dielectric Barrier Discharge (DBD)

Microorganism: Listeria innocua (surrogate for L. monocytogenes)

DBD

99% reduction after 2 minutes of treatment;99% reduction after 2 minutes of treatment;

Complete after 6 min

Glidi AGliding Arc

96% reduction after 4 minutes of treatment (current: 260mA) (discharges along the apple)260mA) (discharges along the apple)

Anthrax (BA spores)( spo es)

Gram positive, spore-forming bacteriap , p gCutaneous – most common (95% of cases)Inhalational – 18 U.S. cases in 20th century

Gastrointestinal – difficult to diagnose, 50% fatal

C be e d e il th h iCan be spread easily through airPersists in the environment for decades

Dry spores are very resistant to destruction by conventional sterilization methods

Experimental Results: Floating DBD sterilization

Bacillus anthracis spores – dimensions 1-1.5 X 3-10 microns

Original concentration of dry spores 1 mln per microgram Treatment time 2, 4, 6 minSterilization efficiency 100%Substrate temperature - room

Surface Sterilization and Disintegration of Microorganismsg

• Most sterilization efforts focus on the inactivation of

i i

Moogega Cooper

microorganisms

• NASA Goal: Surface sterilization of spacecraftsterilization of spacecraft materials with complete disintegration of spores and bacteria.

• Sterilization by cold ambient-air plasma has been successfullyplasma has been successfully demonstrated to lyse and completely disintegrate FE-DBDmicroorganisms

Efficiency of FE-DBD Plasma Treatment of B subtilis SporesTreatment of B. subtilis Spores

(Morphological Changes)100% sterilization after > 2 min DBD plasma

treatment (temperature 35 -45C)

Before 2 min

SEM images

Deinococcus Characteristics• Typically grows as clusters of two cells (diplococci) in the

early stages of growth and as clusters of four cells (tetracocci) in the late stages of growth

• Withstands extreme heat and Cold– Cultures grown at 30°C that have been

rapidly shifted to 52°C can be held at that temperature for up to 40 minutes with no loss of viabilitytemperature for up to 40 minutes with no loss of viability.

• Withstands Dehydration• Withstands Vacuum

E t ( 10 6 P ) d d ll– Exposure to space vacuum (~ 10-6 Pa) decreased cell survival by four orders of magnitude.

• Withstands Acid• Withstands Radiation• Withstands Radiation

– An instantaneous dose of up to 5,000 Gray with no loss of viability

– 100 rad = 1 gray (Gy) = 1 J/kgg y ( y) g– An instantaneous dose of up to 15,000 Gray with 37%

viability• 10 Gy is sufficient to kill a human

60 G ili l f E li• 60 Gy sterilizes a culture of E. coli

"Deinococcus radiodurans." Wikipedia, The Free Encyclopedia. 9 Nov 2006, 18:25 UTC. Wikimedia Foundation, Inc. 10 Nov 2006 <http://en.wikipedia.org/w/index.php?title=Deinococcus_radiodurans&oldid=86761044>.

Viability of Plasma Treated D. radioduransBefore Before

20 min DBD30 min DBD 20 min DBD

• Initial concentration of D radiodurans: 10E8• Initial concentration of D. radiodurans: 10E8

• Current: 0.25 Amps

• Temperature was 26 OC on average and did not exceed 30 OC

Efficiency of FE-DBD Plasma Treatment of Deinococcus di d i W t d D C ditiradiodurans in Wet and Dry Conditions

1 00E+06

1.00E+07

Expt 1 Expt 2

Dry D. radiodurans Wet D. radiodurans

1 00E+05

1.00E+04

1.00E+05

1.00E+06

cocc

us

(cfu

/ml)

1 00E 02

1.00E+03

1.00E+04

1.00E+05

oco

ccu

s(cf

u/m

l)

1.00E+01

1.00E+02

1.00E+03

Via

ble

Dei

no

c

1.00E+00

1.00E+01

1.00E+02

0 10 20 30 40 50 60 70

Via

ble

Dei

no

1.00E+00

0 5 10 15 20 25 30 35Time (min)

Time (sec)

FE-DBD

Applications of Non-Thermal Atmospheric Pressure Plasmas

•APPLICATIONS IN FUEL CONVERSION AND HYDROGEN PRODUCTION

•Plasma Conversion of Natural Gas, Liquid and Solid Hydrocarbons, Production of H2 and SynGas

•Plasma Decomposition of H2S, Production of Hydrogen and Elemental Sulfur

•APPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGY

•Plasma Decontamination of Air and Water Streams from Chemical Pollutants

•Plasma Disinfection and Sterilization of Surfaces, Air and Water Streams

•APPLICATIONS IN MATERIAL TREATMENT

•Plasma Polymerization and Processing of Polymers: Low Pressure vs. Atmospheric Pressure

•Plasma Processing of Electronic Materials

•Plasma in Tissue Engineering1mm

•PLASMA MEDICINE

•Plasma Sterilization of Living Tissue

•Plasma-Stimulated Blood Coagulation

Pl T t t f W d d Ski Di•Plasma Treatment of Wounds and Skin Diseases.

•NON-THERMAL ATMOSPHERIC PRESSURE DISCHARGES: How to Keep them Cool?•Cold Plasmas vs. Transitional (Warm) Plasmas: Specifics of Applications•Examples of Cold and Warm Plasma Sources•Examples of Cold and Warm Plasma Sources•Gliding Arc Tornado and FE-DBD as Examples of the Cold and Transitional (Warm) Plasma Sources

Interaction and Structuring of gDBD Microdischarges

ENHANCEMENT of OSTEOBLAST ATTACHEMENT andATTACHEMENT and

PROLIFERATION on 3D POLY (ε-CAPROLACTONE) SCAFFOLD

Precision Extrusion Deposition S t

Dielectric BarrierDi h S t

CAPROLACTONE) SCAFFOLDEda D. Yildirim

System Discharge System

PlasmaSample

250 μm

300 μm

15 mm×15mm×2mm(W×L×H)

7F2 Mouse osteoblast cells

Cell Suspension Seeded on Scaffoldsosteoblast cells

Surface wettability and functionalization are increased with plasma treatmentincreased with plasma treatment

>C=OFTIR-ATR

I d i>C=O

Increased in carboxyl and carbonyl

Contact Angle MeasurementSurface wettability is increased with

plasma treatment

functionalities with prolonged treatment time p

1790 1770 1750 1730 1710 1690 1670 1650 1630 1600

Wavenumber

CELL PROLIFERATION on PLASMA

TREATED SCAFFOLDSLive/Dead Essay with

untreated

yFluorescence Microscopy

550000

600000

650000

er

untreated

1 min

3 min

5 min

400000

450000

500000

Cell

Nu

mbe

250000

300000

350000

5 10 15

5-min treated

Incubation Time (hours)

Increased cell proliferation with plasma treatment

Plasma BioPrinter

1mm

Microplasmas for Micropatterning

Minimal current of glow discharge - 0.5 mA (below – dark):

•Cathode spot size - 90 mkm

•Anode spot size (channel diameter) - 30 mkm

•Diffusion radius for radicals 30 mkm•Diffusion radius for radicals - 30 mkm

Lower sizes – pulses, nano-corona in dense media

10 μm tungsten wire (Cathode)

Droplets condensed on surface from breath

800 μm

50 - 60 μm

800 μm

100 μm25 - 30 μm50 60 μ

800 μm

Silicon substrate

Silicon Oxidation

Applications of Non-Thermal Atmospheric Pressure Plasmas

•APPLICATIONS IN FUEL CONVERSION AND HYDROGEN PRODUCTION

•Plasma Conversion of Natural Gas, Liquid and Solid Hydrocarbons, Production of H2 and SynGas

•Plasma Decomposition of H2S, Production of Hydrogen and Elemental Sulfur

•APPLICATIONS IN ENVIRONMENTAL CONTROL AND BIOLOGY

•Plasma Decontamination of Air and Water Streams from Chemical Pollutants

•Plasma Disinfection and Sterilization of Surfaces, Air and Water Streams

•APPLICATIONS IN MATERIAL TREATMENT

•Plasma Polymerization and Processing of Polymers: Low Pressure vs. Atmospheric Pressure

•Plasma Processing of Electronic Materials

•Plasma in Tissue Engineering1mm

•PLASMA MEDICINE

•Plasma Sterilization of Living Tissue

•Plasma-Stimulated Blood Coagulation

Pl T t t f W d d Ski Di•Plasma Treatment of Wounds and Skin Diseases.

•NON-THERMAL ATMOSPHERIC PRESSURE DISCHARGES: How to Keep them Cool?•Cold Plasmas vs. Transitional (Warm) Plasmas: Specifics of Applications•Examples of Cold and Warm Plasma Sources•Examples of Cold and Warm Plasma Sources•Gliding Arc Tornado and FE-DBD as Examples of the Cold and Transitional (Warm) Plasma Sources

Slide 70

PLASMA MEDICINEPLASMA MEDICINE

Floating Electrode DBDFloating-Electrode DBD

1010--30 kHz30 kHz1010--30 kV30 kV

0.50.5--5mm gap5mm gap0 10 1--10 cm10 cm22 electrodeelectrode0.10.1--10 cm10 cm electrodeelectrode

1 W/cm1 W/cm22 plasma powerplasma power

Slide 72

DBD Tissue Treatment Electrodes

“Round” – 25mm diameter,any surface

“Wand” – 3mm tip,any small surface

“Roller” – 50cm width,large flat surface

Electrode modelElectrode model

FEFE--DBDDBD

Slide 73

Living TissueLiving Tissue

Tissue Sterilization

DBD: 12 KHz, 22KV,1W/cm2,

Atmospheric airSlide 74

Atmospheric air

Tissue SterilizationComplete sterilization in 4 seconds of DBD

treatment from skin flora:

St tStreptococcus (spherical gram-positive bacteria occurring in pairs or chains; cause e.g. scarlet fever and

tonsillitis)

St h l

Before DBD Treatment

Staphylococcus (spherical gram-positive parasitic bacteria that tend to form irregular colonies; some cause boils

or septicemia or infections)

YeastYeast (common name for an artificial assemblage of higher fungi which have temporarily or permanently

abandoned the use of hyphal thalli; they are unicellular, and

i d i i ll b b ddi fi i )vegetative reproduction is generally by budding or fission)

No Gross (visible) or microscopic tissue damage in up

i

to 5 minutes of DBD treatment

Tissue sources: cadaver abdomen, leg, and arm skin,

Slide 75

After 1-minuteDBD Treatment

gplastic surgery discards, wound tissue, and other

tissue samples.

Tissue Sterilization

No treatment controlNo treatment control

No treatment 15 DBD 15 DBDNo treatment 15 sec DBD 15 sec DBD

iSlide 76

Tissue Source: cadaver abdomen (stomach)

No treatment 5 min DBD 5 min DBD

Skin ToxicityComplete Sterilization in 4 seconds of

plasma

No tissue damage in 40 seconds of plasma and animal stays alive and well

Up to 10 minutes of continuous FE-DBD plasma

16 seconds of16 seconds ofFE-DBD treatment

40 seconds of

Slide 77

40 seconds ofFE-DBD treatment

Non-Destructive Blood Coagulation“…He is holding an electric cauterizing wand, which looks like a

g

cheap bank pen on a cord but functions like a scalpel. The wand b th t d b th t thboth cuts and burns, so that as the incision is made, any vessels that are severed are simultaneously meltedsevered are simultaneously melted shut. The result is that there is a good deal less bleeding and a good deal more smoke and smell. It’s not a bad smell, but simply a seared-meat sort of smell ”meat sort of smell…”

- Mary Roach in “Stiff. The Curious Lives of Human Cadavers”

Slide 78

Human Cadavers .

Non-Destructive Blood Coagulationg

Electrocautery/coagulation: Non-thermal Plasma:ec oc u e y/co gu o :

• 10,000+ °C – thermal damage

• Severe Pain – anesthetics required

No e s :

• Room temperature

• No painSevere Pain anesthetics required

• Smoke – endoscopic surgery is difficult or impossible

No pain

• No evaporation

• Wound remains wetp

• Post-operative healing problems –too much tissue damage

Wound remains wet

• Smell & look of burnt tissue –generates patient complaints

Slide 79

In Vitro Blood CoagulationIn-Vitro Blood Coagulation

Slide 80DBD: 12 KHz, 22KV, 1W/cm2, Atmospheric air

In-Vitro Blood CoagulationV o ood Co gu o

Gross/Visual examination:Gross/Visual examination:

Normal whole blood treated for 15 seconds completely coagulates in 2 minutes.

Untreated sample coagulates in 13 minutesSlide 81

Untreated sample coagulates in 13 minutes

“In-Vivo” Blood Coagulation

Slide 82DBD Treatment of Spleen (cadaver tissue).

“In-Vivo” Blood Coagulation

Slide 83DBD Treatment of Placenta (explanted tissue).

“In-Vivo” Blood Coagulation

epistaxis

In-Vitro Blood Coagulation

40 0

45.0

50.0

ec)

Prothrombin (Factor II) time

30.0

35.0

40.0in

Tim

e (s

e

Normal Whole Blood

H hili A Bl d

Na-Citrated Blood (with anti-coagulant binds Ca2+

20.0

25.0

Pro

trim

bi Hemophilia A Bloodanti-coagulant, binds Ca +,

Factor IV)

10.0

15.0

0 20 40 60 80 100 120

DBD Treatment TIme (sec)

Prothrombin Time (PT) analysis:Prothrombin Time (PT) analysis:

Prothrombin (Factor II) time of residual blood

Slide 85increases 3 times after 120 seconds of DBD

treatment.

Blood Coagulation Mechanismg

Natural CoagulationMechanism

BloodBloodVesselActivated plateletsActivated platelets

Resting plateletsResting platelets

Slide 86

CoagulationCascade

Slide 87

Blood Coagulation Modeling

Plasma generation ofCa2+ (Factor IV)

Phospholipid oxidation

( )

Phospholipid oxidation

Slide 88

Blood Coagulation Modeling

Natural Coagulation

1 W/cm2

DBD lDBD plasmaProthrombin Kinetics

(Clips Fibrinogen to Fibrin,( p g ,which provides for platelet aggregation)

Slide 89

Treatment of Skin Diseases

AliveAlive

DeadDead DBD Plasma Inactivation ofCutaneous Leishmaniasis

Slide 90

20 seconds of DBD Cutaneous Leishmaniasis

Leishmania Promastigote InactivationLeishmania Promastigote Inactivation

Slide 91

Treatment of Skin Diseasese e o S se ses20-second treatment: near-complete promastigote inactivation

)

4 00E+08

5.00E+08

ion

(1/

ml

3.00E+08

4.00E+08

cen

trac

ti

1.00E+08

2.00E+08

go

te c

on

0.00E+00

rom

asti

g

alive: dead: total:

P

Before treatment 3.48E+08 2.36E+07 3.72E+08

Plasma-treated 8.40E+06 3.80E+08 3.89E+08

Slide 92DBD Plasma Inactivation of Cutaneous Leishmaniasis

Treatment of Skin Diseases

DeadDead

20 seconds of DBD

Macrophage inactivation after 5 minutes of treatment:

Inactivates 100% ofLeishmania

P ti tSlide 93

Macrophage inactivation after 5 minutes of treatment:70% alive (inactivated macrophages are circled).

Promastigotes

Plasma Treatment of Melanoma Cancer CellsPlasma Treatment of Melanoma Cancer Cells

% f d d M l ll ft l% of dead Melanoma cells after plasma treatment

120

60

80

100

120

%

0.33

0 13

0

20

40

60% 0.13

0

0

0 sec 10 sec 20 sec 30 sec

dose of plasma

Slide 94

Apoptosis: Programmed Cancer Cell Death

15+15 sec in 24 hrs30 sec in 24 hrs

% of dead cells to control

15 15 sec in 24 hrs30 sec in 24 hrs

9000

10000

15+15 sec in 1 hr 30 sec in 1 hr 15+15 sec in 4 hrs5000

6000

7000

8000

% 15+15 sec in 1 hr 15 15 sec in 4 hrs30 sec in 4 hrs

2000

3000

4000

5000%

0

1000

2000

Melanoma cells continue dying even 24 hours after treatment

15+15 sec in 1 hr 30 sec in 1 hr 15+15 sec in 4 hrs

30 sec in 4 hrs 15+15 sec in 24 hrs 30 sec in 24 hrs

Slide 95

Melanoma cells continue dying even 24 hours after treatment

Apoptosis in Melanoma Cells

No PlasmaCell ApoptosisCell Apoptosis

TUNEL flow cytometry test: development of apoptosis in cell culture treated with low dose of plasma (5sec).

5 seconds of FE-DBD

TUNEL assay: development of apoptosis in cells culture 24+hrs after treatment with 5

d f l

Apoptosis begins developing at the end of day 1, reaches it maximum at day 2

Slide #96

seconds of plasma.Blue - normal cellsGreen- apoptotic cells

Wound Healing: Suppurated Burns Before Treatment

Phlegmonous Eyelid DefeatPhlegmonous Eyelid Defeat

Before TreatmentAfter 7 days of plasma therapy (5 sessions).

Wo nd Healing: Broad Necrotic S pp rated Ulcer

6 plasma treatments

Wound Healing:Trophic Venous Ulcers

Broad Necrotic Suppurated Ulcer(Diabetic Peripheral Neuropathy)

Before 21 Days 2 Months Before 5 Months (3 course, Treatment

y(10 sess.) (30 sess.) Treatment

( ,12 sess. per course)

FE-DBD Power Supplies

Sterilization ElectrodeSterilization Electrode

TransformerTransformer

Waveform GeneratorWaveform Generator

AmplifierAmplifierAmplifierAmplifier

StateState--ofof--thethe--art power supplyart power supply

Slide 98Portable power supplyPortable power supply