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Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Technological Applications of (Atmospheric-Pressure) (Micro)Plasmas: Opportunities & Challenges
Kurt H. Becker NYU, Polytechnic School of Engineering
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Technology improvements
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
FROM: B.M. Penetrante and S.E. Schultheiss “Non-thermal Plasma Technologies for Pollution Control” Proc. NATO-ASI, Vol. 34, Plenum Press, New York (1993)
“Non-thermal plasmas have an enormous potential of becoming the leading technology for the remediation of environmental pollutants in the near future”
20 Years Later: Much of the “enormous potential” remains unrealized - why ???
What are the challenges, where are the opportunities ???
TO DATE: Only two fully commercialized large-scale plasma-based technologies in
the environmental field: Electrostatic Precipitators & Ozonizers
Not covered: • Plasma Medicine (too early, regulated)
• Plasma Light Sources (quite mature)
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
I. Electrostatic Precipitators (using corona discharge plasmas): Removal of particulates from gas streams
• mature technology • large industrial scale • economical & efficient • reliable • little unknown science • some engineering issues
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Electrostatic Precipitators (using corona discharge plasmas)
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Technology improvements
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
II. Ozonizers (using dielectric barrier discharge, DBD, plasmas): Generation of ozone (O3) for disinfection applications
• mature technology • large industrial scale • fairly economical • fairly reliable • not efficient (< 20% O3) • some unknown science • engineering issues
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Filamentary DBD and O3 Generation (complex interplay between plasma chemistry & discharge physics)
• low power, many weak filaments • low O3 generation efficiency at low O3 background concentrations • high O3 generation efficiency at high O3 background concentration
• high power, few strong filaments • low O3 generation efficiency at high O3 background concentrations • high O3 generation efficiency at low O3 background concentration
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Ozone Generation in DBDs
State of the Art: • Larger ozonizers can produce up to 100 kg of O3 per hour • O3 concentrations are typically 18 wt% in O2 and 6 wt% in air • Use of O2 requires <50 ppm HC contamination • Energy for 1 kg of O3 is 8 kWh for O2 and up to 20 kWh for air • Cost is about $2 per kg of O3
Future Prospects: • Novel concepts (e.g. the IGS) can push max. O3 concentration to >20% • Advances in power semiconductors (improved gate turn-off thyristors and insulated gate bipolar transistors which can switch 1 kA at 5 kV) will reduce size of ozonizers by eliminating the need for step-up transformers and allow use of more efficient excitation waveforms • Use of homogeneous self-sustained volume discharges may lead to more favorable plasma conditions for O3 generation
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Technology improvements
Ozonizers (using dielectric barrier discharge, DBD, plasmas):
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Application of Low-T Plasmas in ‘High Potential’ Area: Removal of VOCs, SOx, and NOx from Gaseous Streams
Low-T plasmas have been used in bench-scale applications to: • convert VOCs in gaseous waste streams • convert SOx and NOx in gaseous waste streams • use in high-flow and low-volume applications • convert contaminants in Diesel exhaust • prepare feed gas for fuel cell
Possible show-stoppers preventing industrial-scale applications : • by-product formation (characterization, control) • carbon closure (accounting for fate of all C atoms) • competing technologies (advanced oxidation techniques, catalysts, …) • energy efficiency • economics (cost of manufacture, cost of operation, …)
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Capillary Plasma Electrode (CPE) Concept
dielectric (pulsed ) dc, ac, or rf voltage
metal
metal dielectric
Capillary Plasma Electrode (CPE) Realizations
Cylindrical Electrodes
(Longitudinal Flow)
Solid Pin Electrodes
(Cross Flow) Hollow Pin Electrodes
(Flow-Through)
Some Low-T Plasma Concepts
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
`
AC
PC LabView
Oscilloscope
Plasma Reactor
Plasma Treatment System
FT-IR
FID
[ VOCs, NOx, COx, and O3 ]
[VOCs]
Chemicals Analysis System
Exha
ust
Carbon Trap
Mass Spectrometer
GC
Mass Spectrometer
GCCS2
Solvent Extraction
[VOCs]
/UV/Vis
(a) Off-line Analysis
(b) On-line Analysis
Gas Preparation
VOCs in dry air 50 – 1500 ppm(v)
Plasma Reactor
I-V, Power Measurement
influent effluent
Off-Line Analysis Carbon Trap
Solvent Extraction GC-MS
On-Line Analysis FTIR Absorption
GC-FID GC-MS (gas phase)
F
Flowmeter 1
F
Flowmeter 2
Impinger
VOCs Vapor
Dilution Gas
Mixtures
Com
pre
ssed A
ir
Seeded Gas Preparation System
Experimental Setup
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
0
160
320
480
640
800
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 Specific Energy, J/cm3
Efflu
ent C
once
ntra
tion,
ppm
0
20
40
60
80
100
Rem
oval
Effi
cien
cy, %
Removal of n-Heptane in an Annular Plasma Reactor
(residence time: 0.6 s; initial
concentration: 700 ppm)
0
100
200
300
400
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 Specific Energy, J/cm3
Efflu
ent C
once
ntra
tion,
ppm
0
20
40
60
80
100
Rem
oval
Effi
cien
cy, %
Removal of Toluene in an Annular Plasma Reactor
(residence time: 0.6 s; initial
concentration: 490 ppm)
Two Examples
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
0 2 4 6 8 100
10
20
30
40
50
60
70
80
90
100
Destr
uctio
n Effi
cienc
y (%)
Energy Density (J/cm3)
Initial contaminant concentration: 200 - 1200 ppm(v) flow rate: 2 - 8 l/min residence for maximum destruction efficiency
Benzene Destruction
A-CPE Reactor
CF-CPE Reactor
In many cases conditions can be found that will achieve essentially 100% destruction. In some cases, however, NOT (toluene !); back-reactions will limit the maximum achievable destruction efficiency.
We also developed a simple kinetic model for the species destruction and simulated the chemical conversion and did some by-product characterization.
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Low-T plasmas for Environmental Applications: • High Percentage of VOC Destruction in Low-Flow Applications • Reasonable Destruction Efficiency in High-Flow Applications • Extensive Characterization of By-Products • High Level of Carbon Closure But: Challenges Remain
Scale-up to high gas flow is non-trivial Cost and energy efficiency (vs. competing technologies) Materials for long-term, maintenance-free operation Control of by-product formation Poorly understood plasma chemistry Coupling of discharge physics to plasma chemistry
SUMMARY: Low-T plasmas can be used effectively for the treatment of gaseous waste streams containing VOCs in a bench-scale R&D environment
Large-scale industrial utilization is still elusive; the technology readiness level is “stuck” at the “proof-of-concept” stage !
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Removal of VOCs, SOx, and NOx from Gaseous Streams
Stuck !
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Solid Oxide Fuel Cell Chemistry
Low-T Plasmas for Fuel Cell Systems
300 kW Fuel Cell
2 m
Idea: Use low-T plasma to generate hydrocarbon feed gas for cell
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Clean Fuel Cell Feed
Diesel Vaporization
Plasma Reactor Diesel CH4,H2, HCs
R-S + H2 H2S + R
ZnO Cartridge ZnO + H2S ZnS + H2O
Water/Steam
Conventional SOFC Process
Diesel Sulfur Removal
Pre- Reforming
Carbonate DFC/SOFC
Heat/Water Recovery
Steam Generation air steam
Exhaust
Power Conditioning
AC Power Two Catalytic Reactors
Low-T Plasma Alternative
H2
Research and Technology Initiatives
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Various DBDs
High Voltage (~10-15 KHz)
Ground Wires
Dielectric
Plasma
Gas in Gas out 10”
2. Parallel-Plate DBD (PP-DBD)
Top electrode removed
1. Surface DBDs (S-DBDs) using Microrods
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
(1) Low & High Sulfur Fuel @ Steam/Fuel = 3
16 14 Higher Hydrocarbons 2/0 1/0 Ethane/Propane 2 5 Acetylene
29 30 Ethene 23 23 Hydrogen 28 27 % (v/v) Methane
High Sulfur Low Sulfur
(2) Effect of Steam/Fuel Ratio for NATO 76 Diesel
14 1/0 5
30 23 27
MEDIUM (3:1)
16 19 Higher Hydrocarbons 1/0 2/1 Ethene/Propane 4 4 Acetylene
33 28 Ethene 21 21 Hydrogen 25 25 % (v/v) Methane
HIGH (8:1) LOW (2:1)
Work was discontinued; technology verification / proof-of-concept stage unsatisfactory + customer validation showed significant market resistance
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Abandoned !
Low-T Plasmas for Fuel Cell Systems
Excimer Emission in Pure Rare Gases
The 2nd Excimer Continua are the Characteristic Emissions: Xe: 170-172 nm; Kr: 144-147 nm; Ar: 126-131 nm – all 3 are fairly narrow Ne: 76-88 nm; He: 60-90 nm – both broader and below LiF cut-off
Rare Gas Excimer Spectra are continua, the so-called 1st & 2nd Continua
Ne (400 Torr)
0
50
100
150
Wavelength (nm) 70 75 80 85 90 95
Dielectric, 250 µm
Mo Electrodes, 100 µm
-Vo, DC or pulsed
RBallast, 50 kΩ
Rcurrent viewing, 1 kΩ
Hollow Cathode, 150µm
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Excimer Formation in Pure Rare Gases (a combination of electron-driven and 3-body processes)
1. Ionization Route (R = He, Ne, Ar, Kr, Xe) e- + R R+ + 2 e- (electron-driven) R+ + 2 R → R2
+ + R (3-body) R2
+ + e- R* + R (electron-driven) R* + 2 R R2
* + R (3-body) hν (excimer) + 3 R 2. Excitation Route e- + R R* + e- (electron-driven) R* + 2 R R2
* + R (3-body) hν (excimer) + 3 R What is needed: • Minimum Electron Energies of 20 – 24 eV in He, 10 – 12 eV in Xe • High Gas Density to Promote 3-Body Collisions
Kurt H. Becker, PhD Vice Dean for Academic Affairs
A High-Pressure Plasma is an Ideal Environment for Excimer Formation
Summer School on Complex Plasmas Seton Hall University, 2014
Ne2* Excimer Emission from a MHCD
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Pure Ne (400 Torr)
0
50
100
150
Wavelength (nm) 70 75 80 85 90 95
Gas purity is critical !
0
2
4
6
8
10
Wavelength (nm)70 9080
Ne + trace of H2
Trace contamination by H2 causes the excimer continua to “disappear”
Summer School on Complex Plasmas Seton Hall University, 2014
Emissions from a MHCD in a Ne-H2 (0.02%) Mixture
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Rel
ativ
e In
tens
ity
Wavelength (nm) 100 150 200 250
0
200
400
600
H Lyman -α
0
2000
4000
Wavelength (nm)120100 110908070
H Lyman-α
H Lyman-β Ne2* Excimer
Emission Spectrum is dominated by H emissions, in particular by H Lyman-α
Origin of Lyman-α: (Near-Resonant) Energy Transfer from Ne2
* to H2
Ne2* + H2 → 2 Ne + H(1s) + H*(2p)
H*(2p) → H(1s) + hν (121.6 nm, Lyman-α)
Energetics: H2→ H + H E ≥ 4.48 eV H(1s) → H*(2p) E = 10.20 eV Total: E ≥ 14.68 eV
(hν) of the Ne2* 2nd Continuum:
16.3 eV (76 nm) – 14.1 eV (88 nm) most Ne2* photons have enough energy to
produce H Lyman-α via the above process
Summer School on Complex Plasmas Seton Hall University, 2014
Attempt to develop a commercializable product
Kurt H. Becker, PhD Vice Dean for Academic Affairs
We built and tested (and patented) a prototype of a compact near-monochromatic H Lyman-α light source (for VUV photolithography applications)
Patterns Printed with 121-nm Source with Near Field Phase Shifter Mask
(97 nm Feature Size)
•Resist: HSQ, ≈25 nm thick
Courtesy of MIT Lincoln Lab
BUT: When our light source was ready, the industry had moved to shorter wavelengths (35 nm); there was no further commercial interest in a 121 nm source.
We had fun with the science and really got to understand the AMO physics behind it; many nice papers (incl. N2, O2, etc. contaminants)
Summer School on Complex Plasmas Seton Hall University, 2014
but no success with the commercialization, product failed at the “customer validation” stage, no way to “recover” !
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Failed
Plasma VUV Lightsource for Photolithography
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
H2 Generation for Small Fuel Cells for Portable Devices
from H. Qiu et al, Int. J. Mass Spectrom. 233, 37 (2004)
0 20 40 60 80 100 120 1400
10
20
30
40
50
60Plasma offPlasma on
N2
H2
NH3
Parti
al Pr
essu
re (T
orr)
Time (min)
Pass a hydro-fuel (NH3, CH4, etc.) through a microplasma reactor and generate H2 for use in small-scale fuel cells to power portable devices.
A few other examples of “promising” plasma technologies
Technology realization failed - abandoned !
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Failed
H2 Generation for small fuel cells for portable devices
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Failed
H2 Generation for small fuel cells for portable devices
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Plasma Treatment of Diesel Exhaust
ENGINE
AIR FUEL
EXHAUST
PLASMA REACTOR
Pass the exhaust emission stream from a Diesel engine through a plasma reactor to convert hydrocarbon, NOx, etc. – as an alternative to a catalytic reactor
Hydrocarbon Reduction in Diesel Exhaust
0
20
40
60
80
100
120
0 50 100 150 200
Engine power (hp)
Exha
ust T
OC
s (p
pmv)
Plasma OFF
Plasma ON
67% Reduction
Technology realization failed - abandoned !
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Potable water harvesting from Diesel exhaust
ENGINE
AIR FUEL
CONDENSER
WATER POLISHING
STORAGE
EXHAUST
PLASMA REACTOR
Engine Power (hp)
Hydrocarbon Reduction in Harvested Water
0
200
400
600
800
1000
0 20 40 60 80 100 120 140 160 180
Wat
er T
OC
s (p
pmc)
Plasma OFF
Plasma ON
51% Reduction
Pass a fraction of the Diesel exhaust stream through a plasma reactor to convert hydrocarbons to water and reduce residual contamination.
Technology realization failed - abandoned !
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Failed
Plasma treatment of Diesel exhaust / potable water harvesting
US Patent 5,872,426 ; E. Kunhardt & K. Becker, February 16, 1999 “Glow plasma discharge device with electrode covered with perforated dielectric” Abstract A method and apparatus for stabilizing glow plasma discharges by suppressing the transition from glow-to-arc includes a perforated dielectric plate having an upper surface and a lower surface and a plurality of holes extending therethrough. The perforated dielectric plate is positioned over the cathode. Each of the holes acts as a separate active current limiting micro-channel that prevents the overall current density from increasing above the threshold for the glow-to-arc transition. This allows for a stable glow discharge to be maintained for a wide range of operating pressures (up to atmospheric pressures) and in a wide range of electric fields include DC and RF fields of varying strength. Inventors: Kunhardt; Erich E. (Hoboken, NJ), Becker; Kurt H. (New York, NY) Assignee: Stevens Institute of Technology (Hoboken, NJ) Appl. No.: 08/820,013 ; Filed: March 18, 1997 + 6 follow-on patents + application patents filed through start-ups
Kurt H. Becker, PhD Vice Dean for Academic Affairs
The “PlasmaSol Story”
Summer School on Complex Plasmas Seton Hall University, 2014
The “PlasmaSol Story” The Plunge: In 1999, four graduate students from Stevens co-founded PlasmaSol to commercialize the non-thermal plasma technology: Kurt Kovach, Seth A. Tropper, Richard Crowe, and Jack Levitt + several faculty inventors. Frank Shinneman joined the company several years later as CEO.
The Approach:
• Leverage government R&D contracts toward commercialization • Collaboration / strategic partnerships
The Business Model: Stevens Institute of Technology, the owner of the IP, provided a royalty-free, exclusive, and restricted (to environmental applications and medical sterilization) license to PlasmaSol in exchange for a dilutable equity position in the company and adequate representation on the company’s Board.
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
The “PlasmaSol Story” PlasmaSol
Develops Products & Hires Employees
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
The “PlasmaSol Story” PlasmaSol, the early years: 1999 – 2003 • Chasing SBIRs and contracts • Hovering from grant to grant to make pay roll • No clear business strategy • Just staying afloat
PlasmaSol, the “focus” years: 2003 – 2005 • The hiring of a “business type” as CEO, Frank Shinneman • A focused business strategy, “exit” in 3 years • Only SBIRs aligned with business strategy • Identify strategic partner for joint venture • Stay focused, stay focused, stay focused, …
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
The “PlasmaSol Story” Stryker-PlasmaSol: From Joint Development to Acquisition
December 2004: – Joint Development (JD) program with Stryker division
February 2005 – Stryker Instruments starts funding JD program
March – August 2005 – Monthly research updates – Stryker feels out PlasmaSol about a possible acquisition
Fall 2005 – Due Diligence – Board members Visit – Division management “sells” idea to Corporate
December 28, 2005: The Deal is Done!
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
The “PlasmaSol Story”
Time of Sale: • Stage: Development, Pre-Revenue • Technology: Sterilization
– Medical Instrument Sterilization – Air Sterilization
• Employees: 8 • Funding: > $1.5M/yr., Gov’t and other Contracts • IP: 4 US Patents granted +
14 US Applications
Factsheet: • 6 years from Concept to Commercialization to Exit • $2.5M equity financing + $7M R&D funding (via gov’t, etc.) • $20M sale of company + patents (to Stryker Instruments)
Then there was Plasmion - a victim of the “valley of death”
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Science breakthrough Engineering realization Bench-scale prototype Technology realization Technology verification, proof-of concept Customer validation Scale-up, economics Large-scale industrial testing Commercialization, industry acceptance
The PlasmaSol Start-up Story
Start-up and IP acquired
Purchaser assumes all further risks !!!
Here: Stryker spent another year on further technology refinement, then shelved the technology, because of corporate restructuring !
Kurt H. Becker, PhD Vice Dean for Academic Affairs
The Landscape of Technology Transfer ST
C
SBIR
I/UC
RC
ERC
GO
ALII I-Corps/POCCs
STTR
AIR
/PFI
Ditch of Death
University
Small Business
Industry
Investors
Foundations Valley of Death
Discovery Development Commercialization
Res
ourc
es In
vest
ed
NSF overall
Company Formation
e.g. NSF Programs
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Proton Transfer Reaction Mass Spectrometry (PTR-MS) PTR-MS (Proton Transfer Reaction – Mass Spectrometry) enables the real-time measurement of volatile organic compounds, VOCs.
Lab in 1998 Ionicon 2010
Originally developed by scientists at the Institut für Ionenphysik at the University of Innsbruck, Austria, this technology has been commercialized by IONICON Analytik.
1. Standard approach: Collection of samples into vessels (or traps) followed by extraction and separation by a GC column plus detector (e.g. ms) proper use of standards and careful calibration yields very reliable results and allow identification and quantification, but not in real-time !!
2. Alternative: Direct inlet mass spectrometry (DIMS) No sample collection into bags necessary, thus real time analysis however, quantification and identification are a challenge + need to ionize reactant in the sample gas fragmentation
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
0
5
10
15
20
25
30
35
40
Methanol Ethanol Acetaldehyd
0
5
10
15
20
25
30
35
Häu
figke
it
Methanol Ethanol Acetaldehyd
15 20 25 30 35 40 45 500
5
10
15
20
25
30
35
Masse [amu]
Methanol Ethanol Acetaldehyd
Fragmentation via DI:
Electron impact @ 70 eV Charge transfer with Xe+, IE(Xe) > IE(R) Soft and efficient ionization, e.g. PTR-MS PA(H3O) < PA(R)
R + e → R+ + fragment ions
Xe+ + R → R+ + Xe
H3O+ + R → RH+ + H2O
Mass (amu)
Rel
. Abu
ndan
ce
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
PTR-MS resulted from ion-molecule reaction studies with various techniques in the 1970s and 1980s, in particular
“selected ion flow drift tube, SIFDT” studies
-------------------- A+ → [R] → R+ -------------------- Determination of reaction rate k from: t, R+/A+, [R]
A novel idea proposed in1985: Reversed SIFDT Determination of [R] from k, t, R+
Next step in 1994: Hollow Cathode Discharge + Drift Tube
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
The technology – ion source principle Hollow cathode discharge: • Water vapor from distilled water reservoir • H3O+ with >99% purity, no mass filter necessary • High primary current, separated from drift tube
e- + H2O H2O+ + 2e- H2
+ + ... H+ + ... O+ + ... H2
+ + H2O H2O + + H2 H+ + H2O H2O + + H
O++ H2O H2O + + O H2O+ + H2O H2O∙H+ + OH
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
exothermic collisions
H2O∙H+ + C3H6 → C3H6∙H+ + H2O + C6H6 → C6H6∙H+ + H2O + CH3OH → CH3OH∙H+ + H2O + CH3CN → CH3CN∙H+ + H2O + hydrocarbon derivatives →
• Sample gas at 2.2 mbar collides with H3O+ ions • Proton (H+) switches to (and ionizes) sample gas, if proton
affinity is higher than that of water (166.5 kcal/mole)
The technology – drift tube principle
No reaction with O2, CO2, CH4, N2, Ar etc. Reaction with VOCs having a higher proton affinity than H3O+
H3O+ + R → RH+ + H2O
endothermic collisions
+ N2 + O2 H2O∙H+ + Ar + CO2 + CH4
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
+ +
Water Air
How does PTR-MS work ?
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Disadvantages:
PTR-MS – advantages • Short response time: below 100 ms - instantaneous detection • Quantification • Sample gas is measured without preparation - on line • Ultra high sensitivity (< pptv range)
Next Step: Improve selectivity and sensitivity
• In addition to H3O+, use NO+ and O2+ as
reagent ions via HC ion source from ambient air (NO+) or oxygen gas reservoir (O2
+) • O2
+ react via non-dissociative and dissociative charge (electron) transfer
• NO+ react mainly via hydride anion transfer
• Identification is more difficult • Not all compounds are accessible
Also: use of TOF instead of a Quad improves the resolution significantly
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Urban air roadside Isobaric compound identification
biogenic compounds (terpene, sesqueterpene) show build up in late afternoon, broad maximum around midnight, minimum next morning exhaust related compounds (benzene, toluene) exhibit traffic related peaks, bimodal peak during morning and evening traffic Sharp spikes: wind gusts
43.0184: protonated ketene 43.0548: protonated propene 47.0133: formic acid 47.0497: ethanol
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Food Flavor Analysis:
Espresso
m/z 73 butanone; m/z 75 methylacetate; m/z 81 furfurylalcohol; m/z 83 methylfuran; m/z 87 methylbutanal & diacetyl
Nose space spectra while “tasting” vs “drinking” espresso. The ion mass at m/z 61 corresponds to acetaldehyde.
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Food Flavor Analysis: Espresso ≠ Espresso
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
The history of PTR-MS
1998: Founding of Ionicon as a spin-out company (“garage operation” of a few entrepreneurially-minded academics)
Instrument Sensitivity: 1998: 10 ppmv 2001: ppbv 2010: pptv 2014: a few 100 ppqv
2013: 250 instruments worldwide in operation (team of ~ 25; annual revenue about $8M in 2012/13)
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
PTR-TOF 1000: smallest, lightest & most affordable PTR-TOF
• Sensitivity: > 40 cps/ppbv (Benzene) • Resolution: > 1500 • Limit of Detection: < 10 pptv
Top of the Line: PTR-TOF 8000 (until now) • Detection limit: < 10 pptv • Sensitivity: > 120 cps/ppbv (Benzene) • Mass Resolution: > 5000 • Full mass range acquisition in a split-second • Linearity range: 6 orders of magnitude (10 pptv - 1 ppmv)
PTR-QiTOF: about to hit the market •Detection limit: < 1 pptv
• Sensitivity: up to 2500 cps/ppbv (Benzene) • Mass Resolution: up to 10,000)
Summer School on Complex Plasmas Seton Hall University, 2014
Kurt H. Becker, PhD Vice Dean for Academic Affairs
Summer School on Complex Plasmas
Seton Hall University, 2014
Science breakthrough
Engineering realization
Bench-scale prototype
Technology realization
Technology verification, proof-of concept
Customer validation
Scale-up, economics
Large-scale industrial testing
Commercialization, industry acceptance
Ionicon Analytik: From breakthrough to full commercialization
Technology improvements
~ 15 years
Kurt H. Becker, PhD Vice Dean for Academic Affairs
PTR-MS & Ionicon: Academic Entrepreneurship in Motion
STC
SBIR
I/UC
RC
ERC
GO
ALII I-Corps/POCCs
STTR
AIR
/PFI
Ditch of Death
University
Small Business
Industry
Investors
Foundations Valley of Death
Discovery Development Commercialization
Res
ourc
es In
vest
ed
NSF overall
Company Formation
e.g. NSF Programs
Ionicon