15 Lecture Short Course at Princeton University

Lecturer: Ronald K. Hanson

Woodard Professor, Dept. of Mechanical Engineering
Ph.D. Stanford, Aero/Astro; at Stanford since 1972
Underlying Science:
Molecular Spectroscopy
Diagnostic Methods:
Laser Absorption, LIF
Example Applications:
Engines, Shock Tubes, Kinetics
Today: Lecture 1
Overview
Introductory Material
Copyright ©2015 by Ronald K. Hanson
This material is not to be sold, reproduced or distributed without prior
written permission of the owner, Ronald K. Hanson.
 15 Lecture Short Course at Princeton University

Lecturer: Ronald K. Hanson

Woodard Professor, Dept. of Mechanical Engineering
Ph.D. Stanford, Aero/Astro; at Stanford since 1972
Underlying Science:
Molecular Spectroscopy
Diagnostic Methods:
Laser Absorption, LIF
Example Applications:
Engines, Shock Tubes, Kinetics
Today: Lecture 1
Overview
Introductory Material
Copyright ©2015 by Ronald K. Hanson
This material is not to be sold, reproduced or distributed without prior
written permission of the owner, Ronald K. Hanson.
 Lecture 1: Overview

Course Objectives and Content

• Introduction to fundamentals of molecular spectroscopy & photo-physics
• Introduction to laser absorption and laser-induced fluorescence in gases
• Introduction to shock tubes as a primary tool for studying combustion
chemistry, including recent advances and kinetics applications
• Example laser diagnostic applications including:
• multi-parameter sensing in different types of propulsion flows and engines
• species-specific sensing for shock tube kinetics studies
• PLIF imaging in high-speed flows

3
 Course Overview:
Spectroscopy and Lasers
Calculated IR absorption spectra of HBr
 What is Spectroscopy?
• Interaction of Radiation (Light) with
Matter (in our case, Gases)
• Examples: IR Absorption, Emission

 Why Lasers?
• Enables Important Diagnostic
Methods
• LIF, Raman, LII, PIV, CARS, …
• Our Emphasis: Absorption and LIF Typical emission spectra of high-temperature air
• Why: Sensitive and Quantitative! between 560-610nm.

Minimum Detectivity using Laser Absorption

1000 1000
CO2 1atm,15cm,1MHz
Minimum Detecitivity [ppm]
Minimum Detecitivity [ppm]

100 C2H4 NH2 100

H2O
10 10

CH3 OH
1
1
CH
0.1
0.1
CN
0.01 1atm,15cm,1MHz 0.01
1000 1500 2000 2500 3000
1000 1500 2000 2500 3000
Temperature [K]
Temperature [K]
44
 Course Overview:
Role of Lasers in Energy Sciences
 Example Applications: Coal gasifiers Swirl burners
Remote sensing, combustion and
gasdynamic diagnostics, process
control, energy systems and
environmental monitoring.

 Common Measurements:
Species concentrations, temperature
(T), pressure (P), density (ρ),
velocity (u), mass flux (ρu).

OH PLIF in spray flame Coal-fired power plants Incinerators

5
 Course Overview:
Roles of Laser Sensing for Propulsion

Characterize test facilities

PLIF imaging of H2 jet
in model SCRAMJET
@Stanford
Optical Validate
simulations and
Diagnostics
models

Understand
TDL Sensing in complex reactive
SCRAMJET @ WPAFB environments

TDL Sensing in IC-Engines

@ Nissan & Sandia

TDL Sensing in 248 nm

Pratt & Whitney PDE Signal
beam
@ China Lake, CA PLIF in plume of Titan IV @ Aerojet

Applicable to large-scale systems as well as laboratory science 6

 7
Course Overview:
Role of Lasers in Combustion Kinetics: Shock Tubes

Transmitted Beam
Detector

Pressure
Diaphragm PZT

Driver Shock Tube

Section Driven Section
UV/Vis/IR
Incident Beam Emission
Detector Detectors

Ti:Sapphire Laser
(Deep UV) Diode Lasers
(Near IR & Mid-IR)
Ring Dye Lasers
(UV & Vis)
He-Ne Laser
CO2 Lasers (3.39 mm)
(9.8-10.8 mm)
 8
Course Overview:
Role of Lasers in Combustion Kinetics: Shock Tubes

Transmitted Beam
Detector

Incident Pressure
Shock Wave PZT

P2 P1
T2 VS T1
UV/Vis/IR
Incident Beam Emission
Detector Detectors

Ti:Sapphire Laser
(Deep UV) Diode Lasers
(Near IR & Mid-IR)
Ring Dye Lasers
(UV & Vis)
He-Ne Laser
CO2 Lasers (3.39 mm)
(9.8-10.8 mm)
 9
Course Overview:
Role of Lasers in Combustion Kinetics: Shock Tubes

Advantages of Shock Tubes

• Near-Ideal Test Platform Transmitted Beam
• Well-Determined Initial T & P Detector

• Clear Optical Access for Laser Diagnostics Reflected

Shock Wave Pressure
PZT

P2 P5
T2 VRS T5
UV/Vis/IR
Incident Beam Emission
Detector Detectors
Applications of Shock Tubes
• Ignition Delay Times
• Elementary Reactions
• Species Time-Histories Ti:Sapphire Laser
(Deep UV) Diode Lasers
Species Accessible by Laser Absorption (Near IR & Mid-IR)
Ring Dye Lasers
• Radicals: OH, CH3 … (UV & Vis)
He-Ne Laser
• Intermediates: CH4, C2H4, CH2O … CO2 Lasers (3.39 mm)

• Products: CO, CO2, H2O … (9.8-10.8 mm)

 Course Overview:
Lasers and Shock Tube: Time-Histories & Kinetics
Time-Histories Rate Constant

1494K, 2.15 atm

300ppm heptane, f=1 H+O2 = OH+O
JetSurF 2.0

 Multi-wavelength laser  Laser absorption provides

absorption species time- high-accuracy measurements of
histories provide quantitative elementary reaction rate
targets for model refinement constants
and validation
10
 Useful Texts, Supplementary Reading
 G. Herzberg, Atomic spectra and atomic structure, 1944.
 G. Herzberg, Spectra of diatomic molecules, 1950.
 G. Herzberg, Molecular spectra and molecular structure, volume II,
Infrared and Raman Spectra of Polyatomic Molecules, 1945.
 G. Herzberg, Molecular spectra and molecular structure, volume III,
Electronic spectra and electronic structure of polyatomic molecules, 1966.
 C.N. Banwell and E.M. McCash, Fundamentals of molecular spectroscopy, 1994.
 S.S. Penner, Quantitative molecular spectroscopy and gas emissivities, 1959.
 A.C.G. Mitchell and M.W.Zemansky, Resonance radiation and excited atoms, 1971.
 C.H. Townes and A.L. Schawlow, Microwave spectroscopy, 1975.
 M. Diem, Introduction to modern vibrational spectroscopy, 1993.

 W.G. Vincenti and C.H. Kruger, Physical gas dynamics, 1965.

 A.G. Gaydon and I.R. Hurle, The shock tube in high-temperature chemical physics, 1963.

 J.B. Jeffries and K. Kohse-Hoinghaus, Applied combustion diagnostics, 2002.

 A.C. Eckbreth, Laser diagnostics for combustion temperature and species, 1988.
 W. Demtroder, Laser spectroscopy: basic concepts and instrumentation, 1996.
 R.W. Waynant and M.N. Ediger, Electro-optics handbook, 2000.
 J.T. Luxon and D.E.Parker, Industrial lasers and their applications, 1992.
 J.Hecht, Understanding lasers: An entry level guide, 1994.
 K.J.Kuhn, Laser engineering, 1998.
 R. K. Hanson et al., Spectroscopy and Laser Diagnostics for Gases, 2016

11
 Lecture Schedule
Monday
1. Overview & Introduction
Thursday
Course Organization, Role of Quantum Mechanics, 10. TDLAS Applications in Energy Conversion
Planck's Law, Beer's Law, Boltzmann distribution Tunable Diode Laser Applications in IC Engines
2. Diatomic Molecular Spectra Coal-Fired Combustion
Rotational Spectra (Microwaves) 11. Shock Tube Techniques
Vibration-Rotation (Rovibrational) Spectra (Infrared) What is a Shock Tube?
3. Diatomic Molecular Spectra Recent Advances, ignition Delay Times
Electronic (Rovibronic) Spectra (UV, Visible) 12. Shock Tube Applications
Multi-Species Time Histories
Tuesday Elementary Reactions
4. Polyatomic Molecular Spectra
Rotational Spectra (Microwaves)
Friday
Vibrational Bands, Rovibrational Spectra 13. Laser-Induced Fluorescence (LIF)
5. Quantitative Emission/ Absorption Two-Level Model
Spectral absorptivity, Eqn. of Radiative Transfer More Complex Models
Einstein Coefficients/Theory, Line Strength 14. Laser-Induced Fluorescence: Applications 1
6. Spectral Lineshapes Diagnostic Applications (T, V, Species)
Doppler, Natural, Collisional and Stark broadening, PLIF for small molecules
Voigt profiles 15. Laser-Induced Fluorescence: Applications 2
Diagnostic Applications & PLIF for large molecules
Wednesday The Future

7. Electronic Spectra of Diatomics

Term Symbols, Molecular Models: Rigid Rotor,
Symmetric Top, Hund's Cases, Quantitative Absorption
8. Case Studies of Molecular Spectra
Ultraviolet: OH
9. TDLAS, Lasers and Fibers
Fundamentals and Applications in Aeropropulsion

12
 Lecture 1: Introductory Material

1. Role of Quantum Mechanics

- Planck’s Law
2. Absorption and Emission
3. Boltzmann Distribution
4. Working Examples

13
 1. Role of QM - Planck’s Law
 Quantum Mechanics:
Quantized Energy levels We will simply accept these


 “Allowed” transitions
} rules from QM.
How are energy levels specified?
Quantum numbers for electronic,
vibrational and rotational states.

Eint = Eelec + Evib + Erot

Erot
Evib
ΔE

Eelec

14
 1. Role of QM - Planck’s Law
 Quantum Mechanics
Energy Energy state or level

Quantized Energy States

(discrete energy levels) ΔE Absorption “Allowed”
Emission transitions

Discrete spectra
Planck’s Law:
 Small species, (e.g., NO, CO, CO2, ΔE = Eupper (E’) – Elower (E”)
and H2O), have discrete = hn
rovibrational transitions = hc/λ
= hcn Energy in wavenumbers
 Large molecules (e.g., HCs) have
blended features Frequency [s-1]
c=λn

Note interchangability of λ & n ~ 3 x 1010 cm/s Wavelength [cm]

15
 2. Absorption and Emission
 Types of spectra:
 Absorption; Emission; Fluorescence; Scattering (Rayleigh, Raman)

 Absorption: Governed by Beer’s Law

Wavelength
Gas

Transmission
L
It
I0, ν
T, P, χi,v

Absorbance

 It 
Beer-Lambert Law    T  exp     exp  n jL   exp  SP iL 
 I 0 

Number density of species j in Cross section for Path length [cm]

absorbing state [molecule/cm3] absorption [cm2/molecule]
16
 2. Absorption and Emission
 Components of spectra: Lines, Bands, System.

Eint = Eelec + Evib + Erot Potential energy curve for 1 electronic state

E
(pot.)

r (distance between nuclei) 17

 2. Absorption and Emission
 Components of spectra: Lines, Bands, System.

Eint = Eelec + Evib + Erot

Line: Single transition
λ
Tλ

Erot

E
(pot.)

r (distance between nuclei) 18

 2. Absorption and Emission
 Components of spectra: Lines, Bands, System.

Eint = Eelec + Evib + Erot

Line: Single transition
λ
Tλ

Band: Group of lines with common

vupper upper + lower vibrational levels
Evib

Two branches,
vlower
R P e.g. P&R

Δv=vupper – vlower=1 is strongest

for rovibrational IR spectra,
but Δv= 2,3, … allowed
19
 2. Absorption and Emission
 Components of spectra: Lines, Bands, System.

Eint = Eelec + Evib + Erot

Line: Single transition
λ
Tλ

Band: Group of lines with common

upper + lower vibrational levels
Evib

vlower Δv=1

But Δv>1 possible Δv=3 Δv=2 Δv=1

20
 2. Absorption and Emission
 Components of spectra: Lines, Bands, System.
Eint = Eelec + Evib + Erot System:
 Transitions between different
C3Πu electronic states
 Comprised of multiple bands between
N2(2+)
two electronic states
 Different combinations of vupper and
B3Πg vlower such that “bands” with
Eelec vupper-vlower=const. appear

Example: N2
N2(1+) A3Σ+ u  First positive SYSTEM:
B3Πg→A3Σ+u

Nitrogen
21
 2. Absorption and Emission
 Components of spectra: Lines, Bands, System.
Eint = Eelec + Evib + Erot System

C3Πu Example: High-temperature air emission

spectra (560-610nm)
N2(2+)

B3Πg 11→7 10→6 vupper=v'

v'-v"=4
vlower=v"
Eelec
12→8 9→5

8→4
7→3
6→2
N2(1+) A3Σ+u

Nitrogen
22
 2. Absorption and Emission
 Components of spectra: Lines, Bands, System.

System
Example: Typical emission spectra of DC discharges

UV Visible-NIR

23
 2. Absorption and Emission
 Components of spectra: Lines, Bands, System.

OH 2Σ−2Π (0,0)

CH 2Δ−2Π

CH 2Σ−2Π

CH 2Σ−2Π

NH 3Π−3Σ

 In early days, spectra were recorded on film!

But now we have lasers.
24
 2. Absorption and Emission
 How is Tλ (fractional transmission) measured?

Tunable Laser Test media; Flame Iλ; Detector

 Do lines have finite width/shape? Yes!
Transmission (Tλ)
1.0
Δλ = Full width at half maximum
Δλ = f(P,T)
Absorption

A resolved line
λ
has shape!
λ0 = Line center

And shape is a f(T,P)  an opportunity for diagnostics!

25
 2. Absorption and Emission

 3 key elements of spectra

 Line positions
Covered in
 Line strengths
course
 Line shapes

26
 3. Boltzmann Distribution
 How strong is a transition? Proportional to particle population
in initial energy level n1
Energy level 2
Boltzmann fraction of absorber species i in level 1

  
g i exp   i  - Equilibrium distribution of
ΔE=hn S12 n
Fi  i   kT  molecules of a single species
n Q over its allowed quantum states.
defines T
n1  i 
Energy level 1 Partition function Q   gi exp     QrotQvibQelec
i  kT 

Hence measurement of two densities, ni and nj  T

since ni/nj = gi/gj exp(-(i-j)/kT)
27
 4. Working Example – 1
 TDL sensing for aero-propulsion
 Diode laser absorption sensors offer prospects for time-resolved, multi-
parameter, multi-location sensing for performance testing, model validation,
feedback control

Inlet and Isolator Exhaust

Combustor Acquisition and Feedback
(velocity, mass flux, species, (T, species, UHC,
(T, species, stability) to Actuators
shocktrain location) velocity, thrust)

Fiber Optics
Diode Lasers
l1 l2 l3 l4 l5 l6
 Sensors developed for T, V, H2O, CO2, O2, & other species
 Prototypes tested and validated at Stanford
 Several applications successful in ground test facilities
 Now being utilized in flight
28
 4. Working Example – 2
 TDL Sensing to Characterize NASA Ames ArcJet Facilities
High-Enthalpy Flow for Materials and Vehicle Testing

High velocity
low pressure
High pressure gas Arc heater Nozzle flow for
hypersonic
vehicle testing

10ft

30ft
10ft
29
 4. Working Example – 2
 TDL Sensing to Characterize NASA Ames ArcJet Facilities
High-Enthalpy Flow for Materials and Vehicle Testing
High velocity
low pressure
High pressure gas Arc heater Nozzle flow for
hypersonic
vehicle testing
Anode Constrictor Tube Cathode

Inlet Air
Test cabin
Cooling Argon Cooling water TDL Sensor

 Goals: (1) Time-resolved temperature sensing in the arc heater: O to infer T

(2) Investigate spatial uniformity within heater (multi-path absorption)
Challenges: Extreme Conditions T=6000-8000K, P= 2-9 bar, I~2000A, 20 & 60 MW
Difficult access (mechanical, optical, and electrical) 30
 4. Working Example – 2
 Temperature from Atomic O Absorption Measurement
Atomic oxygen energy diagram Atomic oxygen absorption
measured in the arc heater

Residuals
Residuals
3P 0.05
2 5P
3P 3 0.00
1 5P
3P 2 -0.05
0 5P 0.6 Tpopulation= 7130±120 K
1
844.6 nm
777.2 nm nO*= 6.64 x 1010 cm-3

Absorbance
Absorbance
0.4
3S0
1 5S0 Data
2
0.2 Fitting
130.5 nm
135.8 nm 0.0
3P
0,1,2
777.12 777.16 777.20 777.24 777.28
Wavelength (nm)

 Fundamental absorption transitions from O are VUV but excited O in NIR

 Equilibrium population of O-atom in 5S02 extremely temperature sensitive
31
 4. Working Example – 2
 Arc current at 2000A, power 20MW
 Last 200 seconds of run arc current decreased 100A
 Measured temperature captures change in arc conditions

Precise temperature measurements

• 18K or 0.3% standard deviation
• 200ms time resolution

T 18 K
Arc current
decreased ~100A

TDL sensor provides new tool for routine monitoring of arcjet performance
32
 4. Working Example – 3
Time-Resolved High-P Sensing in PDC at NPS
Fiber-Coupled Light to Engine
Pitch Optics CO2 OR CO
2678 nm 4855 nm

H2O & T Assumption:

Nozzle
Exit
1469 nm Choked flow T
Nozzle 1392 nm gives velocity
Entrance
Port for Kistler
Flow Pressure Sensor
Detector for CO2
T, P, V & Xi
from Engine
Catch Optics
Wavelength yields
Detector for H2O
Transmitted Light Caught onto Wavelengths Enthalpy Flux
Multi-Mode Fibers

 Pulse-detonation combustor gives time-variable P/T

 Time-resolved measurements monitor performance & test CFD
33
 4. Working Example – 3
Time-Resolved High-P Sensing in PDC at NPS

Pulse Detonation Combustor

At Naval Post-graduate School in Monterey, CA

Optical sensors feasible in

harsh, high pressure engine environment 34
 4. Working Example – 3
Time-Resolved High-P Sensing in PDC at NPS

Pulsed Exhaust to
detonations throat
ambient
chamber

Assumption: Choked flow

T gives velocity
1392 nm 1469 nm
Throat Sensors T, P, V & Xi Enthalpy Flux
T & XH2O
([email protected]; [email protected])

 Pulse-detonation combustor gives time-variable P/T

 Time-resolved measurements monitor performance & test CFD

35
 4. Working Example – 3
Time-Resolved High-P Sensing in PDC at NPS

T- Data Collected in Nozzle Throat vs CFD

 T sensor performs well to >3500K, 30 atm!

 Data agrees well with CFD during primary blow down

36
 4. Working Example – 3
Time-Resolved TDL Yields Mass Flow

V  Vsonic  f (T ,  mix )

m  f (T , P,Vsonic )

 T and P give V and mass flow in choked throat as f(t)

.
 T, X, m and ideal gas can give enthalpy flow rate

37
 4. Working Example – 3
Time-Resolved TDL Yields Enthalpy Flow Rate

4 Consecutive Cycles

· ·
H = m Dhstag (T )
Tref = 298 K

 Time-resolved data provide key measures of engine performance

 Power
 Mass flow dynamics
 H integrated over complete cycle for ηth
38
 4. Working Example – 4
First Multi-Species Sensing for Shock Tube Kinetics

Lasers Oxygen Balance:

Methyl Formate Decomposition
Shock wave Test mixture

O=
Detectors 1420 K

_
H-C-O-C- 1.5 atm

_
 Chemistry progress monitored by
quantitative IR laser absorption

 Multi-species time histories provide

step-changing advantage for
mechanism validation

 Method accounts for nearly 100%

of O-atoms
Next: Diatomic Molecular Spectra
• Rotational and Vibrational Spectra

40