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How To Analyse A Jumbo Jet…..
And Other Analytical Challenges
Rob Wills
Product Specialist Molecular Spectroscopy
UK, Ireland, Nordics and IDO
How Can You Analyse a Jumbo Jet?
Why Move Measurements from Laboratory to Field?
Non-destructive analysis of large objects
Too big for lab
Too expensive to disassemble
Fast, actionable answers
Define sampling strategy based on current results
Decide which areas need more investigation.
Triage - Send more relevant samples back to lab.
Screen incoming materials before it enters the
production process
On-site determination for contamination or adulteration
Instrument Requirements for Field Use
Form Factor – Compact, rugged, portable, versatile
System needs to go where the sample is
Frequent travel subjects it to shock and vibration
Correct sampling interfaces
Little or no sample prep
Multiple uses and matrices
Easy to use and should provide answers
Easy to understand, meaningful results
Effective performance
Achieve required measurement limits
“Spectroscopic performance still matters”
February 2011: Agilent acquired A2 Technologies
1st Quarter Marketing
Agilent’s New POM and Entry FTIR Spectrometers
A2 Technologies developed and manufactured spectroscopy
products for use both inside and outside of the traditional
analytical lab.
• A2’s focus: providing small portable FTIR spectrometers
• Three categories based on how they are used:
I. Compact in-lab 5500 Series FTIR
II. Portable units
4500 Series FTIR
III. Handheld units 4100 ExoScan, 4200 FlexScan
How “Small” Are They?
Measurement Types
A2 instruments can make 2 types of measurements
Concentration by FTIR
Quantitative
Measure concentration
Oil Analysis, fuel analysis, etc.
Component method
0.24
Absorbance
•
IR spectral overlay of turbine oil 5-4300ppm
0.16
0.08
0.00
-0.08
3900
3700
3500
Wavenumber
3300
3100
Calibration allows prediction of the
concentration from the IR spectrum.
•
Qualitative Library Search
Chemical Identification by FTIR
Identify unknown sample
Quality control, product ID, etc.
Library Search method
Chemical can be identified by searching
commercial or user generated libraries.
Entry – In Lab Systems
5500 Dialpath
with triple
Transmission Cell
5500a
with ATR
5500t
with Transmission Cell
5500 Series FTIR Specifications
Wavenumber Range
4000 – 650 cm-1
Resolution
4 cm-1
Non-hydroscopic Optics
ZnSe beam splitter
Power
100 – 250 VAC 47 – 63 Hz,
Output: 15VDC
Operating Temperature
0⁰ to 50⁰ C
Humidity
95% non-condensing
Physical Attributes
•
•
•
•
•
•
3.6 kg
203 x 203 x 114 mm
External Computer
USB connection
External Power
Full spectral analysis
5500 Series FTIR Sampling Interfaces
5500a FTIR
ATR
5500a FTIR
• Simple, easy to use
• Short path length ~2 µm
– Library match, product identification
– Relatively high concentration quantization (%)
• Diamond crystal interface
–
–
–
–
Chemical and scratch resistant
Internal reflection
Only things contacting the diamond will be measured
Path length can be increased by multiple reflections at the sample
surface
• 1, 3 and 9 reflection available – Diamond
• 5 reflection – ZnSe
• 3, 5 & 9 reflection ATRs are LIQUIDS ONLY – No pressure device
5500 Series FTIR Sampling Interfaces
Single Transmission Cell
• Fixed path length liquid transmission cell
Standard 100µm
• Can be special ordered in 50µm or 200µm
• Liquids only
• Quantitative analysis
50 ppm to 5 %
• Reproducible and easy to use
5500t FTIR
5500 Series FTIR Sampling Interfaces
5500 DialPath FTIR
•Fixed path length liquid transmission cell
•Two Standard configurations
• Pathlengths of 50, 100, and 200 um
• Pathlengths of 30, 50, and 100 um
•Can be special ordered @ 30µm or 250µm
•Liquids only
•Quantitative analysis
•50 ppm to 5 %
•Reproducible and easy to use
4500 Series FTIR Specifications
Battery driven versions of the 5500
Designed for Field Use
•
4500a (with ATR)
•
4500t (Transmission Cell)
•
4500
(Dialpath)
Physical Attributes
• 6.8 kg
• 203 x 280 x 190mm
• Integrated PDA computer
• Optional PC
• Internal battery
• Dedicated sample interface
Application Example
Application: Quantitative Analysis of Water in Turbine Oils
Challenges:
Fast accurate determination of water in a range of
turbine oils.
Results must be comparable to Karl-Fischer reference method
Solution:
4500t field portable FTIR
Benefits:
Fast!
Save time and money
Eliminate potential errors caused
by sampling, storage, transport
Can be done by “unskilled” labour
Agilent Profile
November 22, 2010
Oil WITHOUT surfactant
• Water in mineral oil forms irregular droplets
• Water droplets that are of similar dimensions
lead to scattering of the IR Beam
• Baseline is shifted
• Reproducibility affected
• Absorbance is reduced
Oil WITH Agilent surfactant water stabiliser
• Water in mineral oil forms smaller regular
droplets
• Water droplets that are now smaller than the
wavelengths of the IR Beam and therefore
scattering is no longer an issue
• Baseline improves
• Reproducibility with surfactant much greater
• Absorbance is increased
• Accuracy greatly improved and comparable
with KF
Surfactant
Quick Guide
1.
Collect Kit and 4500
2.
Load Method
3.
Decant 20ml of Oil sample
into a suitable container.
4.
Add 545µl of water-in-oil
stabiliser
5.
Gently Swirl both
clockwise and anti (~30s)
6.
Run background for
method then place a small
drop of the stabilised
sample into the well and
run.
3410.8
Results
0.022
0.020
0.016
Absorbance
Poor
Reproducibility
Reduced
Absorbance
0.018
0.014
WITHOUT surfactant
0.012
0.010
0.008
0.006
0.004
Baseline
shift
0.000
-0.002
0.045
0.040
0.035
0.030
0.025
0.020
0.015
0.010
0.005
0.000
4400
4200
4000
3800
3600 3400
3x Abs
3200
3000 2800 2600 2400 2200
Wavenumber
2000 1800 1600
4000
3800
3600
3400
3200
3000
2800
2600 2400 2200
Wavenumber
800
WITH Agilent
surfactant
Reproducibility
greatly improved
Baseline much
improved
4200
1400 1200 1000
1127.5 0.3136
Absorbance
4600
3454.3
0.002
2000
1800
1600
1400
1200
1000
800
600
600
Results
turbine water surf actant.tdf ,25 (R ² = 0.998029969)
5500
67
66
68
WITH
Agilent Technologies Water Stabiliser
64
63
61
32
31
29
R2 = 0.9980
60
58
59
57
28
26
27
25
54
56
55
22
21
24
23
2500
50
52
49
51
turbine oil water.tdf,105 (R² = 0.859309544)
20
18
19
17
1400
46
48
47
45
1000
Predicted Concentration ( F11 C1 )
Predicted Conc entration ( F4 C 1 )
4000
15
16
14
13
41
43
44
42
38
10
9
12
39
3711
40
7
35
36 6
5
8
33
34
2
3
1
4
WITHOUT
surfactant
800
306
199
200
201
106
268
161
265
146
147
500ppm
Span
214
211
213
212
200
118
121
120
119
267
266
279
238
239
254
253 172
133
136
185
186
187
277
280
278 148
281
256
134
255
308
174
173
175
307
225
300ppm span
224
227
103
294
295
158
160
159
135
188
202
297
296
240
242
145
107
226
104
105
92
93
-500
122
94
-500
1000
2500
4000
91
5500
-400
-100
Actual Concentration ( C1 )
200
500
800
Actual Concentration ( C1 )
1100
1400
1700
Results
Calibration Curve 0 – 300ppm
Karl-Fischer ref values plotted
against peak absorbance area
Validation Test Results 0 – 1500ppm
4500t reported values plotted
against Karl-Fischer reference
values for a suite of unknowns
Application Example 2 – Monitoring Antioxidants
in Turbine Oils
Phenolic DBPC,
di-tertiary-butyl
paracresol
Aminic aDPA, alkyl di-phenylamine
R
OH
R
N
H
Absorbance
Absorbance
R
3680
3675
3670
3665
3660
3655
3650 3645 3640
Wavenumber
3635
3630
3625
3620
3615
3610
3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 3405 3400 3395
Wavenumber
Example of Phenolic Antioxidant in Turbine Oil
10000
Quant Validation Plot for Phenolic (ppm)
R²=1.000
16
9000
8000
4
19
6000
5000
25
4000
3000
10
2000
7
1000
13
0
Absorbance
Concentration
7000
Range
50 ppm to 5000 ppm
Accuracy
+/- 10% relative
28
22
1
3700
0.0
0.2
0.4
0.6
0.8
Peak Area
1.0
1.2
3690
1.4
3680
3670
3660
3650
Wavenumber
3640
3630
3620
3610
PASS
MONITOR FREQUENTLY
CHANGE IMMEDIATELY
120.00
25.00
Aminic Antioxidant
100.00
Phenolic
20.00
80.00
Relationship Between
Antioxidant Depletion
and Oxidation
60.00
15.00
10.00
(Peak Area Absorbance)
Oxidation
Oxidation
and Aminic Antioxidants (% of Conc. in New Oil)
Phenolic Antioxidant
40.00
5.00
20.00
0.00
0.00
New
ISO 32
Oil
Day 1
Day 2
Day 5
Day 6
Day 8
Day 9
Day 12
Day 13
Day 16
Day 19
Day 22
Day 23
Day 24
Day 26
1.
Phenolic Diminishes 40% right away- Evaporation and low molecular weight
flash off
2.
Aminic stays above 70% until near the end of useful life
3.
Aminic Stages of depletion
Stage 1: Mid-way point in oil lifespan, 25% depletion
Stage 2: Decent from 80% to 40% after phenolic reaches 30%
PASS
MONITOR FREQUENTLY
CHANGE IMMEDIATELY
120.00
25.00
Aminic Antioxidant
100.00
80.00
Phenolic Antioxidant
Oxidation
2
1
20.00
3.Stage 2
60.00
15.00
3.Stage 1
10.00
40.00
5.00
20.00
Critical Saturation of
Oxidation Products
0.00
0.00
New
ISO 32
Oil
Day 1
Day 2
Day 5
Day 6
Day 8
Day 9
Day 12
Day 13
Day 16
Day 19
Day 22
Day 23
Day 24
Day 26
Oxidation(Peak Area Absorbance)
Phenolic and Aminic Antioxidants (%of Conc. in New Oil)
•
•
Product Portfolio – Out of Lab Handheld
4100 ExoScan Handheld FTIR
4100 ExoScan Specifications
Frequency range
• 4000 – 650 cm-1
Maximum Resolution
• 4 cm-1
Non-hygroscopic optics
• ZnSe beam splitter
Power
• Onboard Lithium Ion Battery
• 100 – 250 VAC 47 – 63 Hz, Output:
15VDC
Operating temperature
• 0⁰ to 50⁰ C
Humidity
• 95% non-condensing
Physical Attributes
• 3.2 kg with standard battery
• 172 x 119 x 224 mm excluding
handle and sampling technology
• Std PDA or External Computer
• USB connection
• Full spectral analysis
4100 ExoScan Sampling Flexibility
Changing the Interface
from an ATR to a …
2
Diffuse 1.
.
4
.
5
.
3
.
1.
Twist the retaining
knurled ring nut off.
2.
Pull off the current
sampling accessory.
3.
Note that there is a
large pin and a small pin
to ensure that the
accessory is correctly
orientated.
4.
Place the new
accessory on and twist
on until hand-tight.
5.
Choose / Create an
appropriate method for
the accessory then
analyse sample.
4200 FlexScan
Head Attributes
• 2.2 kg with standard battery
*Electronics and Optics are
separated to make the sampling
head lighter
* Dedicated Sampling interface for
routine analysis
So, How Can You Analyse a Jumbo Jet?
So, How Can You Analyse a Jumbo Jet?
Application Example
Application: Assessment of Composite Thermal Damage
Challenges:
Exploration of degradation processes as a result of
external physical and chemical stresses
Correlate physical effect of heat damage to FTIR data
Solution:
4100 ExoScan
Benefits:
Fast!
Save time and money
Definitive “actionable result” given.
Application Example
Graph shows “short beam shear” strength (calculated from FTIR data)
plotted against degradation temperature. R2 = 0.95.
A validation test on a separate suite of samples comparing “actual”
SBS calculated from physical tests vs FTIR predicted SBS showed an
overall average error of just 1.89%
Application Example
http://pubs.acs.org/cen/science/
Measurement of
Composite Heat
Damage
The Boeing Company
NavAir (U.S. Navy)
“Boeing has put enough
faith in the handheld
spectroscopic methods that
the company has included
them in the repair manual
for the 787 Dreamliner.”
Other “Real World” Examples
Hydrocarbon Contamination in Soil
“The technology requires no
toxic solvents or
consumables, and sampling
positions can also be logged
automatically using GPS
coordinates”
http://www.ziltek.com.au
Other “Real World” Examples
Composite Evaluation for High
Performance Sailboats etc.
Red: white gelcoat
Blue: yellowing
gelcoat (originally
white).
FTIR spectra of two gelcoat samples taken from same
boat:
Red: Correct laminate
Q.I. Composites s.r.l. does non destructive testing
of composite structures in the field of
nautical, automotive, wind mills and aerospace.
Blue: Same laminate
exposed to heat
http://www.qicomposites.com/FTIR spectra of two carbon-epoxy samples:
Markets
• Petrochemical
• Power Generation
• Incoming QA/QC
• Aerospace
• Specialized Coatings
• Surface Characterization
• Art conservation
• Geology
• Academic
• Out of Lab Analysis
Questions?