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Rob WillsProduct Specialist Molecular SpectroscopyUK, Ireland, Nordics and IDO
How To Analyse A Jumbo Jet…..And Other Analytical Challenges
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 adultera tion
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”
1st Quarter Marketing
February 2011: Agilent acquired A2 Technologies
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 FTIRII. Portable units 4500 Series FTIRIII. Handheld units 4100 ExoScan, 4200 FlexScan
Agilent’s New POM and Entry FTIR Spectrometers
How “Small” Are They?
A2 instruments can make 2 types of measurements
• Quantitative
Measure concentration
Oil Analysis, fuel analysis, etc.
Component method
• Qualitative Library Search
Identify unknown sample
Quality control, product ID, etc.
Library Search method
Chemical Identification by FTIR
Chemical can be identified by searching commercial or user generated libraries.
Calibration allows prediction of the concentration from the IR spectrum.
IR spectral overlay of turbine oil 5-4300ppm
3900 3700 3500 3300 3100
0.24
0.16
0.08
0.00
-0.08
Wavenumber
Abs
orba
nce
Concentration by FTIR
Measurement Types
Entry – In Lab Systems
5500awith ATR
5500twith Transmission Cell
5500 Dialpathwith triple
Transmission Cell
5500 Series FTIR Specifications
Wavenumber Range4000 – 650 cm-1
Resolution4 cm-1
Non-hydroscopic OpticsZnSe beam splitter
Power100 – 250 VAC 47 – 63 Hz, Output: 15VDC
Operating Temperature0⁰ to 50⁰ C
Humidity95% 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
ATR• 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
5500a FTIR
5500a FTIR
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
Agilent ProfileNovember 22, 2010
Application:
Challenges:
Solution:
Benefits:
Quantitative Analysis of Water in Turbine Oils
� Fast accurate determination of water in a range of �turbine oils.� Results must be comparable to Karl-Fischer reference method
� 4500t field portable FTIR
� Fast!� Save time and money� Eliminate potential errors causedby sampling, storage, transport� Can be done by “unskilled” labour
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
.84600 4400 4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
0.022
0.020
0.018
0.016
0.014
0.012
0.010
0.008
0.006
0.004
0.002
0.000
-0.002
Wavenumber
Abs
orba
nce
WITHOUT surfactant
1127
.5 0
.313
6
3454
.3
4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
0.0450.0400.0350.0300.0250.0200.0150.0100.0050.000
Wavenumber
Abs
orba
nce
3x Abs
Reproducibility greatly improved
Baseline much improved
WITH Agilent surfactant
PoorReproducibility
Baseline shift
Reduced Absorbance
Results
turbine water surf actant.tdf ,25 (R² = 0.998029969)turbine water surf actant.tdf ,25 (R² = 0.998029969)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed
Con
cen
tra
tion
( F
4 C
1 )
Pre
dict
ed
Con
cen
tra
tion
( F
4 C
1 )
-500
1000
2500
4000
5500
-500 1000 2500 4000 5500
-500
1000
2500
4000
5500
-500 1000 2500 4000 5500
12345678
9101112
13141516
17181920
21222324
252627
28
2931
32
3334353637383940
41424344
45
46
4748
49505152
545556
57585960
616364
666768
-500
1000
2500
4000
5500
-500 1000 2500 4000 5500
turbine oil water.tdf,105 (R² = 0.859309544)turbine oil water.tdf,105 (R² = 0.859309544)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F
11 C
1 )
Pre
dict
ed C
once
ntra
tion
( F
11 C
1 )
-400
200
800
1400
-100 200 500 800 1100 1400 1700
-400
200
800
1400
-100 200 500 800 1100 1400 1700
91
92
93
94
103
104105
106
107
118
119
120
121
122
133
134
135
136
145
146147
148
158
159
160
161
172
173
174
175
185186187
188
199200201202
211212213214
224
225
226
227
238239
240242
253254
255
256
265
266
267
268
277
278
279
280281
294295
296297
306
307
308
-400
200
800
1400
-100 200 500 800 1100 1400 1700
300ppm span500ppm Span
WITHOUTsurfactant
WITH
Agilent Technologies Water Stabiliser
R2 = 0.9980
Results
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
3680 3675 3670 3665 3660 3655 3650 3645 3640 3635 3630 3625 3620 3615 3610Wavenumber
Abs
orba
nce
3680 3675 3670 3665 3660 3655 3650 3645 3640 3635 3630 3625 3620 3615 3610Wavenumber
Abs
orba
nce
3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 3405 3400 3395Wavenumber
Abs
orba
nce
3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 3405 3400 3395Wavenumber
Abs
orba
nceR
OH
R
OH
NH
R R
NH
R R
Aminic aDPA, alkyl di-phenylaminePhenolic DBPC, di-tertiary-butyl paracresol
Application Example 2 – Monitoring Antioxidants in Turbine Oils
3700 3690 3680 3670 3660 3650 3640 3630 3620 3610Wavenumber
Abs
orba
nce
Example of Phenolic Antioxidant in Turbine Oil
Peak Area
1
4
7
10
13
16
19
22
25
28
Quant Validation Plot for Phenolic (ppm)R²=1.000
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
10000
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
Con
cent
ratio
n
Range50 ppm to 5000 ppm
Accuracy+/- 10% relative
0.00
20.00
40.00
60.00
80.00
100.00
120.00
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
Phe
nolic
and
Am
inic
Ant
ioxi
dant
s (%
of
Con
c. in
New
Oil)
0.00
5.00
10.00
15.00
20.00
25.00
Oxi
dati
on(P
eak
Are
a A
bsor
banc
e)
Aminic Antioxidant
Phenolic Antioxidant
Oxidation
PASS MONITOR FREQUENTLY CHANGE IMMEDIATELY
Relationship Between Antioxidant Depletion and Oxidation
1. Phenolic Diminishes 40% right away- Evaporation an d low molecular weight flash off
2. Aminic stays above 70% until near the end of usef ul life
3. Aminic Stages of depletion
• Stage 1: Mid-way point in oil lifespan, 25% depleti on• Stage 2: Decent from 80% to 40% after phenolic reac hes 30%
0.00
20.00
40.00
60.00
80.00
100.00
120.00
NewISO 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
Phe
nolic
and
Am
inic A
ntio
xida
nts (%
of C
onc.
in N
ew O
il)
0.00
5.00
10.00
15.00
20.00
25.00
Oxi
datio
n (P
eak
Are
a A
bsor
banc
e)
Aminic Antioxidant
Phenolic Antioxidant
Oxidation
PASS MONITOR FREQUENTLY CHANGE IMMEDIATELY
Critical Saturation of Oxidation Products
1 2
3.Stage 1
3.Stage 2
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 splitterPower
• Onboard Lithium Ion Battery• 100 – 250 VAC 47 – 63 Hz, Output:
15VDC Operating temperature
• 0⁰ to 50⁰ CHumidity
• 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 …Diffuse
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.
1.
2.
3.
4.
5.
4200 FlexScan
*Electronics and Optics are separated to make the sampling head lighter
* Dedicated Sampling interface for routine analysis
Head Attributes• 2.2 kg with standard battery
So, How Can You Analyse a Jumbo Jet?
So, How Can You Analyse a Jumbo Jet?
Application Example
Application:
Challenges:
Solution:
Benefits:
Assessment of Composite Thermal Damage
� Exploration of degradation processes as a result of external physical and chemical stresses�Correlate physical effect of heat damage to FTIR data
� 4100 ExoScan
� 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
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.”
http://pubs.acs.org/cen/science/
Other “Real World ” Examples
http://www.ziltek.com.au
Hydrocarbon Contamination in Soil
“The technology requires no toxic solvents or consumables, and sampling positions can also be logged automatically using GPS coordinates”
Composite Evaluation for High Performance Sailboats etc.
http://www.qicomposites.com/
Q.I. Composites s.r.l. does non destructive testing of composite structures in the field of nautical, automotive, wind mills and aerospace.
Other “Real World ” Examples
FTIR spectra of two gelcoat samples taken from same boat:
Red: white gelcoat
Blue: yellowing gelcoat (originally white).
FTIR spectra of two carbon-epoxy samples:
Red: Correct laminate
Blue: Same laminate exposed to heat
• Petrochemical
• Power Generation
• Incoming QA/QC
• Aerospace
• Specialized Coatings
• Surface Characterization
• Art conservation
• Geology
• Academic
• Out of Lab Analysis
Markets
Questions?