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

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238239

240242

253254

255

256

265

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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?