A2 Technologies / Agilent TechnologiesiPAL / PAL

with specific

reference to:1.Biodiesel in Diesel

2.Oil in Water

3.Anti-oxidants

levels of an oil

4.Water in oil

A2 Technologies Portable FTIR Spectrometers• A2 is focused on providing small portable FTIR spectrometers

– ML, MLp, PAL, iPAL

• Designed for use on a table or bench-top

– The ML and the PAL require mains power whereas the MLp and the iPAL are the battery powered analogues of the bench top instruments that can also function from mains power

– PAL and iPAL utilise A2 technologies patented Tumblir transmission cell that enables high throughput without the need for sample cells.

– Other sampling technologies available are:• ATR (a choice of either 1 bounce, 3 bounce or 9 bounce)• Gas cell (a choice of either 15cm or 50 cm)

A2 Technologies Portable FTIR Spectrometers

• All of A2 products measure mid-infrared spectra– Selective

• Spectra measured are unique to the chemistry of the sample

– Sensitive• Small changes in sample chemistry can be measured

– Universal• Most covalent chemical bonds can be measured

– All organic chemicals– Inorganics such as nitrates, phosphates, chlorates,

sulfates, etc.

• 8 lbs

• 8” x 8” x 4.5”

• External Computer

• USB connection

• External Power

• Full spectral analysis

• Designed for mobile/temp. labs

• 15 lbs

• 8” x 11.5” x 7.5”

• Integrated PDA computer

• Optional PC

• Internal battery

• Designed for field use

Common Specifications• Frequency range

– 4000 – 650 cm-1

• Maximum Resolution– 4 cm-1

• Non-hygroscopic optics– ZnSe beam splitter

• Power– 100 – 250 VAC 47 – 63 Hz, Output: 15VDC

• Operating temperature– 0 to 50 C⁰ ⁰

• Humidity– 95% non-condensing

PAL and iPAL• Particularly suited to Oil Analysis

– Predefined methods for many oil types• Turbine• Hydraulic• Motor oil• Gear• Bio-diesel in diesel

• Single sample interface-TumblIR– Oils, greases, pastes, emulsions– Oil in Water filtration technique– Fuels

ML/MLp Sample Interfaces• TumblIR

– Fixed path length liquid transmission cell• Standard 100µm

– Can be special ordered to 50µm or 200µm• Pre-defined Methods have been calibrated using 100µm

– Liquids only– Quantitative analysis

• 50 ppm to 5 %

– Reproducible and easy to use

ML/MLp Sample Interfaces

• TumblIR

1. Place Sample on Lower Window

3. Once TumlIR is in place analyze

the sample

2. Rotate TumblIR into place

4. Cleaning is easy!

• Typical Methods supplied with instrument– Gear Oil - Mineral Oil Based

• Gear Oil condition monitoring “Gear – ASTM E2412 EP Fluid Condition monitoring version 3”

– ASTM 2412 – Engine oil• Crankcase, polyol ester, EP fluid

“Engine – ASTM E2412 Crankcase Condition monitoring Version3”

• Transformer Oil • ASTM D2668

“Transformer oil – ASTM D2668 Version 3”

• Biodiesel in diesel• EN 14078, LOQ of 1%• A2 technologies Method, LOQ of 0.025%

“Fuel – Biodiesel % in Diesel Version4”

Measuring Biodiesel in Diesel Fuel• Biodiesel (FAME) can cause problems in stored

diesel fuel• Water, biological buildup, cold flow…

• % Biodiesel regulated in some areas• B5 – 5%, B10 – 10%, B20 – 20%

• Methods specified for blending B5 to B20• EN 14078• Specifies FTIR with transmission cell• PAL meets specification and has method installed

Note we have a an ASTM method (D73571-07) for B1-B100 (1%-100%) that uses a multi reflection diamond.

1.Measuring Biodiesel in Diesel Fuel

• A2 developed a more sensitive method to look at biodiesel contamination• 0.025% to 20% • Based on EN 14078 method (1% TO 15%)

• Developed for situations where biodiesel contamination can damage equipment Fuel injectors Filters Seal damage Microbial growth

1.5%

0.8%

0.5%

0.1%

0.05%

0.0%

0.025%

Measuring Biodiesel in Diesel Fuel

Biodiesel (FAME) has a strong infrared absorbance at 1745 cm-1

• Completely free of any diesel interference

Absorbance at 1745 cm-1 of biodiesel in diesel fuel at 0.0, 0.025, 0.05, 0.1, 0.5, 0.8 and 1.5 % (v/v).

Measuring Biodiesel in Diesel Fuel

Validation results for the Biodiesel in diesel method showing an average relative error of only 1%.

Calibration plot for Biodiesel in Diesel method showing excellent correlation

2. Measuring Oil in Water with iPAL/PAL

• Oil content in water is an important measurement• Discharge consent• Proper cooling water operation

• Both oil and water are strong IR absorbers• Traditionally solvent extraction used to separate the two

• Expensive, hazardous, environmental regulations

• A2 developed a filtration technique • Measure directly through filter.• Solventless extraction method• Reduced glassware, solvent use and simpler

Novel Oil in water Method using FTIR

Measuring Oil in Water with A2 OIW KitA2 sells a kit for measuring oil in water• Filters, glass wear and oil stabiliser included

• Only A2 filters should be used, other filters will yield inaccurate readings as our model has a method to compensate for the filter thickness that is specific to the type of filters used for extraction of the oil

• A2 method also warns the user if the filter has not been allowed to dry completely

Measuring Oil in Water

Spectra (A) and calibration curve (B) for oil in water using the A2 filter based method utilising Oil Stabiliser. Mineral oil in water from 0.5 to 45 ppm.

Spectra from filters Calibration chart from filters

SAMPLE RESULT10 mins

• Advantages• Completely Solvent free &

novel oil extraction method.• Only three steps.• Well established FTIR

technique.• <ppm limit of detection.• Sample to spectra then

actual result in ten minutes.• Very little sample

preparation.• On site testing possible.• Much reduced glass ware

usage compared to liquid-liquid extractions.

Microlab PC

3. Measuring Antioxidants in Turbine Oil with iPAL/PAL

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

3700 3690 3680 3670 3660 3650 3640 3630 3620 3610

Wavenumber

Abs

orb

anc

e

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

A

min

ic A

ntio

xida

nts

(% o

f C

onc.

in N

ew O

il)

0.00

5.00

10.00

15.00

20.00

25.00

Oxi

dati

on (

Pea

k A

rea

Abs

orba

nce)

Aminic Antioxidant

Phenolic Antioxidant

Oxidation

PASS MONITOR FREQUENTLY CHANGE IMMEDIATELY

Relationship Between Antioxidant Depletion

and Oxidation

1. Phenolic Diminishes 40% right away- Evaporation, Low molecular weight flash off

2. Aminic stays above 70% until near the end of useful life3. 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%

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

Ph

eno

lic an

d Am

inic A

nti

ox

ida

nts

(%

of

Co

nc.

in

New

Oil

)

0.00

5.00

10.00

15.00

20.00

25.00

Ox

ida

tio

n (

Pea

k A

rea

Ab

sorb

an

ce)

Aminic Antioxidant

Phenolic Antioxidant

Oxidation

PASS MONITOR FREQUENTLY CHANGE IMMEDIATELY

Critical Saturation of Oxidation Products

11 2

3.Stage 13.Stage 2

4. Water-in-Oil Analysis with iPAL/PAL• Traditionally water by FTIR is difficult • A2 has developed new methods to overcome these

limitationsFor all mineral oil based methods, two types of methods exist

– Water Stabilized– Non-stabilized

• Water stabilized methods use a surfactant to minimize water droplet size

– Improved water predictions– Both application note and video are available

• A2 Technologies sells a kit for water stabilization

A2 water stabilization method makes droplets uniform and small

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 A2 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

3410

.8

4600 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

34

54

.3

4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200

2000 1800 1600 1400 1200 1000 800 600

0.045 0.040 0.035 0.030 0.025 0.020 0.015 0.010 0.0050.000

Wavenumber

Abs

orba

nce

3x Abs

Reproducibility greatly improved

Baseline much improved

WITH A2 surfactant

PoorReproducibility

Baseline shift

Reduced Absorbance

Surfactant Quick Guide

1. Collect Kit and PAL2. Load Method3. Decant 20ml of Oil

sample into a suitable container.

4. Add 545l 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.

A2 Water Stabilization Method• Addition of surfactant to the oil

– Creates a stable emulsion– Maximum IR water absorbance achieved at 3% surfactant– Two different non-ionic PEO based surfactants used

• Three fold increase in water absorbance– Less IR scattered light, more absorbed– Smaller water particle (micelle) sizes, with a narrower

distribution• Water measurements are very reproducible• Variability in the non-surfactant method has been eliminated • Compares favourably with ‘Gold’ standard Karl Fischer method

turbine water surfactant.tdf,25 (R² = 0.998029969)turbine water surfactant.tdf,25 (R² = 0.998029969)

Actual Concentration ( C1 )Actual Concentration ( C1 )

Pred

icted

Con

cent

ratio

n ( F

4 C

1 )

Pred

icted

Con

cent

ratio

n ( 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

33343536

37383940

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

dic

ted

Co

nc

en

tra

tion

( F

11

C1

)P

red

icte

d C

on

ce

ntr

ati

on

( F

11

C1

)

-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

A2 technologies

Water Stabiliser

Part no# 0020-900

A2 Stabilized Water Method PerformancePAL (ppm) KF (ppm

Difference (ppm) % Error

525 504 21 4.2

1052 965 87 9.0

2027 2002 25 1.2

2914 2838 76 2.7

4835 4753 82 1.7

• Range– 75 – 5000 ppm– 0.075-5.0%

• Accuracy – +/- 10%

Benefits of A2 technologies method compared to KF:

• ppm of water results take the same spectral acquisition time and interpretation time regardless of the level of water.

•Virtually independent from operator removing the requirement of subjective ‘end point’ assignment.

•Does not interfere with any of the major additives or components in a oil therefore can measure water-in-oil concomitant with additives, breakdown products and contaminants

Application1.Biodiesel in DieselCorrelation of the carbonyl of the FattyAcidMethylEster (biodiesel) in Diesel.

2.Oil-in-Water (OIW)filtration with based technique requiring A2 technologies OIW surfactant and lipophilic filters.

3.Anti-oxidants levels of an oil Spectral analysis of peaks corresponding to the additives concurrent with oxidation. Other additives and/or breakdown products and/or contaminants can be quantified simultaneously.

4.Water-in-oil (WIO)A 20ml aliquot of the oil is mixed with a 545ul volume of WIO stabiliser, gently swirled, rested then analysed as normal.

1. iPAL, no additional requirements plus optional GC-MS accredited biodiesel in diesel Stds of 0%, 0.05% and 0.5% are available. (12 packs each with a set of three abovementioned stds).

2. iPAL + OIW kit / refill Kit For those without glassware and pipettes OIW kit is most appropriate alternatively the refill kit for those who either have the requisite glassware or have used up all their surfactant and filters).

3. iPAL, no additional requirements.

4. iPAL + WIO kit / refill KitFor those without pipettes the full WIO kit is most appropriate alternatively the refill kit for those who either have the requisite pipettes (one adjustable micro pipette and 20ml disposable pipettes or have used up all their surfactant and filters). Note sample bottles required for the mixing of the surfactant with the oils are not included and will require to be ordered by the end user.

Requirements

Nb: 3.&4. can be combined into a single method

Biodiesel in Petroleum Diesel