A2 Technologies / Agilent Technologies

iPAL / 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 C 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 100m Can be special ordered to 50m or 200m Pre-defined Methods have been calibrated using 100m

Liquids only Quantitative analysis

50 ppm to 5 %

Reproducible and easy to use

ML/MLp Sample Interfaces

TumblIR

1. Place Sample on Lower Window

2. Rotate TumblIR3. Once TumlIR is in place analyze into place the sample

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% 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). 0.8% 0.5% 0.1%

0.05% 0.025% 0.0%

Biodiesel (FAME) has a strong infrared absorbance at 1745 cm-1 Completely free of any diesel interference

Measuring Biodiesel in Diesel Fuel

Measuring Biodiesel in Diesel Fuel

Calibration plot for Biodiesel in Diesel method showing excellent correlation

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

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 Kit

A2 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 from filters Calibration chart from filters

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.

10 mins

SAMPLE

RESULT

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 liquidliquid extractions.

Mro ic la bP C

3. Measuring Antioxidants in Turbine Oil with iPAL/PAL

Phenolic DBPC, di-tertiary-butyl paracresol Aminic aDPA, alkyl di-phenylamine
O H

N H

Absorbance

Absorbance
3630 3625 3620 3615 3610

3680

3675

3670

3665

3660

3655

3650 3645 3640 Wavenumber

3635

3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 3405 3400 3395 Wavenumber

Example of Phenolic Antioxidant in Turbine Oil

10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0
22 1 13 28 7 10 25

Quant Validation Plot for Phenolic (ppm) R=1.000

16

Range 50 ppm to 5000 ppm Accuracy +/- 10% relative

19

Concentration

Absorbance

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 120.00

MONITOR FREQUENTLY

CHANGE IMMEDIATELY 25.00

100.00

Aminic Antioxidant Phenolic Antioxidant Oxidation

20.00

and Aminic Antioxidants (% of Conc. in New Oil)

60.00

Relationship Between Antioxidant Depletion and Oxidation

15.00

10.00

40.00

Phenolic

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

Oxidation

(Peak Area Absorbance)

80.00

1. 2. 3.

Phenolic Diminishes 40% right away- Evaporation, Low molecular weight flash off Aminic stays above 70% until near the end of useful life 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%
Phenolic Aminic and Antioxidants (% of Conc. in New Oil)
120.00 PASS M N RFR Q E TL O ITO E UN Y C AN EIM D H G ME IATE Y L 25.00

100.00

Ox idation

80.00

3.Stage 1
60.00

3.Stage 2
15.00

10.00 40.00

5.00 20.00

Critical Saturation of O xidation Products

0.00

0.00

New ISO 32

D 1 ay

D 2 ay

D 5 ay

D 6 ay

D 8 ay

D 9 ay

D 12 ay

D 13 ay

D 16 ay

D 19 ay

D 22 ay

D 23 ay

D 24 ay

D 26 ay

Oxidation (Peak Area Absorbance)

A in A tiox m ic n idant Ph olic A tiox en n idant

20.00

4. Water-in-Oil Analysis with iPAL/PAL

Traditionally water by FTIR is difficult A2 has developed new methods to overcome these limitations For 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

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

A2 water stabilization method makes droplets uniform and small

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

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 4600 4400 4200 4000

3410.8

Reduced Absorbance

Poor Reproducibility

WITHOUT surfactant

Absorbance

Baseline shift
3454.3
3800 3600 3400 3200 3000 2800 2600 2400 2200 Wavenumber 2000 1800 1600 1400 1200 1000 800 600

0.045 0.040 0.035 0.030 0.025 0.020 0.015 0.010 0.005 0.000

Absorbance

3x Abs

Reproducibility greatly improved Baseline much improved

WITH A2 surfactant
1127.5 0.3136
2000 1800 1600 1400 1200 1000

4200

4000

3800

3600

3400

3200

3000

2800

2600 2400 Wavenumber

800

600

2200

1. 2. 3. 4. 5. 6.

Surfactant Quick Guide

Collect Kit and PAL Load Method Decant 20ml of Oil sample into a suitable container. Add 545 l of water-inoil stabiliser Gently Swirl both clockwise and anti (~30s) Run background for method then place a small drop of the stabilised sample into the well and run.

 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

A2 Water Stabilization Method

t u r b in e w a t e r s u r f a c t a n t . t d f , 2 5 (R = 0 . 9 9 8 0 2 9 9 6 9 )

WITH
5 50 0

A2 technologies Water Stabiliser Part no# 0020-900

32 31 29 64 63 61

4 00 0

60 58 59 7

tu ine oil w r.tdf,10 (R = 0 93 54 rb ate 5 .85 09 4)

28 26 25 7
2 68 16 1 2 65

Predicted Concentration ( F4 C1 )

1 400

P redicted Concentration ( F11 C1 )

WITHOUT surfactant
1 88 10 6

54 56 55
13 5 254 1 253 72 13 6 3 256 13 4 255 308 307 1 74 1 73 1 75 306 1 99 2 00 2 01 2 02 1 85 1 86 1 87

14 5 14 6 14 7 2 79

2 40 42

15 8 16 0 15 9

2 67

2 66

2 38 2 39 2 77 2 14 80 8 2 78 2 81

2 50 0

80 0

22 21 24 3

20 0

500ppm Span
2 14 2 11 13 2 12 92 93 94

2 97 1 2 96 18 1 21 2 94 2 95 1 20 1 19

22 5 22 4 22 3 7 10 10 7 22 4 6 10 10 5

300ppm span

50 52 51 49

1 22

91 -4 00 -10 0 20 0 5 00 8 00 11 00 14 00 17 00

20 8 17 9 1 00 0 46 48

A al C ncen tio ( C ) ctu o tra n 1

A2 Stabilized Water Method Performance

P L( p ) A pm 55 2 15 02 22 07 21 94 43 85 K(p Fp m 54 0 95 6 20 02 23 88 45 73 D e ne iff re c (p ) pm 2 1 8 7 2 5 7 6 8 2 % rro E r 4 .2 9 .0 1 .2 2 .7 1 .7

Range

Benefits of A2 technologies method compared to KF:

ppm of water results take the same spectral acquisition time and 75 5000 ppm interpretation time regardless of the level of water.

0.075-5.0%

Accuracy
+/- 10%

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

Application
1.Biodiesel in Diesel
Correlation of the carbonyl of the FattyAcidMethylEster (biodiesel) in Diesel.

1.

iPAL, no additional requirements plus

Requirements

2.

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.

3. 4.

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). 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). iPAL, no additional requirements.

iPAL + WIO kit / refill Kit

For 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.

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

Biodiesel in Petroleum Diesel