ASTM D5185-13 Analyzing 22 Elements in

Used & Unused Lubricating and Base Oils

Houston, TXJune 21, 2017

Lindsey WhitecottonApplications Chemist

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Overview

• Challenges associated with elemental analysis of organic solvents using

ICP

• Agilent 5110 ICP-OES

- Key features

-Instrument suitability to elemental analysis of organic samples

• Instrument Performance

-Application: ASTM D5185-13

• Conclusions

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Elemental analysis- organic solvents

Many laboratories are required to perform element analysis in organic solvents and

chemicals:

• Additive elements and wear metals in lubricating oils and base oils

• Metals in Crude petroleum, gas oil, asphalts

• Volatile organics, eg. Methanol, gasoline, naphthalene

Challenges of running organics using ICP

• Maintaining a stable and robust plasma throughout analysis

• Interferences due to C-based molecular bands

• Carbon build up on torch

• Reproducible measurements

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5110 ICP-OES

• Uncompromised speed

• Uncompromised performance

• Uncompromised ease of use

Agilent’s 5110 ICP-OES key benefits

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• Fastest sample throughput of difficult samples

• Low gas consumption

Lowest cost of ownership

• Analytical performance

• System robustness and reliability

Enhanced Performance

• Hardware

• SoftwareSimple Operation

How is Low Cost of Ownership facilitated…HIGHEST SPEED?

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DSC AVS 6/7 Vista Chip II

High Speed

Peristaltic Pump

SPEED

DSC technology - how does it work?

• Fast, single reading of the plasma for both radial and axial.

• Vertical torch gives high matrix capability

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Dichroic

Spectral

Combiner

(DSC)

To detector

Mirror

DSCHole

Vertical

torch

5110 SVDV Pre-optics5110 SVDV Mode Selector

Unique DSC technology for ICP-OES provides DV without compromise.

Future Proof Your Lab5110 SVDV ICP-OES is 4 instruments in 1

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2. Radial Mode 3. Axial Mode1. Synchronous VDV Mode

4. Conventional Dual View Mode

+

RAD AX

Fully integrated Advanced Valve System (AVS)

• Installation

• Control with integrated software

• Maintenance

Simple

• 2X sample throughputFast

• Controlled Ar bubble injection provides long term stability

Precise

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Reduce sample uptake, stabilization times, and rinse delays using the

optional AVS switching valve.

Controlled bubble injection for highest analytical precision.

Basic AVS 6/7 Operations: Standby mode

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Basic AVS 6/7 Operations: Refilling

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Basic AVS 6/7 Operations: Stabilizing

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Basic AVS 6/7 Operations: Reading

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Basic AVS 6/7 Operations: After reading

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Bubble Injection read time

Maximize read time and speed up wash in and wash out

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• Without bubble9 s

• With bubble19 s

Fitted Background Correction

Deconvolution Techniques - FACT

IntelliQuant

August 1, 2017

Agilent Confidential

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Identifies and calculates an approximate concentration for up to 70

elements in a sample

• Heatmap shows

relative

concentrations of

elements in

sample.

• Concentration

thresholds can be

adjusted

Full spectrum (done

in < 15 s) shows all

elements present &

any potential

interferences

Vista Chip II CCD detector

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• Fastest clocking speed of any ICP-OES detectorFast

• Sealed detector reduces gas consumption and protects from corrosion creating excellent longevity

Low Cost of Ownership

• Continuous wavelength coverage

• >98% wavelengths between 167-785nm

Wide λcoverage

• -40 °C triple stage peltier cooling provides excellent detection limits

• Full wavelength scan provides rapid screening and semi quantitative analysis

High Performance

Agilent’s 5110 ICP-OES key benefits

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• Fastest sample throughput of difficult samples

• Low gas consumption

Lowest cost of ownership

• Analytical performance

• System robustness and reliability

Enhanced Performance

• Hardware

• SoftwareSimple Operation

AVS - Integrated Switching Valve

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Elegant design - easy installation Simple, integrated software Easy maintenance

Step 2

Step 1

Step 3

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What makes the 5110 ICP-OES suitable for organic sample analysis?

• High performance

• Simplicity

Key features:

• Solid state RF (SSRF) system

• Vertically oriented torch

5110 ICP-OES: Solid State RF (SSRF) system

• Operates at 27MHz to provide a robust and stable plasma

• The SSRF can rapidly adjust to changes in the plasma

• Plasma conditions similar to those used for aqueous solutions can be used for organics without the need for higher plasma gas flows

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5110 ICP-OES: Vertically oriented torch

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High throughput wear metals application

Energy & Chemical

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Wear metal analysis using the 5110 RV ICP-OES with Advanced Valve System (AVS 6)

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• Rapid determination of 22 elements

in used and unused oils according

to ASTM Standard Test method

D5185-13

• To monitor condition of equipment

for wear, indicate efficiency of

blending of additive packages or

QA of base oil for metal content

• Agilent 5110 Radial View ICP-OES,

offers robustness, speed and

reduced running costs

Wear metals analysis - Measurement challenge

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Solution

Agilent 5110 RV ICP-OES

Fitted with an AVS 6 Advanced Valve System and

SPS 4 autosampler

Challenge

Without compromising performance

Increase sample

throughput

for ASTM D5185-13

AVS 6 improves sample throughput

With AVS 6 Without AVS 6

Sample to sample time (s) 22 52

Ar consumption per sample (L) 7 17.4

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Comparison of sample throughput for analysis of wear metals in oils with and without

an AVS 6 accessory

AVS 6 improves

sample throughput

by reducing delay

and rinse times

Sample Introduction

The standard sample introduction system

• Seaspray nebulizer

• double-pass glass cyclonic spray

chamber

• standard 1.8 mm torch

• Use 1.4 mm I.D. for wear metals/biodiesel

• Use 0.8 mm I.D. foe more volatile solvents

August 1, 2017

Confidentiality Label

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Use double

pass or

baffle for

organics

Experimental

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Parameter Setting

Read Time (s) 2

Replicates 2

Sample uptake delay (s) 4.5

Stabilization time (s) 6

Rinse time (s) 2 (Fast pump: Off)

Pump speed (rpm) 12

RF power (kW) 1.3

Aux flow (L/min) 1.0

Plasma Flow (L/min) 12.0

Nebulizer flow (L/min) 0.65

AVS 6 Settings

Loop volume (mL) 0.25

Pump rate: Valve uptake (mL/min) 36.0

Pump rate: Inject (mL/min) 10.0

Bubble injection time (s) 2.5

Pre-emptive rinse time (s) 1.5

Agilent 5110 RV ICP-OES operation and method parameters

Parameter Setting

Ar/O2 addition Not required

Nebulizer Glass concentric

Spray chamber Double pass cyclonic

Torch Organic 1.4 mm id

Sample pump tubing White-white Solvaflex

Waste pump tubing Grey-grey Solvaflex

Background correction Fitted

Full application note available at www.agilent.com

ExperimentalOperating parameters

Table 1. Agilent 5110 RV ICP-OES operating parameters

Parameter Setting

Read time (s) 2

Replicates 2

Sample uptake delay (s) 4.5

Stabilization time (s) 6

Rinse time (s) 2 (fast pump: Off)

Pump Speed (rpm) 12

RF power (kW) 1.30

Aux flow (L/min) 1.0

Plasma flow (L/min) 12.0

Nebulizer flow (L/min) 0.65

Table 2. Agilent 6 port Advanced Valve System (AVS 6)

operating parameters

Parameter Setting

Loop volume (mL) 0.25

Pump rate: Valve uptake (mL/min) 36.0

Pump rate: Inject (mL/min) 10.0

Bubble injection time (s) 2.5

Pre-emptive rinse time (s) 1.5

Standard and sample preparation

Analysis

• Using 5110 RV ICP-OES

Sample

• Used engine oil samples

• 1 in 10 dilution with A-solv ICP solvent

• Viscosity matrix matched with Agilent Mineral Oil Blank (75 cSt)

Standard preparation

• Calibration standards prepared from Agilent S21 + K

• Viscosity matrix matched with Agilent Mineral Oil Blank (75 cSt)

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Results

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Linear calibration range

Excellent linearity for Ca 422.673 nm up to 250 ppm

Results

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Method Detection Limits & Recoveries• Excellent detection limits were obtained

• Spike recoveries were all within 10% of the expected values

Element

nm

Method Detection

Limit (mg/kg)

Spike Recovery

(%)

Ag 328.068 0.020 97

Al 308.215 0.13 97

B 249.772 0.032 101

Ba 233.527 0.029 99

Ca 317.933 0.068 103

Cd 226.502 0.021 99

Cr 267.716 0.042 99

Cu 327.395 0.032 96

Fe 238.204 0.049 103

K 766.491 0.83 96

Mg 285.213 0.049 99

Mn 293.305 0.0035 98

Mo 202.032 0.089 104

Na 588.995 0.456 96

Ni 231.604 0.269 106

P 213.618 0.479 103

Pb 220.353 0.601 107

Si 288.158 0.115 102

Sn 242.170 1.40 104

Ti 337.280 0.023 105

V 309.310 0.022 98

Zn 202.548 0.028 96

Seconds

22

7.0 L

Wear metals analysis – Results

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6 hours!

%RSD <3%

Conclusions

The Agilent 5110 ICP-OES ideal for determining metals in oils as per ASTM D5185:

• Providing the high sample throughput when fitted with AVS 6

- Analysis time 22 secs per sample

- Total gas consumption 7 L Ar per sample

• High performance

- Excellent LTS, <3% RSD over 6 hours

• Ease of use

- AVS calculator for easy valve method development

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ASTM Method Update…

ICP-MS Trace Elements in Distillate FractionsParameter Value

Forward Power 1600 W

Sampling Depth 8 mm

Carrier Gas 0.5 L/min

Makeup Gas 0.1 L/min

Option Gas 30 %

Solution Uptake Rate Self-Aspirated

Spraychamber Temperature -5 ˚C

Extraction Lenses Autotune

KED 4 V

Cell Gas Flow Rates 5.0 ml/min (He)

6.0 ml/min (H2)

Results…

7900 ICP-MS

Sample 24 Mg 27 Al 47 Ti 51 V 52 Cr 56 Fe 63 Cu 75 As 107 Ag 111 Cd 208 Pb

Light

Naphtha

Spike

RSD (%) 0.2 5.9 2.7 0.5 0.2 0.8 0.1 1.0 0.1 0.9 0.9

Recovery

(%)102 103 100 100 101 100 100 96 98 105 97

Diesel

Spike

RSD (%) 0.8 2.3 0.5 1.2 0.4 0.2 1.1 0.2 1.2 0.3 0.3

Recovery

(%)104 103 102 101 103 100 104 103 99 101 101

Gasoline

Spike

RSD (%) 0.8 5.1 2.7 0.4 1.6 0.1 0.3 0.9 0.1 1.0 0.9

Recovery

(%)106 106 98 100 101 100 100 96 99 104 96

Questions?

Leading the way in atomic spectroscopy innovation www.agilent.com/chem/atomic

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Agilent AA Agilent MP-AES Agilent ICP-OES Agilent ICP-MS Agilent ICP-QQQ

Reduce Vapor Load by Decreasing the Temperature of the Spray Chamber when Running Volatile Organics

Peltier chilled chambers

Reduces vapor loading

Ideal for volatile organic solvents

Programmable temperature

-5 C, -10C, -20C