LUBRICANT TESTING AND

DIFFERENTIATION IN LABORATORY
BETWEEN MINERAL AND SYNTHETIC OIL

Roberto Lava
Regional Environmental
Protection Agency of Veneto

TAIEX Workshop on Quality

Analysis of Lubricant Oil
(60124)
Cairo (Egypt) 11-12 April 2016
 ARPAV - Regional Agency for Environmental Protection
and Prevention of Veneto

The goal of the Agency is to control and preserve the environment in order to
help the identification and elimination of risks to humans and to the environment.

Main goals are:

· Controlling of the environment including sources of pollution

(e.g. industrial emissions, waste, radiation);

· Monitoring of the state of the environment,

particularly the quality of air, water, and soil;

· Preventing risk factors and promoting an education aimed at favouring

life styles, which respect the environment.

ARPAV coordinates its activities closely with others Public Bodies

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 ARPAV

ALPI
(Dolomiti URBAN AREA
Mountains) (Verona, Padova)

SURFACE WATERS
(Garda Lake,
Po/Adige/
VENICE
Brenta Rivers)
and Venice
Lagoon

PADANA PLAIN
(rural and industrial) ADRIATIC SEA
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 ARPAV

LABORATORY SERVICE

2012-2014: Re-organization of the laboratory network

Two main regional laboratories:

1) ENVIRONMENT (air, water, soil and waste, REACH)

2) FOOD
Organic Micro-Pollutants Unit

ADVANCED ANALYTICAL INSTRUMENTATIONS

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 AGENDA

09:30 - 10:30
Lubricant testing and their environmental impact
Differentiation between mineral and synthetic oil in lab

10:30 – 10:45
Coffee break

10:45 - 12:00
Measurement of oil in produced water

12:00 – 12:15
Q&A. Discussion
 OUTLINES

- Introduction
- Definition
- Test of the base stock
- Elemental and structural analysis
- Environmental Impact
- References and further readings

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 INTRODUCTION

LUBRICANT TESTING

Physical and chemical tests / spectroscopic and chromatographic techniques

used to establish the structural and compositional identity of lubricant.

LUBRICANT = BASE STOCK + ADDITIVES

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 INTRODUCTION

LUBRICANT TESTING

Physical and chemical tests / spectroscopic and chromatographic techniques

used to establish the structural and compositional identity of lubricant.

LUBRICANT = BASE STOCK + ADDITIVES

TRIBOLOGICAL TESTs = tests (mostly mechanical) about the performances

requirements of finished lubricant and their in-service
condition monitoring

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 MINERAL OIL

Purified and extracted from crude oil in refineries. Depending from the origin and
separation processes used, the chemical composition can vary.

- AROMATICS (high solubility)

- NAPHTHENICS (good low-temperature properties)
- PARAFFINS (high viscosity, low sulphur content, good oxidative stability)

Variable distribution of chain length and ramification

More complicated refinery processes (separation, degradation, hydrogenation,
hydrocracking) produce a wider range of compounds, quite impossible to separate

Highly available on the market = INEXPENSIVE

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SYNTHETIC OIL

SYNTHETIC OIL
Synthesised with industrial production - big advantage that can be customized
chemical composition modified for the specific requirements (molecular structures
more uniform).

-Improved stability (viscosity)

-Less internal fraction Cost of the production
-Lower toxicity (less volatiles) higher
-Compatibility with rubber and plastic
-Lower environmental impact

POLYALPHAOLEFINS (PAO) = hydrocarbon based polyglycols and esters

saturated oligomers manufactured via catalytic oligomeration of alpha-olefins
(Group IV)

Group V = other types of synthetic oils

MINERAL VS SYNTHETIC I

M
S

K. Bannister, Machinery’s Handbook (lubrication chapters) and Lubrication for Industry,

part of the ICML and ISO Domain of Knowledge
 Gandelli M, http://www.maconresearch.com/blog/olio-sintetico-e-olio-minerale-5-caratteristiche-a-confronto, 2014
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 MINERAL VS SYNTHETIC II

BIO-BASED LUBRICANT
Attractive alternative to petroleum-based lubricant, biodegradable, mostly
formulated from renowable agricoltural plant and animal resources. Lately
cost competitive and their market is increasing

Synthetic fluid and bio-based lubricant market is growing

(expected +13% for 2020)

New products are continuously coming out in the market for very specific application

NEW ADDITIVES/FORMULATIONS

NEEDS OF SPECIFIC CONTROLS AND TARGET ANALYSES

13 New performances specifications and test methods development as consequence

 MINERAL VS SYNTHETIC III

Unfortunately there are no reliable ways or methods to exactly distinguish between

mineral and synthetic oils.

COLOR.
Synthetic oil are TRANSPARENT, while mineral are DARKER (aromatics, sulphur).
Not reliable for the use of colour additives and dyes (darkening or whitening)

In LABORATORY
Looking at the combination of the physical properties such as:
- VISCOSITY INDEX
- FLASH POINT
- POUR POINT
- ANILINE POINT
- THERMAL STABILITY
A mixture of synthetic and mineral oil become a very big analytical challenge
study the composition of BASE STOCK and ADDITIVES.
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 BASE STOCK

Physical properties of the finished lubricants are primarily

attributable to the structure and the properties if the lubricant
base stock (bulk of the lubricant).

Chemical properties, on the other hand, are due to the presence of the additives
used to formulate them.
- VISCOSITY
- VAPOR PRESSURE
- DENSITY
- BULK MODULUS
Properties that are evaluated - THERMAL PROPERTIES
by the various physical and - SURFACE TENSION
analytical tests: - GAS SOLUBILITY
- FOAMING TENDENCY
- ELECTRICAL PROPERTIES
- THERMAL STABILITY
15 - OXIDATION STABILITY
 VISCOSITY
SYNTHETIC OIL MINERAL OIL
Gandelli M, http://www.maconresearch.com/blog/olio-sintetico-e-olio-minerale-5-caratteristiche-a-confronto, 2014

Measure of the resistance of a fluid to flow

For a lubricant are reported at 40 °C and 100 °C, measured in Stroke (St = mm2/s)
Viscosity decrease with the increase of temperature.
HIGH VISCOSITY INDEX (VI) = BETTER OIL (more stable)

Mineral oil = VI up to 100-120

Synthetic oil = >140 (140-170), >250 for silicone oil

ASTM D445, kinematic viscosity at 100 °C (most common method)

The method specifies a procedure for the determination of kinematic viscosity of
transparent and opaque oil by measuring the time for a volume of liquid to flow
under gravity through a calibrated glass capillary viscometer
ASTM D445-03 corresponds to the ISO 3104
16 range covered = 0.02 to 300000 mm2/s
 FLASH POINT I

Measure of the ignitability of an oil.

It is the lowest temperature at which vapours of a fluid ignite.
Required an ignition source, a spark or flame
(vs auto-ignition point of temperature)
2 methodologies (closed and open cup)
ISO 2719, ASTM D93, EPA1010a: Pensky-Martens Closed Tester
ASTM D92: Cleveland Open Cup (less used for oil)
“It is a function of the apparatus design, the condition of the apparatus used, and the operational
procedure carried out. Flash point can therefore only be defined in terms of a standard test method,
and no general valid correlation can be guaranteed between results obtained by different test
methods, or with test apparatus different from that specified” (ASTM D93)

In general event it is not a rule:

flash point increase with the increase of the molecular weight (matter of volatility)
E.g: an abnormal low flash point in a automotive oil - possible presence of gasoline

Gear oil = 190-300 °C Motor Oil = 210-252 °C

17 Petroleum Oil = max 200-230 °C Synthetic oil = > 230 °C, up to 270 °C
 FLASH POINT II

Pensky-Martens Closed Tester

2 mL of lubricant
Calibration with distilled water and n-decane
Ignition source: flame burning butane
 POUR POINT

J. Wang Pour point, Encyclopedia

of Tribology, 2013 Springer ed, pp 2673-2678
Primary related to the low-temperature properties of a fluid

POUR POINT = is the temperature become semi-solid and loses flow

characteristics (ASTM D97, ISO 3016)
The lower is the temperature, the better quality is the oil.

In a lubricant indicates the paraffinic content, to lower with additives.

Synthetic oil contains no paraffins. They don’t need pour point depressant
additives.

Most petroleum lubricant: > -34°C even with additives

Synthetic lubricant without additives: -45 °C
Synthetic lubricant with additives: -60 °C

CLOUD POINT = the temperature at which the oil loses its clarity, i.e. develops
haze or cloudiness due to the start of crystal formation
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 ANILINE POINT

Defines the temperature at which equal volume if the lubricant and aniline are
miscible.

This temperature is indicative of the solvency characteristics of the oil.

In general, the lower is the aniline point, the greater is the solvency of the oil

ASTM D611 (last version 2012)

“useful as an aid in the characterization of pure hydrocarbons and in the analysis of hydrocarbon
mixtures. Aromatic hydrocarbons exhibit the lowest, and paraffins the highest
values. Cycloparaffins and olefins exhibit values that lie between those for paraffins and
aromatics. In homologous series the aniline points increase with increasing molecular
weight. Although it occasionally is used in combination with other physical properties in
correlative methods for hydrocarbon analysis, the aniline point is most often used to
provide an estimate of the aromatic hydrocarbon content of mixtures.”

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 THERMAL STABILITY

Thermal stability = resistance of a lubricant to break down or to change its

molecular structure (under influence of heat and absence of O2).
ASTM D2879 - isoteniscope method
ASTM E1131, ISO 11358 Thermogravimetric analysis
ASTM E1782, E537 Differential Thermal Analysis (DTA)
Significant decomposition (liquid decomposition and gas formation)

MINERAL SYNTHETIC (PAO)

340 - 380 °C 310 - 340 °C
methane, ethane, ethylene more differentiated monomers
Aromatic compounds: more stable 450 - 480 °C (PCB, PAH)
Organic esters: (260 - 316 °C) - the ester functional group the first degradation
site
A lot of additives has a low thermal stability
OXIDATION STABILITY = resistance in presence of air or O2. Good oxidation
stability = highly desirable. Unlike thermal stability that is more inherent to the
21 base stock, oxidation stability can be greatly improved by additives.
 ELEMENTAL AND STRUCTURAL ANALYSIS

On the other hand, chemical analysis can be applied also to the base stock

Mineral oil contains a wide variety of elements (some at ppm levels)

Refined process remove most of elements apart C, H, O, N, S.

Trace elements: AAS, ICP-AES, ICP-MS, X-RF, micro-elemental analysis

Not only to detect impurities, but also wear metals part and friction products
(B, Ba, Ca, Cd, Cr, Cu, F, Hg, Mg, Mo, Ni, P, Pb, Sb, Se, Si, Sn, Zn)

Micro-elemental analysis mostly for non-metal elements

The sample is burn at the elementary form and analysed into gas product with
different techniques
C, H, N ASTM D5291 IR or GC
Cl, organics ASTM D4929b microcoulometry
N ASTM D4629/D5762 Chemioluminescence
O ASTM D5622 Reductive Pyrolysis
22 S ASTM D5453/D6667 UV Fluorescence
 ISO TEST METHODS

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 HYDROCARBON / ORGANIC ANALYSIS

To identify the chemical structures that make the basis both of base stock and
additives.

MINERAL OIL: a challenge is the determination of the base stock composition

because it is a complex mixture (various types, sizes and structures).

SYNTHETIC OIL: structure determination is relatively straight forward for

well-defined structures and purities, in known-unknown proportion. The challenge
is done by the POLYDISPERSIVITY (wide molecular weight distribution).

More complex techniques: - GAS CHROMATOGRAPHY (GC, GCxGC)

- LIQUID CHROMATOGRAPHY (e.g. GPC)
- UV and IR SPECTROSCOPY
- NUCLEAR MAGNETIC RESONANCE (NMR)
- MASS SPECTROMETRY (MS)
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 GC-FID and GC-MS

www.chromatographyscience.it (2012)

Column: 15 - 105 m
specific for mineral
separation

solvent: n-hexane or
iso-octane

injection: 0.5-1 uL on-column

typical oven program:

W. Krasodomski and M. Krasodomski, Nafta-gaz 08-2010 ROK LXVI
50 °C to 300 °C at 10 °C/min
20 min hold time
Carrier gas: Helium, Nitrogen, Hydrogen
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 GC-FID II

26 K. Grob, Kantonales Labor Zurich (2011)

 GC x GC

2 GC columns:
one polar and
the second
non-polar

W. Krasodomski and M. Krasodomski, Nafta-gaz 08-2010 ROK LXVI

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 INFRARED SPECTROSCOPY I

- Probably the most accepted test to obtain structure and composition of a

lubricant
- Widely applied because non-destructive method (movement of molecules)
- Spectra range: 500-4000 cm-1
- IR spectra are sufficiently unique to help identify structural features of many
individual compounds

- Powerful if combined with different analytical techniques (GC, LC, MS)

- Easy to identify organic groups (heteroatoms: N, O, S, P)
- More difficult with all hydrocarbons (double bonds, aromatic rings)

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 INFRARED SPECTROSCOPY II

29 Rizvi (2009)
 EXAMPLE I: IR

R. Johnson,
The case of the poorly
blended fluid,
Hydraulics & Pneumatics
(2008)

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 EXAMPLE II: GPC

Gooss W, Korn A. BMW Group Dep. Lab, Germany

-Specific for automotive lubricants

-Chemical composition important to meet high performance requirements
-Analytical challenge from the analytical point of view, quantitative measurements
It is nearly impossible in a mixed base oil to identify typical groups
Chromatographic overlapped peaks

Example of modern lubricant: mineral oil + PAO + synthetic esters

1) Pre-separation step via Solid Phase Extraction (SPE) to separate esters based
components from PAO + mineral (POLARITY)
2) GEL PERMEATION CHROMATOGRAPHY (GPC) = LC, fractionation in accordance
to the size of solvated polymer clusters (porous separation matrix) +
commercial deconvolution software to separate overlapped peak-area
31 (separation of mineral oil from PAO)
 EXAMPLE II: GPC

Gooss W, Korn A. BMW Group Dep. Lab, Germany

FULL SYNTHETIC
MINERAL

Differential molar
mass distribution
(UV-PDA detector
at 280 nm)

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 LUBRICANT AND THE ENVIRONMENT

Since there are limitation of the use of the lubricant (recycling is possible, but
not a indefinite recondition), sooner or later used lubricant enter into the
environment.
It is necessary a specific regulation for environmental protection and
occupational health & safety.

Last generations of lubricant tent to be ENVIRONMENTALLY friendly,

compatible, acceptable, harmless, responsible.
GREEN FLUIDS like bio-base lubricant.

- BIODEGRADABILITY

- TOXICITY (AQUATIC)
In EUROPE an ECOLABEL for commercial lubricant

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 REFERENCES and USEFUL READINGS

- S.Q.A. Rizvi, Lubricant Chemistry, Technology, Selection and Design (a

comprehensive review), ASTM Publication MNL 59, 2009
ISBN 978-0-8031-7000-1

- L.R. Rudnick (eds), Synthetics, Mineral Oils, and Bio-Based Lubricants –

Chemistry and Technology, 2nd ed, CRC Press, 2013
ISBN 978-1-4398-5538

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 ANY QUESTIONS….?

THANK YOU FOR

YOUR ATTENTION
‫ا‬
Contact:
Dr. LAVA ROBERTO, PhD
email: roberto.lava@arpa.veneto.it

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