A new insight into the benefits of

synthetic esters in lubrication

Siegfried Lucazeau

STLE Annual meeting May, 2015

 Agenda

I. General properties of synthetic esters

The relationship between chemical structure and properties
The useful features of esters in lubrication

II. Traditional use of esters

Various demanding or severe lubricating applications :
from jet engines to oven chains

III. Requirements on future lubricants :

how esters will contribute
High performance and lowered environmental impact :
esters take up the challenge

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GENERAL PROPERTIES OF
SYNTHETIC ESTERS

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 Volatility, Rheology
Esters show lower volatility and higher flash points than
hydrocarbons of equivalent viscosity, thanks to stronger -
intermolecular attraction
+
Esters show high Viscosity Indices and low Pour Points -
as they generally exhibit linear, asymmetric structures

Alkyl Neopolyol Complex

Property Unit Naphthenic Gr I Gr III PAO Naphthalene
Diester ester ester

Viscosity at 100C mm/s 4.6 5.0 5.1 5.1 4.8 5.3 4.9 5.7

Viscosity at 40C mm/s 31.3 29.8 26 24.1 28.7 26.6 22.6 28

Flash point COC C 194 195 226 245 232 234 267 265
Evaporation
% 43.4 38.3 19.3 5.6 12.0 4.7 2.3 2.6
250C 1 h*
Viscosity Index - 25 92 122 145 81 136 148 160
Pour Point C -51 -10 -18 -46 -48 -54 -38 -38

* Correlation by TGA - ASTM D6375

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 Tribology

Esters show high affinity with positively charged

metal surfaces, generating friction modification

Alkyl Neopolyol Complex

Property Unit PAO Gr III Naphthalene Diester
ester ester

Viscosity at 100C mm/s 3.95 4.25 4.82 3.22 4.40 5.73

Viscosity at 40C mm/s 17.3 19.7 28.7 11.6 19.7 28.0

HFRR -5N 60C 75 mn --

0.492 0.311 0.296 0.225 0.230 0.220
Friction coefficient

Alkyl Neopolyol
Property Unit Gr I Gr III Naphthalene PAO Diester
ester
Viscosity at 100C mm/s 4.18 4.25 4.82 3.95 3.56 4.40

Viscosity at 40C mm/s 21.3 19.7 28.7 17.3 13.7 19.7

4 ball Wear Scar mm

40 kg, 1 h 1.10 0.76 0.91 0.73 0.85 0.64
(ASTM D4172)
60 kg, 30 min mm - - - 1.78 - 0.71

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 Polarity

Esters are good polar solvents and help dissolve

components into non polar base stocks
Esters show detergency and dispersivity properties

Micro-Coking Test
PAG Neopolyol ester Anilin Points
GFC-Lu-27-A-13 PAO 40
230-280C 40 mm2/s 40 mm2/s

Oil quantity: 0.6 cm

Plate inclination: 1 to the

100C
hot point Group I, II, III, PAO
130C
Cold point temperature:
variable (200C to 280C)
90C Naphthenics
Hot point temperature:
variable (250C to 330C)
32C Alkyl Naphthalenes
Duration: 90 minutes

10C Esters

-30C PAG

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 Thermo-oxidative stability
Ester function is highly resistant to oxidation, and increases oxidation stability of adjacent carbon atoms
Neopentyl structure inhibits -elimination and greatly improves thermal stability
Branched, short hydrocarbon chains further improve resistance to oxidation

Chemical function -elimination Neopentyl structure Branched acid

ASTM D4636 Alkyl Neopolyol Neopolyol

204C 72 h Gr I Gr III PAO Diester
Naphthalene ester 1 ester 2

Test tube

Deposits

5 mm2/s @100C fully formulated fluids

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 Coking propensity
Esters show low coking and deposit formation properties
Use of branched hydrocarbon chains favours clean decomposition pathways once
oxidation is initiated
Micro-coking Test
Complex Complex Neopolyol
230-280C Unit PAO PAG
ester 1 ester 2 ester
40 mm/s
Deposit temperature C <230 <230 <230 <230 273

Average Merit - 6.6 5.5 7.9 6.9 8.8

Metal plates -

ASTM D4636 Ester Ester

Test tube Deposits
204C nC8-10 Iso-C8, iso-C9

Ester
nC8-10

Ester
Iso-C8
iso-C9

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 Environmental profile
Ester function may be degraded by bacteria, making these
compounds biodegradable
Esters can be made of acids coming from vegetable
sources : they may contain high amounts of renewable
carbon

Base fluid Mineral PAO PAG Esters

Typical
biodegradability
OECD 301B
Max. 40% Max. 60% 10 - 70% 10 - 95%

Renewable
0% 0% 0 20% 0 - 100%
carbon content

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TRADITIONAL USE OF ESTERS

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 Jet engines, compressors
Aircraft gas turbines require lubricants showing :

superior thermal and oxidative stability (up to 220C in bulk)

low liquid and vapour phase coking (hot parts in
the engine up to 375C)

Refrigeration compressors using HFC require lubricants showing :

the right miscibility/immiscibility profile with HFC

very low pour points
good lubricity

In volumetric air compressors, lubrication may take place in the

compression chamber :

Need for high resistance to oxidation (up to 230C)

Need for excellent deposit control (safety issue : valve sticking,
auto-ignition)

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 2-stroke engines
2-stroke engine oils :

settle on the metal surface of combustion chamber

mix with gasoline/air and burn, for the most part
is released unburnt with gasoline, for a significant part (total loss
lubrication)

Clean burning properties of esters, detergency, natural lubricity, good

biodegradability : precious features for 2-stroke engines

Compared to mineral oils, ester based 2-stroke engine oils :

reduce exhaust smoke

reduce wear in engines
reduce deposit and varnish formation
reduce polycyclic aromatic hydrocarbon levels in exhaust
gases by up to 25%
show a much better environmental profile

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 Oven chains

High temperature chain oils face :

High evaporation rates

Thermal decomposition
Oxidation and formation of gummy or carbonaceous residues
Safety issues through ignition and fires

Synthetic esters have been providing :

very low volatility, consequently high flash and fire points

high resistance to thermo-oxidation
Low deposit formation features

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 From high to low temperatures

Use of monoester base fluid allows to formulate a hydraulic

fluid for extremely low temperature environments :

KV 40C : 3.4
KV -70C : 2100
Pour Point : -80C
Flash Point COC : 160C

Synthetic esters combine :

Excellent low temperature properties

Low volatility and high flash points

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REQUIREMENTS ON FUTURE
LUBRICANTS : HOW ESTERS
WILL CONTRIBUTE

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 Tougher requirements in modern lubrication

Evolution on lubrication requirements is driven by :

Commercial competition : the race for better performance, more durability,

reduced costs

OEM requirements, standards and legislation : require more energy efficiency,

induce higher power density, provide better safety

Sustainability : increasing demand for low environmental impact,

renewable lubricants

This translates into :

Stronger temperature stress on lubricants Thermo-oxidative stability

Increased durability, cleanliness Lower deposit formation
Reduced friction Friction modification
Lower viscosities Lower volatility
Biodegradable, renewable and harmless lubricants Without compromising performance

Market drivers will favour synthetic performance products

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 Modern PCMO
PAO 4 POLYOL ESTER
Future engine oils will be :
KV100 3.9 4
KV40 17.4 17.4
thinner (fuel economy improvement) VI 124 134
submitted to higher temperatures, for longer times Pour Point -68 -63
CCS-35 1424 1766
submitted to the increasing presence of biofuels NOACK 13.2 6.4

hence the need for lower volatility, higher thermo-oxidative stability and improved cleanliness

Tests on 5W-30 engine oils, ACEA C1-2012 and ILSAC GF-5 performance level

ILSAC GF-5 ACEA C1-2012

Additives - 14,72 Additives - 26,20

Group III 4 mm2/s 9,85 Group III 4 mm2/s 53,80
PAO 4 mm2/s 20,00 PAO 4 mm2/s 20,00
Group III 6 mm2/s 55,43
ILSAC GF-5 test
ACEA C1-2012 test
Additives - 14,72
Group III 4 mm2/s 9,85 Additives - 26,20
Neopolyol ester 4 mm2/s 20,00 Group III 4 mm2/s 53,80
Group III 6 mm2/s 55,43 Neopolyol ester 4 mm2/s 20,00

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 Volatility, cleanliness
MCT 230-280 GF-5 GF-5 + ester C1-2012 C1-2012 ester
TGA 200C O2 TDD 232 243 248 248
Merit A 7.7 8.6 5.3 7.7
Merit B 8.4 9.0 9.6 9.8
Moyenne 8.0 8.8 7.4 8.7

TEOST 33C GF-5 GF-5 + ester

Rod Deposit mg 18.4 13.1
Filter Deposit mg 5.0 3.2
Total Deposit mg 23.4 16.3

Esters may be used to reduce

volatility and deposit
formation in engine oils

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 Chain oils, a step further
The ideal profile of branched neopolyol esters :
Evaporation

Slow evaporation
Quick decomposition
Pyrolysis
Little residue left

280 mm2/s, trimellitate/neopolyol ester based

250 mm2/s, 100% branched neopolyol ester based
TGA Residue 400 mm2/s, 100% branched neopolyol ester based, AO 1
250C - O2 400 mm2/s, 100% branched neopolyol ester based, AO 2

Micro-Coking Test 250 mm2/s - trimellitate/iso-paraffin 250 mm2/s branched neopolyol ester
230-280C
Deposit Temperature C 253 > 280
Average Merit -- 9.3 10.0

250-300C
Deposit Temperature C 250 259
Average Merit -- 7.9 8.6

280-330C
< 280 < 280
Deposit Temperature C
-- 2.3 6.7
Average Merit

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 Optimizing ester chemistry
Properties Results Units Test methods Micro-Coking Test Fully formulated chain oil
Kinematic viscosity at 40C 380 mm2/s ISO 3104 230-280C
Deposit Temperature C > 280
Kinematic viscosity at 100C 26 mm2/s ISO 3104 Average Merit -- 10.0
Flash point COC 290 C ISO 2592
Volatility, 6h 200C 2.2 mass % ASTM D972
Volatility, 1h 250C 0.3 mass % ASTM D6375
250-300C
Thermogravimetric analysis Deposit Temperature C > 300
280 C -
Onset temperature, O2 Average Merit -- 10.0

Dynamic TGA
Neat ester 280-330C
Deposit Temperature C < 280
Average Merit -- 7.1

Optimized ester chemistry, suitably

additized, achieves outstanding high
temperature performance

Such chain oils can withstand

temperatures of up to 300C
TGA 250C - O2
Formulated chain oil

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 Pushing the limits on greases

TEST RESULTS RESULTS

PROPERTIES CONDITIONS UNITS
METHODS Grease 1 Grease 2

P0 ASTM D217 -- 1/10 mm 343 322

P60 ASTM D217 -- 1/10 mm 346 330
Dropping
ASTM D2265 -- C >300 >300
point
Oil separation ASTM D6184 30 h - 200C %m 6.9 5.9
Evaporation ASTM D2595 22 h - 200C %m 4.2 4.6

Bentonite/neopolyol ester greases

High temperature greases suitable for

temperatures of up to 230C may be
formulated on the basis of high thermal
ESTER stability neopolyol ester
based
greases

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 Performance and low environmental impact
Whilst future hydraulic fluids will need to be:

Resistant to higher temperatures

Robust anti-wear fluids
Cleaner products
More consistent in viscosity
Fire resistant

they will also have to account for improved environmental profile, as requested by latest standards (European Ecolabel, Vessel General
Permit, US Biopreferred)

Test ISO VG 46 ISO 15380

Properties
Method European Ecolabel compliant Biodegradability : >60% (OECD 301B)
Composition -
Saturated ester :
Additives :
98.746% Complex ester :
1.254% Additives :
99.095%
0.905%
Renewable carbon content : >50%
2
Kinematic Viscosity, mm /s
100C ISO
7.9 8.31
3104
40C 45.6 45.0

Viscosity Index ISO

2909
144 162 Synthetic esters provide:
ISO
Flash Point, C 281 260
2592
Foam properties, ml ISO
0-0, 0-0, 0-0 0-0, 10-0, 10-0
High resistance to oxidation
Sequence I, II, III 6247
ISO 9.1
Natural lubricity
Air release (50C), min 1.9
9120
ISO 25
High VI, improved shear stability
Water separability (54C), min 10
6614
Dry TOST, hours
ISO
>7000 >2100
High flash and fire points
4263-3
RPVOT, min
ASTM
833 - High biodegradability
D2272
FZG Load Carrying (A/8.3/90) ISO
10 >12
High renewable carbon content
Fail Load Stage 14635-1
Van Pump wear (V104C)
ISO 4.1
Cam ring, mg 2.0
20763
Vanes, mg 12.3 1.1

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 High viscosity and low environmental impact

High viscosity does not mean no biodegradability

Highly viscous ester chemistry can achieve high levels of biodegradability

High viscosity ester chemistry

ISO VG 320 : 67% biodegradability (OECD 301B)

ISO VG 1000 : 79% biodegradability (OECD 301B)

Biodegradable, viscous esters can be used to

formulate greases for

bearings
wire ropes
open gears

in compliance with the Vessel General Permit or the

European Ecolabel requirements

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 New trends, growing interest

Power density Energy efficiency Durability

SYNTHETIC ESTERS
Environmental
impact
Sustainability Safety

High performance
Sustainability

Low environmental
impact
Demand for higher Durability
performance will
exploit unexpected
benefits of esters

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THANK YOU !

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