Four Stroke Presentation

www.crodalubricants.
com
Four-stroke Engine Oils
www.crodalubricants.com
Engine Oils, Friction and Wear
Industry Drivers
Improved fuel economy/lower CO
2
emissions
Low viscosity engine oils (e.g. OW, 5W)
Organic Friction Modifiers (OFMs) which give lower friction
and low friction durability
Chemical limits to ensure protection of emissions
systems
additives which reduce wear allowing for the reduction of
ZDDP levels
Improved ZDDP compatibility
Enhanced oil robustness
Base oils and OFMs which have greater stability
OFMs which have improved additive compatibility e.g. DI
packs
.
.
.
.
.
.
. .
.
. .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. .
.
.
.
.
.
.
.
.
.
. .
.
. .
.
. .
.
.
Oxide
Metal
Ester
lubricant
Group I IV
Lubricant
Organic
FM
Detergent
ZDDP
Anti-wear
Inorganic
FM
Dispersant
Surface Competition
= Interactions
Other additives
e.g. anticorrosion, etc
Croda Technologies
Esters and Organic Friction Modifiers
Ester lubricants
to reduce viscous drag
(low viscosity, low polarity and
low volatility)
C
O
F
Organic Friction Modifiers to reduce
friction coefficient and wear
High viscosity /
medium polarity
complex esters to
reduce wear.
Organic friction
modifiers to reduce
friction
Ester Lubricants and Organic Friction
Modifiers
Esters for Four-stroke
Applications
Esters for 4T applications
Priolube
1936
Priolube
1973
Priolube
1976
Priolube
3949
Priolube
3967
Priolube
3970
Priolube
3972
Priolube
3999
Chemistry Diester Polyol Mono-ester Diester Dimerate Polyol Diester Polyol
Kinematic viscosity @
100C (mm/s)
5.3 8.0 5.4 4.5 13 4.4 7.6 14
Kinematic viscosity @
40C (mm/s)
26 46 26 16 94 20 41 90
HTHS viscosity (m.Pas) 1.54 3.15 2.07 - 4.64 1.93 3.23 4.65
CCS at -25C (m.Pas) 2270 3790 - - 11000 870 3600 14000
CCS at -30C (m.Pas) 4130 6940 1460 - 19700 1400 6360 29400
CCS at -35C (m.Pas) 8150 14000 2550 - 36700 2430 12000 65700
Non polarity index (NPI) 82 130 214 - 210 61 113 186
Viscosity index 139 148 157 186 145 140 156 144
Flash point COC (C) 244 280 260 230 290 250 261 290
Pour point (C) -54 -44 -33 -18 -45 -51 -51 -27
Noack weight loss at
250C/1hr (%)
6 <1 3 - 1 3 3 1
Typical / maximum
treat-rates w/w (%)
12 25 25 60 <=100 5 15 80 100 8-15 20 45 65 100
Non Polarity Index (NPI) of Esters
Number of Carbon atoms x Molecular weight
Number of Carboxylic groups x 100
NPI =
High Seal Swell
High Wear
Low Seal Swell
Low Wear
P3970
P3972
P1976
P1973
Low Viscosity Esters
Improved fuel economy / lower CO
2
emissions can be gained by
using low viscosity engine oils (e.g. OW, 5W)
This requires the use of low viscosity Gp III and Gp IV base fluids
Low viscosity base oils are more volatile i.e. give higher Noack
volatility
Esters can be used as co-base fluids with Gp III or Gp IV base
oils to give desired viscometric profiles and meet volatility
requirements
Low viscosity esters are well suited for use in niche high
performance racing oils
0
5
10
15
20
25
30
35
2 3 4 5 6 7 8
Vi scosi ty at 100C
%

N
o
a
c
k

2
5
0
C
/
1
h
r
Group III Group IV Group V
Noack Volatility
Low Viscosity Low Volatility Esters
Priolube 1544 Priolube 1976 Priolube 3949 Priolube 3963
Chemistry Saturated Mono-
ester
Saturated Mono-
ester
Saturated Di-
ester
Saturated Di-
ester
Kinematic viscosity @ 100C (mm/s) 2.6 5.4 4.5 3.2
Kinematic viscosity @ 40C (mm/s) 8.2 26 16 11
HTHS viscosity (m.Pas) - 2.07 - -
CCS at -25C (m.Pas) - - - <500
CCS at -30C (m.Pas) - 1460 - <500
CCS at -35C (m.Pas) - 2550 - <500
Non polarity index (NPI) 90 214 - 55
Viscosity index 168 157 186 149
Flash point COC (C) 225 260 230 230
Pour point (C) -3 -33 -18 <-60
Noack weight loss at 250C/1hr (%) 20 3 - 13
Ester Lubricants Summary
Croda has a range of esters for use in engine oil formulations
Different chemical compositions different attributes
P1936, P3970 and P3972 are effective as:
Additive solubilisers
Seal swell agents
P1976, P1973, P3949, P3967 and P3999 are suitable for use as
(co-) base fluids in high performance engine oils
New fuel efficient, low viscosity engine oils will require the use of
low viscosity, high oxidatively stable base oils. P1976, P3949 and
P3963 can be considered as high performance components in the
development of such engines oils
Organic Friction Modifiers
O O
adhesive
hydrogen bonding
dipole-dipole
interactions
Van der Waals
forces
Oxidised and/or hydroxylated metal surface
Van der Waals
forces
Polar heads
Long, non-polar chains
NH
2
O
OH
OH
O
O
Oleylamide
Glycerol mono-oleate
FM examples
Organic Friction Modifiers (OFMs)
Which OFM To Use ?
Friction modifiers are required to improve performance in a
number of areas
Reduce friction deliver improved fuel efficiency
Friction durability maintain improved fuel efficiency over longer
drain intervals
Reduce wear contribute to lower SAPS
Friction modifiers formulatory issues
Solubility in the base oil
Compatibility with antiwear agents
Compatibility with inorganic FMs
Compatibility with DI packs
Each formulation may need a different solution
A range of OFMs is required
Ca(OH)
2
CaCO
3
PAO PAO
PAO
PAO
PAO PAO
PAO
PAO
Ca(OH)
2
CaCO
3
PAO PAO
PAO
PAO
PAO PAO
PAO
PAO
Ca(OH)
2
CaCO
3
PAO PAO
PAO
PAO
PAO PAO
PAO
PAO
Ca(OH)
2
CaCO
3
PAO PAO
PAO
PAO
PAO PAO
PAO
PAO
0 0.5% GMO
>= 1.5% GMO
=AB Sulphonate
=GMO
=AB Sulphonate
=GMO Work carried out in collaboration
with Bristol University and Infineum
OFM + Detergent Interactions
Crodas Friction Modifiers
Oxidatively stable OFMs
Partial esters (conventional)
Atsurf 595
Priolube 1407
Cithrol PG32IS
Perfad FM 3336
Priolube 2040
Fatty Amides (conventional)
Crodamide O
Perfad FM 3339
Perfad 4000
Polymeric Friction Modifiers (new !)
Perfad 3000
Perfad 3050
Croda OFMs are free from sulphated ash, phosphorous and sulphur
Functionality Pour point (C) Iodine
value
(gl/100g)
Cloud
point (C)
Hydroxyl
value
(mgKOH/g)
Atsurf 595
Partial ester 11 79 8 220
Cithrol PG32IS
Polymeric partial ester -15 2 15 190
Crodamide O
Amide
Pastille (melt
point 69C) 90 Pastille 9
Perfad 4000
Amide -30 10 -25 131
Perfad FM 3336
Partial ester -25 5 12 204
Perfad FM 3339
Amide/ester blend -12 5 -5 289
Priolube 1407
Partial ester 0 79 8 220
Priolube 2040
Partial ester -6 1 7 197
Physical Properties of Conventional
Friction Modifiers
Coefficient of Friction Properties
Mini-Traction Machine (MTM)
MTM Run Conditions
Ball on smooth disk
ANSI 52100 Steel
Load = 36N
(1GPa contact pressure)
Speed = 0-2m/s
Slide/Roll/Ratio (SRR) 50%
Sample
Each plot is an average of three runs
Sample heated to 100C, tested three times and results averaged
Sample heated to 150C, tested three times and results averaged
MTM 91.5% PAO 6 + 8% P3970 +
0.5% OFM at 100C
0
0.02
0.04
0.06
0.08
0.1
0.12
0.01 0.1 1 10
log m/s Speed
F
r
i
c
t
i
o
n

C
o
-
e
f
f
i
c
i
e
n
t
Priolube 1407 Crodamide O Perfad 3336 Cithrol PG32IS
Perfad 4000 PAO6/Priolube 3970 BLK Perfad 3339 Crodamol PDO
0
0.02
0.04
0.06
0.08
0.1
0.12
0.01 0.1 1 10 log m/s Speed
F
r
i
c
t
i
o
n

C
o
-
e
f
f
i
c
i
e
n
t
Priolube 1407 Crodamide O
Perfad 3336 Cithrol PG32IS
Perfad 4000 PAO6/Priolube 3970 BLK Perfad 3339 Crodamol PDO
MTM 91.5% PAO 6 + 8% P3970 +
0.5% OFM at 150C
OFM Testing
Testing OFMs in just the base oil can be misleading as it does not
readily take into account the interactions with other additives
Some friction modifiers may appear to have limited solubility in
some base oils but are more readily soluble in fully formulated
engine oils
Croda has found that sometimes changing one component
/additive in the base oil can have a marked effect on friction
modifier performance
What may appear to be a moderately performing OFM in a
partially formulated oil may actually be an excellent OFM in a fully
formulated engine oil
If possible, OFMs should be screened in the fully formulated base
oils
MTM Friction Evaluation
5W/30 Formulation
5W/30 Formulation - Friction vs Temperature
MTM - 30 N - 0.06 m/s - Ball-on-disk - Rough disk
0,06
0,07
0,08
0,09
0,10
0,11
0,12
0,13
0,14
0,15
0,16
40 50 60 70 80 90 100 110 120 130 140
Temperature [C]
F
r
i
c
t
i
o
n

c
o
e
f
f
i
c
i
e
n
t

[
-
]
5W/30 formulation + 1.5% P1407 + 1.5% FM 3336
+ 1.5% FM 3339
Fuel Economy M111FE Test
1.6
1.8
2
2.2
2.4
2.6
2.8
% FEI
5W30 Oil 1.5% P1407 1.5% FM 3339 1.5% FM 3336
Good agreement between ranking in MTM and M111FE results
Conventional OFM Summary
Croda has a range of conventional organic friction modifiers
Different chemical compositions different attributes
OFMs are known to be effective in:
Reducing friction and helping to deliver improved fuel efficiency
Enhancing low friction durability, hence maintaining improved fuel
efficiency over longer drain intervals
Reducing engine wear, hence can be used in lower SAPs oils
Selection of OFMs is key to maximising engine oil performance
It is dependent upon base oil and other additive components used in
the formulation of engine
A range of OFMs should be considered in developing new engine oils
OFMs should be tested in fully formulated engine oils
Polymeric Organic Friction Modifiers
Croda has developed a new range of organic friction modifiers based on
polymer chemistry:
Perfad 3000
Perfad 3050
Perfad 3000 and Perfad 3050 display an outstanding ability to reduce the
coefficient of friction of engine oils to levels unachievable with
conventional organic friction modifiers
This enables formulators to develop engine oils that improve fuel
economy and reduce emissions
Perfad 3000 and Perfad 3050 also demonstrate excellent film forming
properties which offers the potential to reduce engine wear and to
improve engine durability
Key Features of the Perfad 3000 Series
Perfad 3000 and Perfad 3050 are high viscosity polymers which can be
provided in a diluted form for improved ease of handling
Perfad 3000 and Perfad 3050 are based only on C, H and O and do not
contain sulphur, phosphorus or sulphated ash
Perfad 3000 and Perfad 3050 are more oxidatively stable than conventional
organic friction modifiers
Engine oils formulated with Perfad 3000 and Perfad 3050 can have
coefficients of friction significantly lower than oils formulated with
conventional organic friction modifiers
Perfad 3000 and Perfad 3050 are effective at low dose rates, typically 0.1% -
0.5%
Typical Physical Properties
* Kinematic viscosity mm
2
/s
Perfad 3000 Perfad 3050 Glycerol mono-oleate
Physical form
Viscous liquid Viscous liquid Liquid
Colour
Dark brown Dark brown Pale yellow
Dynamic viscosity @ 40C (mPa.s)
10640 114000 84*
2730 23300 -
990 6690 -
440 2700 10*
Iodine value (gl/100g)
25 6.5 79
Acid value (mgKOH/g)
7.5 4 0.5
Density at 20C (g/ml)
0.97 0.97 0.96
Flash point (C)
270 280 215
Pour point (C)
>21 >21 0
SAPS (% w/w)
Zero Zero Zero
Demonstration of Friction Properties in a
Simple Reference Fluid
A blend of 90% PAO6 + 10% Priolube 3970 has been used a reference
fluid
Perfad 3000 and Perfad 3050 have been added to the reference fluid in
order to demonstrate their effectiveness in the absence of any other
surface active components that are used in engine oil formulations
(0.5%)
Perfad 3000 has been added to the reference fluid at different treat-rates
to demonstrate concentration effects (0.1%, 0.2% and 0.5%)
Priolube 1407 (glycerol mono-oleate) has been used as a reference
friction modifier
Frictional Properties at 40
O
C
0.5% Treat-rate
O
C
0.5% treat-rate
O
C
0.5% treat-rate
Perfad 3000 at 40
O
C
0.1%, 0.2% and 0.5% Treat-rates
Perfad 3000 at 100
O
C
Perfad 3000 at 150
O
C
Example of their Use in an Engine Oil
Formulation
Perfad 3000 and Perfad 3050 can be used in the formulation of
passenger car motor oils and heavy duty diesel engine oils
As an example, Perfad 3050 has been used in the formulation of a
10W40 HDDEO:
Reference oil:
13% CatenexT121 (Shell - Group II basefluid)
6% Paratone 8002 (VII +PPD)
13% Add pack
Perfad 3050 has been added to the reference oil at 0.5%, 1.0% and 2.0%
treat-rates
Perfad 3050 in a 10W40 HDDEO
O
C
O
C
O
C
Film Forming Characteristics
Perfad 3000 and Perfad 3050
both form films between
moving surfaces
Their film forming
characteristics can be
demonstrated using a thin
film interferometry test rig
The reference fluid is PAO6 +
10 % Priolube 3970
Perfad 3000 and Perfad 3050 form thicker
films than conventional lubricants 40
O
C
O
C
O
C
Current Registration Status
Europe (REACh
compliant - polymer
exempt)
USA (TSCA)
Canada (DSL)
J apan (ENCS)
China (IECSC)
Korea (ECL)
Australia (AICS)
Perfad 3000 Perfad 3050
Europe (REACh
compliant - polymer
exempt)
USA (TSCA)
J apan (ENCS)
Incorporating Perfad 3000 and Perfad
3050 in Engine Oil Formulations
Perfad 3000 and Perfad 3050 can be used effectively in the
development of new engine oils but:
their effective use is dependent upon using other additives which are
compatible and do not act antagonistically with them
components within some engine oils are surface active and can prevent the
polymeric friction modifiers reaching the metal surfaces and reducing the
friction between moving parts
Croda recommends testing Perfad 3000 and Perfad 3050 in a range of
formulations to determine their suitability and effectiveness
In formulating the engine oil, Croda recommends blending Perfad 3000 and
Perfad 3050 with the most polar additives first before blending into the less
polar components , such as, the base oil
Summary for Polymeric Friction Modifiers
Perfad 3000 and Perfad 3050 are a new generation of friction modifiers, exhibiting
outstanding friction reducing characteristics in base oils and in formulated engine oils
Perfad 3000 and Perfad 3050 are SAPs free
Perfad 3000 and Perfad 3050 can be used to formulate both PCMO and HDDEOs but
care needs to be taken when formulating to ensure that they are fully solubilised within
the engine oil and in the selection of other components, most typically the detergent /
dispersant additives
Perfad 3000 and Perfad 3050 offer the potential to reduce friction and to contribute to
both fuel efficiency improvements and in the reduction of emissions
Perfad 3000 and Perfad 3050 exhibit excellent film forming properties with the potential
to reduce wear and improve engine durability
Perfad 3000 and Perfad 3050 are high viscosity polymers but can be supplied in a
diluted form
Croda looks forward to working with you on developing formulations containing Perfad
3000 and Perfad 3050 !
High Viscosity Complex Esters
Priolube 3986
Novel ester based technology which has been
optimised for anti-wear boosting effect
Acts by forming stable surface films
Zero SAPS
Can be used to replace some ZDDP and still give
equal or better wear performance
Typical dose-rate 0.5%
Typical physical properties
Priolube 3986
Viscosity at 40C (mm/s)
47000
Viscosity at 100C (mm/s)
2000
Viscosity index
277
Flash point COC (C)
325
Pour point (C)
6
TAN (mgKOH/g)
0.10
Noack weight loss at 250C/1 hr (%)
<1
Renewability (%)
82
= Complex polymeric ester
Hydrodynamic The more polar thick
complex ester sticks to the surface.
Bulk viscosity can still be low giving
good efficiency
EHD At low speed the bulk
lubricant is squeezed out of the
contacts. The thicker, more polar
complex ester remains. This boosts
film thickness, reducing wear and
improving fatigue life
Base stock
By cleverly controlling polarity a viscous surface film can be developed
Film forming properties of high viscosity
esters
Film Thickness Test Rig
EHL film thickness 1 to 1000 nm
Speed 0 to 5 m/s
Slide/roll ratio 0 to 200%
Load 0 to 50 N
Temperature Ambient to 150C
Contact pressure Max. 0.7 GPa
1
10
100
1000
0.001 0.01 0.1 1 10
Entrainment speed, U m/s
F
i
l
m

T
h
i
c
k
n
e
s
s
,

h
0

n
m
8% P3970 in PAO6
+0.5% Priolube 3986
Base stock
= Complex ester
Film Forming Characteristics of Priolube
3986 in PAO6
Metal
Metal oxide
Hard Polyphosphate Chemisorbed ZDDP reacted layer
Organic rich ZDDP film
ZDDP
Mechanisms
Physical vs. Chemical
Polarity
Viscosity
Esters and ZDDP Containing
Formulations
0
10
20
30
40
50
60
Follower
Scuffer (%)
Cam Nose
wear (u)
Cam Lobe
Wear (u)
Fe (ppm)
Standard ZDDP Treat Rate 0.5% ZDDP + 0.5% P3986
Camshaft Lobe Wear in a Nissan KA 24E engine. Tested on Group III 5W formulated oil
Sequence IVA Valve Train Wear
Complex Esters Summary
Priolube 3986
Forms thick films at low speeds
giving excellent wear and anti-
fatigue performance
Can be used to improve engine
wear performance of ZDDP
containing formulations
Disclaimer
The information in this publication is believed to be accurate and is given in good faith
but no representation or warranty as to its completeness or accuracy is made.
Suggestions for uses or applications are only opinions. Users are responsible for
determining the suitability of these products for their own particular purpose.
No representation or warranty, express or implied, is made with respect to information
or products including without limitation warranties of merchantability or fitness for a
particular purpose or non-infringement of any third party patent or other intellectual
property rights including without limit copyright, trademark and designs.
Any trademarks identified herein are trademarks of the Croda group of companies.
Copyright Croda Europe Ltd 2011. All Rights Reserved

Four Stroke Presentation

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Four Stroke Presentation

Uploaded by

Copyright:

Available Formats

www.crodalubricants.

You might also like