Sarah Lundgren
Tribo Days 6-8 November 2012
Organic friction modifiers in engine oils –
Fatty amines and fatty amine ethoxylates
Overview
-What is AkzoNobel Surface Chemistry’s Fatty Amine
Chemistry
-Ongoing investigations
- Friction and wear of fatty amines and fatty amine ethoxylate
-Summary
Petroleum and Water applications
AkzoNobel’s position in the Lube Oil
Additive Market
Surface Chemistry | Lubes & Fuels
3
AkzoNobel Surface Chemistry
Fatty Amines Process Overview
Neo-Fat®
Armid®
Amidation
Raw Materials:
Animal Based Fats
Vegetable Based Oils
Fat Splitting
Distillation
Nitrilation
Esterification
Quaternization
Arquad®
Ethoquad®
Armosoft®
Armolube T®
Armeen®
Duomeen®
Triameen®
Hydrogenation
Alkoxylation
Ethomeen®
Propomeen®
Ethomid®
Ethofat®
Oxidation
Oxidation
Aromox®
Half Crude Gly.
Petroleum and Water applications
Petroleum and Water applications
A world of Fatty Amine Derivatives
Ethomeen
Propomeen
Triamine
Duomeen
Triameen
Tetrameen
Tetraamine
Petroleum and Water applications
Diamine Chemistries
O
OH
N
R
NH
R
+
NH N
2
N
OH
ed diamine
Diamine
HO
+
CH3
uaternary
OH
+
R
N
OH
CH3
2 Cl
N
CH3
CH3
Trimethyl diamine
diquaternary
DuomeenEthoxylated
T
Duomeen TTM
NH
R
Also ethoxylate di, tri and
tetra amine chemistries
CH3
N
CH3
CH3
+
CH3
N CH
3
CH3
NH2
O
2 O
2 Cl
R
+
NH2
R'
+
NH3
Diamine salt
Duomeen TDO
Petroleum and Water applications
Fatty chain
OH
N
OH
Fatty chain
Tallow, oleyl, coco, and erucyl
Coco (12)  Tallow (18) Erucyl (22)
Longer chain
Oleyl (95%)  Tallow (46%)  18 (0%)
Less unsaturation
Petroleum and Water applications
Ongoing research
Two long term investigations in-house
• Screening of existing products (catalogue) and new in the MTM
in combination with ZDDP only
• Fundamental understanding of friction modifiers in oil – both in
bulk and at surfaces
Many additives in an oil
and a lot interactions
taking place.
Beginning with
interactions of amine
friction modifiers and
antiwear additive ZDDP
Petroleum and Water applications
Samples
• A primary / secondary blend of ZDDPs (0.5wt%)
• Group III base oil from Nesteoil
• 0.5wt% FM
Petroleum and Water applications
Background ZDDP
Distribution of ZDDP antiwear film
Patchy film
81GPa
25GPa
10-100nm
150nm
Properties – hardness
Chemical composition(3)
• Increasing hardness closer to the
surface
• Alkyl phosphate precipitates rinse off
with solvent.
25-40GPa
Alkyl
phosphate
precipitates
• Long chains
• Short chains
Zinc Sulphide
90GPa
ZnS
(1) Warren et el, Trib. Letters, 4 (1998) 189
(2) Graham et al. Trib. Letters 6 (1999) 149; Nicholls et al. Trib. Internat. 38 (2005) 15
(3) Bec et al. Proc. R. Soc. London, 455 (1999) 4181
(Poly)phosphate
Steel surface
Petroleum Applications
Techniques for measuring friction and
wear
Valve Train
Journal Bearings
Hydrodynamic
lubrication
Mixed lubrication
Boundary lubrication
Friction Coefficient
Piston Rings
Oil Film Thickness/Surface Roughness (or
N/P)
12
Techniques
Minitraction machine (MTM) with film thickness measurement
• The MTM is run with 120C, 20N and a slide roll ratio of 50%.
• Measure at constant speed (200mm/s), load and temperature for two
hour but stop for Stribeck curves at 0, 15, 30, 60 and 120 min.
• A lot of data, here we show the Stribeck curve after two hours and the
friction vs time curves.
High frequency reciprocating rig (HFRR)
• The HFRR is run at 120 C, 400gram, 50Hz with stroke length of 1mm.
• Here we report wear scar data.
µ
Time
Petroleum and Water applications
Changes backbone and head group
- Adding methyl groups to an amine increases the friction.
- Secondary amine performs worse than primary.
-It is worse to change the head group than the hydrocarbon chain.
Perhaps two chain per molecule helps with the packing.
R
NH
R
Secondary amine
Petroleum and Water applications
Number of EO groups and comparison to
PO groups
OH
R
Increased degree of ethoxylation increases the friction.
N
OH
Propoxylate worse than ethoxylate.
O
R
m
N
H
Not all friction modifiers reduce friction compared to ZDDP.
OH
O
n
H
R
N
OH
Petroleum and Water applications
O
Number Hof
amines
OH
R
N
CH3
CH3
N
N
+
+
R
OH
N
OH
2 Cl
Increasing from one to two amines
OH increased the friction.
HO
Ethoxylated diamine
Methyl groups on diamine increases friction.
NH
R
Ethoxylated
NHdiquaternary NH
R
2
N
N
NHR
2
Diamine
CH
3
Salt of oleic acid and diamine better than only diamine.
CH3
R
+
N
CH3
+
CH3
N CH
3
CH3
CH3
CH3
O
Trimethyl diamine R'
2 O
2 Cl
R
+
NH2
+
NH3
Three amine groups performs really well.
Diquaternary
Diamine salt
Petroleum and Water applications
Film thickness
All friction modifiers reduce the antiwear film thickness.
A thin film usually provide low friction.
A disturbance in the antiwear film formation does not have
to result in increased wear.
ZDDP
Armeen DMTD
311µm
242µm
Duomeen T
Ethomeen T
197µm
219µm
Armeen T
246µm
Petroleum and Water applications
Summary
-ZDDP anti wear films show high friction giving a negative effect on
Fuel Efficiency.
-Early work suggests that optimal choice of Fatty Amine
Chemistries can bring benefits in reduction of friction and film
thickness
-Most amines tested reduce friction in boundary and mixed
-Methyl Groups on amine and diamine and Ethoxylates on amine
perform worse than only amine. Two hydrocarbon chains worse
than one. But changing head groups worse than fatty chain.
-Diamines show an increase in friction compared to primary
Amines. Adding oleic acid to diamines is better than without.
Triamine show better performance than primary amine and this
product is the best performing candidate presented.
All FMs lower the film thickness compared to ZDDP. However, this
does not result in poorer wear protection.
Petroleum and Water applications
Thank you for your attention!
Petroleum and Water applications