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Organic friction modifiers in engine oils – Fatty amines and fatty amine ethoxylates Sarah Lundgren Tribo Days 6-8 November 2012.

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Presentation on theme: "Organic friction modifiers in engine oils – Fatty amines and fatty amine ethoxylates Sarah Lundgren Tribo Days 6-8 November 2012."— Presentation transcript:

1 Organic friction modifiers in engine oils – Fatty amines and fatty amine ethoxylates Sarah Lundgren Tribo Days 6-8 November 2012

2 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

3 AkzoNobel’s position in the Lube Oil Additive Market Surface Chemistry | Lubes & Fuels3

4 AkzoNobel Surface Chemistry Fatty Amines Process Overview Petroleum and Water applications Fat Splitting Distillation NitrilationHydrogenation EsterificationQuaternization Alkoxylation Oxidation Arquad® Ethoquad® Armosoft® Armolube T® Ethomeen® Propomeen® Ethomid® Ethofat® Armeen® Duomeen® Triameen® Raw Materials: Animal Based Fats Vegetable Based Oils Half Crude Gly. Oxidation Armid® Amidation Aromox® Neo-Fat®

5 Petroleum and Water applications

6 A world of Fatty Amine Derivatives Petroleum and Water applications Triamine Tetraamine Ethomeen Propomeen Duomeen Triameen Tetrameen

7 Duomeen T Duomeen TTM Duomeen TDO Petroleum and Water applications Diamine Chemistries Also ethoxylate di, tri and tetra amine chemistries

8 Fatty chain Petroleum and Water applications Fatty chain Tallow, oleyl, coco, and erucyl Coco (12)  Tallow (18)  Erucyl (22) Oleyl (95%)  Tallow (46%)  18 (0%) Longer chain Less unsaturation

9 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

10 Petroleum and Water applications Samples A primary / secondary blend of ZDDPs (0.5wt%) Group III base oil from Nesteoil 0.5wt% FM

11 Background ZDDP Distribution of ZDDP antiwear film Steel surface Zinc Sulphide ZnS (Poly)phosphate Alkyl phosphate precipitates Long chains Short chains nm 150nm Patchy film Properties – hardness Chemical composition (3) Increasing hardness closer to the surface Alkyl phosphate precipitates rinse off with solvent. 81GPa 25GPa 90GPa 25-40GPa (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 Petroleum Applications

12 12 Techniques for measuring friction and wear Oil Film Thickness/Surface Roughness (or  N/P) Boundary lubrication Mixed lubrication Hydrodynamic lubrication Friction Coefficient Valve Train Piston Rings Journal Bearings

13 Petroleum and Water applications 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. Time µ

14 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. Petroleum and Water applications

15 Number of EO groups and comparison to PO groups Increased degree of ethoxylation increases the friction. Propoxylate worse than ethoxylate. Not all friction modifiers reduce friction compared to ZDDP. Petroleum and Water applications

16 Number of amines Petroleum and Water applications Increasing from one to two amines increased the friction. Methyl groups on diamine increases friction. Salt of oleic acid and diamine better than only diamine. Three amine groups performs really well.

17 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. Petroleum and Water applications ZDDP311µm Armeen DMTD242µm Duomeen T197µm Ethomeen T219µm Armeen T246µm

18 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

19 Thank you for your attention! Petroleum and Water applications


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