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Sarah Lundgren Tribo Days 6-8 November 2012

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Presentation on theme: "Sarah Lundgren Tribo Days 6-8 November 2012"— Presentation transcript:

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

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 & Fuels

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

5 Petroleum and Water applications

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

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

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

9 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

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

11 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. Steel surface Zinc Sulphide ZnS (Poly)phosphate Alkyl phosphate precipitates Long chains Short chains 25-40GPa 90GPa Warren et el, Trib. Letters, 4 (1998) 189 Graham et al. Trib. Letters 6 (1999) 149; Nicholls et al. Trib. Internat. 38 (2005) 15 Bec et al. Proc. R. Soc. London, 455 (1999) 4181 Petroleum Applications

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 Journal Bearings Piston Rings

13 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 Petroleum and Water applications

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 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. Petroleum and Water applications

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. ZDDP 311µm Armeen DMTD 242µm Duomeen T 197µm Ethomeen T 219µm Armeen T 246µm Petroleum and Water applications

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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