r. t. vanderbilt co. new molybdenum additive technology

1. R. T. VANDERBILT CO.New Molybdenum AdditiveTechnology Tom Karol, Ph. D. Research Director This presentation is designed to promote two molybdenum friction modifiers developed by our Research Division at R.T.VANDERBILT Company (RTV). Both products are particularly suited for GF-3 and GF-4 engine oil development. RTV is expanding production capacity for their manufacture. This presentation is designed to promote two molybdenum friction modifiers developed by our Research Division at R.T.VANDERBILT Company (RTV). Both products are particularly suited for GF-3 and GF-4 engine oil development. RTV is expanding production capacity for their manufacture.

2. The two molybdenum friction modifiers are based on two different organic chemical functional groups. The MOLYVAN 2000 is a molybdenum dithiocarbamate and MOLYVAN 855 is a molybdate ester (no sulfur). The two molybdenum friction modifiers are based on two different organic chemical functional groups. The MOLYVAN 2000 is a molybdenum dithiocarbamate and MOLYVAN 855 is a molybdate ester (no sulfur).

3. MOLYVAN 2000 Sulfurized Molybdenum Dithiocarbamate With improved Friction Retention We attempted to improve a motor oil’s ability to maintain low friction during the life of the motor oil. In the dithiocarbamate chemistry this is accomplished by further sulfurization. We attempted to improve a motor oil’s ability to maintain low friction during the life of the motor oil. In the dithiocarbamate chemistry this is accomplished by further sulfurization.

4. OVERVIEW OF OBJECTIVESfor MOLYVAN 2000 Match or exceed competitive sulfurized MoDTC with regards to: a. Performance, and b. Physical/Chemical Characteristics Utilize a Modified C13 Molybdenum Dithiocarbamate The goals of the MOLYVAN 2000 are delineated above. We wanted improved performance in DTC technology that we could commercialize. The goals of the MOLYVAN 2000 are delineated above. We wanted improved performance in DTC technology that we could commercialize.

5. Competitor’s Patent where R1 = R2 and R3 = R4 but R1 does not = R3 R1 R2 R3 and R4 represent a C8 to C13 alkyl group having a branched chain and/or a straight chain US Patent 5,627,146 A competitor’s patent (non-expired) is shown here. We have improved on our Molybdenum Dithiocarbamate (MoDTC) chemistry based on C13 dialkylamine which affords higher oil solubility over the asymmetric with lower alkyl chains. Our modification involved the additional sulfurization of the molybdenum dithiocarbamate plus process modifications. A competitor’s patent (non-expired) is shown here. We have improved on our Molybdenum Dithiocarbamate (MoDTC) chemistry based on C13 dialkylamine which affords higher oil solubility over the asymmetric with lower alkyl chains. Our modification involved the additional sulfurization of the molybdenum dithiocarbamate plus process modifications.

6. R = C13 alkyl groups MOLYVAN 2000 = S/Mo Mole Ratio 2.5 - 3.0 Competitive sulfurized MoDTC = S/Mo Ratio 2.6 MOLYVAN 2000 MOLYVAN 2000 is the optimized C13 sulfurized MoDTC chemistry. This slide shows the chemical structure of the MOLVAN 2000 and the optimized range of sulfur incorporation to achieve the performance desired. We determined that the sulfur content becomes aggressive at levels above 3.15 S/Mo ratio. MOLYVAN 2000 is the optimized C13 sulfurized MoDTC chemistry. This slide shows the chemical structure of the MOLVAN 2000 and the optimized range of sulfur incorporation to achieve the performance desired. We determined that the sulfur content becomes aggressive at levels above 3.15 S/Mo ratio.

7. OXIDATION METHODTest Procedure: Modified ISOT*(Indiana Stirring Oxidation Test) Test Conditions Temperature: 165.5°C Time: 48h Stirring Speed: 1300 rpm Catalyst: Copper and Steel *JIS K 2514 Measuring the friction of the oil before and after oxidative stressing is a bench method to determine if the oil meets the retention requirements. The Modified ISOT is one oxidation test used in the industry to oxidatively stress a motor oil. Unstressed oil performance is then compared to stressed oil performance in an attempt to define performance life requirements of oil additives. Measuring the friction of the oil before and after oxidative stressing is a bench method to determine if the oil meets the retention requirements. The Modified ISOT is one oxidation test used in the industry to oxidatively stress a motor oil. Unstressed oil performance is then compared to stressed oil performance in an attempt to define performance life requirements of oil additives.

8. SRV Test Conditions Load: 50 Newtons Frequency: 50 Hertz Specimen: Ball on Disc Friction Run: 1 mm Temperature: 80°C Time: 30 minutes This slide depicts the set of test conditions utilized for the SRV frictional test. This is a method of measuring frictional properties for motor oil that is currently being used widely for GF-3 and GF-4 bench testing. This slide depicts the set of test conditions utilized for the SRV frictional test. This is a method of measuring frictional properties for motor oil that is currently being used widely for GF-3 and GF-4 bench testing.

9. MOLYVAN 2000SRV TEST RESULTS Coefficient of Friction* Before ISOT After ISOT MOLYVAN 2000 0.08 0.08 MOLYVAN 822 0.09 0.11 Competitive MoDTC 0.09 0.09 *Determined on fully formulated oil containing 560 ppm phosphorus and 700 ppm molybdenum Here we compare the friction coefficient of an oil before and after the ISOT oxidative stressing of the oil. The lower the frictional coefficient, the less friction the oil has. The measurement “before ISOT” is to simulate the fresh motor oil and the measurement “after ISOT” is to simulate motor oil at the recommended drain time. This data indicates that MOLYVAN 2000 has low friction and would be expected to retain that low friction throughout the drain interval of the motor oil. Here we compare the friction coefficient of an oil before and after the ISOT oxidative stressing of the oil. The lower the frictional coefficient, the less friction the oil has. The measurement “before ISOT” is to simulate the fresh motor oil and the measurement “after ISOT” is to simulate motor oil at the recommended drain time. This data indicates that MOLYVAN 2000 has low friction and would be expected to retain that low friction throughout the drain interval of the motor oil.

10. MOLYVAN 855 Organo Molybdate MOLYVAN 855 is a organo-molybdate. This part of the presentation will demonstrate some of the unique properties of this additive technology. MOLYVAN 855 is a molybdenum enhanced ashless friction modifier. MOLYVAN 855 is a organo-molybdate. This part of the presentation will demonstrate some of the unique properties of this additive technology. MOLYVAN 855 is a molybdenum enhanced ashless friction modifier.

11. Ashless Friction Modifier OD-896B technology The active chemical structures in commercially available OD- 896B that achieve ashless friction modification are shown here. These friction modifiers have been known for many years. It has long been believed that each structure optimally performs in specific conditions such as load and temperature. Therefore, the more structures you have afford a broad spectrum of potential friction reduction. The R group here varies from 8 to 16 carbons and this combination is very effective. The active chemical structures in commercially available OD- 896B that achieve ashless friction modification are shown here. These friction modifiers have been known for many years. It has long been believed that each structure optimally performs in specific conditions such as load and temperature. Therefore, the more structures you have afford a broad spectrum of potential friction reduction. The R group here varies from 8 to 16 carbons and this combination is very effective.

12. Molybdate Ester Formation This animated slide shows how the ashless friction modifiers can be derivatized to molybdenum friction modifiers. Molybdic acid esterifies with the diols to form diester molybdates. Diol diester molybdates have good hydrolytic stability so that they can be utilized in lubricants. This animated slide shows how the ashless friction modifiers can be derivatized to molybdenum friction modifiers. Molybdic acid esterifies with the diols to form diester molybdates. Diol diester molybdates have good hydrolytic stability so that they can be utilized in lubricants.

13. 4 component system MOLYVAN 855 technology The excellent performance of MOLYVAN 855 is believed to be linked to the four components, each being friction modifiers, which all work together to afford optimized frictional reduction. Sulfur chemistry facilitates molybdenum activity. We will explain our perspective on this effect and why benefits are seen. The excellent performance of MOLYVAN 855 is believed to be linked to the four components, each being friction modifiers, which all work together to afford optimized frictional reduction. Sulfur chemistry facilitates molybdenum activity. We will explain our perspective on this effect and why benefits are seen.

14. Iron Oxide to Iron Sulfide This animation depicts the long known effect that sulfur additives (a sulfur source) can form iron sulfide on the surface. Sulfur exchanges with iron oxides to form iron sulfide. This formation affords a wear-protective coating on the surface. This animation depicts the long known effect that sulfur additives (a sulfur source) can form iron sulfide on the surface. Sulfur exchanges with iron oxides to form iron sulfide. This formation affords a wear-protective coating on the surface.

15. Fe Sulfide Coordination Our test data indicates that the iron sulfide coating on the surface affords complexation sites for molybdenum which coordinates exceptionally well with sulfur. This complexation affords a “magnet” for the molybdenum on the surface raising the concentration of molybdenum. The higher level of molybdenum on the surface affect the rate of molybdenum doping (absorption) into the metal. We see atomic molybdenum doping into the metal about 60 angstroms down. Molybdenum-iron is harder and has a lower coefficient of friction (more slippery) than iron affording antiwear and friction reduction. Our test data indicates that the iron sulfide coating on the surface affords complexation sites for molybdenum which coordinates exceptionally well with sulfur. This complexation affords a “magnet” for the molybdenum on the surface raising the concentration of molybdenum. The higher level of molybdenum on the surface affect the rate of molybdenum doping (absorption) into the metal. We see atomic molybdenum doping into the metal about 60 angstroms down. Molybdenum-iron is harder and has a lower coefficient of friction (more slippery) than iron affording antiwear and friction reduction.

16. Molybdenum Thiadiazole Coordination This animated slide depicts thiadiazole (e.g. VANLUBE 871) coordination which allows doping of molybdenum. Most sulfur compounds are readily sacrificed serving as antioxidants. VANLUBE 871 is a metal deactivating antioxidant (deactivate metals as pro-oxidants) and appears not to deplete with oxidative stressing of the oil. Since the thiadiazole ring is very stable, oxidative deterioration of the concentration of VANLUBE 871 is not achieved. The thiadiazole serves as a powerful coordination site (“magnet”) for the molybdenum. VANLUBE 871 is a lubricity additive which affords antiwear protection in Sequence III testing similar to zinc dithiophosphate. Additionally the 871 demonstrates high coefficient of friction reduction and therefore is a very effective ashless friction reducer by itself.   This animated slide depicts thiadiazole (e.g. VANLUBE 871) coordination which allows doping of molybdenum. Most sulfur compounds are readily sacrificed serving as antioxidants. VANLUBE 871 is a metal deactivating antioxidant (deactivate metals as pro-oxidants) and appears not to deplete with oxidative stressing of the oil. Since the thiadiazole ring is very stable, oxidative deterioration of the concentration of VANLUBE 871 is not achieved. The thiadiazole serves as a powerful coordination site (“magnet”) for the molybdenum. VANLUBE 871 is a lubricity additive which affords antiwear protection in Sequence III testing similar to zinc dithiophosphate. Additionally the 871 demonstrates high coefficient of friction reduction and therefore is a very effective ashless friction reducer by itself.