Manufacture grease makes simple

Content Simple Lithium, Lithium Complex Grease production New way to improve production efficiency Background of calcium sulfonate grease New calcium sulfonate grease making process Finished based grease performance Performance enhancement

Performance Additives Typical Grease Composition Base Stock 86 - 90% Performance Additives 0 - 4% Soap 10%

Function and Chemical Composition Simple Soap Organic Fatty Acid + Metallic Hydroxide = Soap Lithium 12 Hydroxystearate Soap H O C 2 3 + L i · - 1 y d r o x s t e a c h u m

Function and Chemical Composition Complex Soap Thickener structure formed by two or more compounds: Long chain fatty acid Short chain carboxylic acid Optionally intermediate chains Lithium Complex Soap H O C 2 3 + 4 L i · - 8 1 y d r o x s t e a c h u m A z l p S

Fiber formation, cooling Grease Manufacturing Saponification stage Fiber formation, cooling Is There a Better Method ? Foam Data extracted from “A Comparison of Grease Manufacturing Methods”, K. R. Masters, Stratco. Presented at the European Lubricating Grease Institute AGM, 1992, Chester, UK

New Product An oil-based dispersed micron sized anhydrous lithium hydroxide Fluid, pumpable, mineral oil-based; PAO based product is available Anhydrous – a virtually waterless process, reduced foaming and less energy consumption Micron sized particles (~100 times smaller than lithium hydroxide monohydrate) Greater surface area Enhanced reactivity Good storage stability Stable – no evidence of reacting to CO2 and moisture in the air Anhydrous Smaller particle size Oil based fluid

Lithium Hydroxide Monohydrate Crystals LIOH.H20 New Product . .

Comparison between Lithium Hydroxide Monohydrate and new product Physical form White crystals Opaque dispersion in oil % lithium hydroxide 57%, balance is water 36%, anhydrous Packaging Bags Drums or bulk Particle size 500-1000 micron <10 micron Method of addition Added as powder or as slurry in water Meter in via pump

Grease Manufacturing A Simple Lithium Grease Recipe Material LiOH•H2O New Product 12-HSA 9.8kg Base oil 90kg 88.7kg* Lithium base 1.37kg 2.10kg Target soap content (% wt) 10.0 * Less oil is needed due to oil introduced by Lubrizol® 5280GR

Process Profiles: Simple Lithium Grease 50 100 150 200 250 0% 20% 40% 60% 80% 100% Time % Temperature deg C Ref Li OS 196909

Process Profiles: Lithium-Complex Greases LiOH dispersion Lithium Complex 50 100 150 200 250 0% 20% 40% 60% 80% 100% Time % Temperature deg C Ref LiX OS 196909

Lithium Grease 12-HSA 9.8% New Product 2.1% Oil from new product 1.3% Base oil, 600N 88.7% Water (byproduct) - 0.6% Test Result Dropping point ASTM D2265 202° C ASTM D218 P0 P60 P1000 224 222 232 Soap content 10%

Lithium-Complex Grease 12-HSA 9.6% Azelaic acid 3.0% New Product 4.1% Oil from new product 2.6% Base oil 84.4% Water (byproduct) -1.2% Test Result Dropping point ASTM D2265 >285° C ASTM D218 P0 P60 P1000 297 288 Soap content 13%

Lithium-Complex Grease Property Comparison Grease C Grease D Base LiOH-H2O New Product Soap content (% Wt) 10.7% 10.4% ASTM D128: neutralization # 1.3b 1.0b ASTM D217: penetration P0 278 270 P60 279 275 P10K --- 296 ASTM D2265: dropping point 284° C 309° C

Benefits of New Product Faster soap manufacture Reactivity greatly enhanced by small particle sizes/larger surface areas Faster saponification - acid and base both present in oil phase Less foaming during heating to slow process down No added water to remove Increased manufacture throughput with existing equipment Shorter manufacture cycle, more batches can be made Slightly larger batches allowed due to reduced foaming

Benefits of New Product Manufacture cost savings Shorter production time, increased capacity with existing equipments, lower unit manufacture cost Lower peak reaction temperature, energy savings Minimum water to be removed, energy savings High quality, more consistent products, less costly batch re-work Operational Pumpable liquid, the quantity added can be very easily and precisely controlled. Comes in drums or bulk, no dusty waste sacks to dispose Safer handling compared to dusty solid powder of lithium hydroxide monohydrate No need for a special pre-mixing side vessel for making water and lithium hydroxide monohydrate slurry Minimum foaming hazard Less waste oil disposal; less steam during soap manufacture

Benefits of New Product Lithium complex greases New Product enables a reliable, single step process for making lithium-complex grease, with less work-off The product has a high dropping point (> 300° C) The period of time at max temperature of approx 200° C is much reduced Simple procedure using New Product enables high-quality lithium complex greases to be made in plants with basic grease kettles Ester or vegetable-based grease New Product is proven to be effective in making lithium and lithium- complex soaps in esters and vegetable oils This is not possible for conventional LiOH.H2O process where hydrolysis of ester or vegetable oils during saponification is a concern

Calcium Sulfonate Grease make simple

Calcium Sulfonate Grease Calcite-thickened greases have been known since the 1960’s Typically made from overbased calcium sulfonates High dropping point, and good mechanical stability Strong, inherited EP/antiwear performance: Timken Four ball wear Four ball weld Further additized for enhanced performance

High Temperature Grease Growth Trend Calculated annual growth rate 8% 5.3% 2.3% Fastest growing type of greases High temperature, wet and heavy load operation conditions: Mining, Steel Mills, Railroad, Paper Mills, Truck, Marine, etc Inherent AW/EP: Food grade (H1 and H2) 13.6% Source: NLGI Survey

High Temperature Grease Comparison Li Complex Al Complex Polyurea Ca sulfonate Advantage Multi-purpose Good pumpability Readily available Water resistance Ashless Excellent oxidation resistance Low noise Seal for life Inherent EP/AW Good mechanical stability Good corrosion resistance Disadvantage Additives needed for performance Rising raw material cost Poor oxidation resistance Manufacturing requirements high Poor mechanical stability Needs additive for Rust, EP and corrosion Poor low temperature Pumpability Availability

Calcium Sulfonate Grease Colloidally Stable Wafer-Like Calcite Crystals in Oil Calcium Sulfonate Hydrocarbon and Oil Tails Colloidal Dispersion of Amorphous CaCO3 in Oil Stabilized by Surfactants Converting Process Promoter Solvent Calcium sulfonate greases begin as an colloidal dispersion of amorphous calcium carbonate particles in oil. Conversion to the crystalline carbonate form is accomplished by promoters to form a platelet-like structure. The size of these calcite particle have been measured to be in the nanoparticle range, which is very important for their performance characteristics.

Extreme Pressure Contact Zone Metal surface Voids Contacting Surfaces Mating Surface Asperities If one were to look at the extreme contact zone of a metal under a microscope, one would see irregularities on the surface. There are voids and contacting surfaces also called asperities that would contact one another upon movement and if no additive were present they would wear or weld. Standard grease contain EP agents such as sulfur additives or anti-wear agents like ZDP’s to protect the surface. These additives would adhere to the surface and upon extreme pressure and heat they would decompose on the surface and actually adsorb into the metal. These surfaces are weaker than the metal themselves are easily removed upon metal contact, thereby reducing the temperature and preventing welding from occurring

Extreme Pressure Contact Zone with Sulfonate Grease Metal surface Calcium sulfonate grease Contacting Surfaces Now looking at the same extreme pressure contact zone with a calcium sulfonate greases one can expect to see that these small particles filled in the voids between the metal surface by adhering to the surface with their polar head groups. These crystalline structures are capable of protecting the surface by having their platelet structure momentarily sheared under load conditions which prevents the metal surfaces from experiencing contact.

New Calcium Sulfonate grease precursor A new, enhanced 400TBN calcium sulfonate grease substrate Simple predictable grease procedure “Add water, oil, cook, you get grease!” Excellent AW/EP performance Superior water spray off properties

New Calcium Sulfonate grease precursor Vs. Conventional Process Conventional Sulfonate Grease Process New Sulfonate Grease Process Temp (°C) Add 12-Hydroxystearic acid 160 Add oil Remove H2O Add lime and boric acid solutions 140 Add acetic acid 120 Add water and Sulphonic acid, Add oil 100 Add oil Remove H2O 80 cool Stir, increase temp 60 Charge starting Materials: Lubrizol ® 86GR, base oil, water 40 20 60 120 180 240 300 360 420 Process Time (Minutes) Lubrizol®86GR all ingredients are added up front Conventional sulfonates require multiple steps

Performance of Calcium Sulfonate grease from new process 1 2 3 4 Base oil added 325N Group I 600N Group I Bright Stock PAO-100 Oil viscosity @ 40°C 32.9 49.8 121.3 305 Total oil (%wt) 56.5 59.7 62.6 66.9 D217 Penetration 297 290 266 303 D2265 (Dropping Point °C) >316 D2509 (Timken load, lbs) 60 70 D2596 (Four-Ball EP, kg) 400 D2266 (Four-Ball Wear, mm) 0.28 0.31 0.30 0.40 D1743 (Rust, distilled water) pass fail, tr D1264 (Wash out, %) 3.3 1.6 1.4 1.3 D4049 (Spray off, %) 24.4 8.1 14.2 6.8

Comparison of Ca Sulfonate Greases Competitive Process New Precursor D2266 ( mm) - 4ball wear 0.33 0.31 D2265 (ºC) - DP >316 D2596 (kg) – 4Ball EP 400 D1264 (%) – Water Washout 2.4 1.6 D4049 – Water Spray-off 67 8.1 D2509 (#) Timken 60 70

Advantages of New Calcium Sulfonate grease precursor Synthetic calcium sulfonate – security of supply Simple, fast, Lubrizol unique procedure requires only water as promoter Compatible with Group I, Group II, and synthetic oils Ca sulfonate greases base on new precursor provides High dropping points Excellent AW/EP Good rust protection Excellent water spray off protection

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