SULFURIZED EP ADDITIVE SERIES PART I - DARK S-EP FOR METALWORKING FLUIDS

I. DIFFERENCE BETWEEN EP AND AW ADDITIVE

Extreme Pressure (EP) and Anti Wear (AW) additives are very common in metalworking fluids (MWF) industry. The classification of those additive are very confused for those who is just involved in this industry as I used to be 4 years ago. However, I will not talk about their lubricity mechanism, so I will distinguish them very short and easy to understand as follow.

- AW become effective at relatively low contact temperatures and become ineffective at moderate contact temperatures. Four-ball Test ASTM D 4172 (lubricating fluids) can be used to check the scar diameter at 1200 rpm in 60 mins with a force of ~ 40 Kg, 1/2 inch steel balls. Some products can be run up to 98 Kg, even more.

- EP additive remains its effective at relatively high contact temperatures. Four-ball Test ASTM D 2783, 1,770 rpm, RT, 10 sec, 1/2-inch steel balls. Welding load and Last Non-Seizure Load (LNSL) are the key important parameters in this test.

As you can see in the Fig. 1, A to B is "ball to ball" contact, B to C to D is "face to face" contact. 

- AW will affect B point, when formulators can accept metal shape change, they will expand the B point by adding more AW additive.

Figure 2: Real test data of ADEKA Additive for AW/EP test.

- EP additive will enhance the D point. If lubricant-makers want to continue machining even though the metal shape change happens.

II. SULFURIZED EP ADDITIVE

- There are 4 typical types of S-EP additive based on their chemical structure: S-olefin, S-triglyceride, S-ester, S-fatty acid. Some manufacturers can make a mixture containing more than 2 of those types to enhance the EP performance.

Figure 3: Sulfurized Olefin

Figure 4: Sulfurized Ester

Figure 5: Sulfurized Triglyceride (Dark Sulfur)

Figure 6: Sulfurized fatty oil/olefin mixture (light color).

- In term of their color, EP additive can be classified into 2 types: Dark and Light colors.

- Some people will pay attention to its activity, so there are Active and Inactive S-EP additives. Some manufacturers distinguish those 2 types based on the Sulfur chain in the chemical structure. Inactive is less than 3 Sulfur, and Active is from 4 to 5 Sulfur. Others will pay attention to the result of ASTM D-130 and ASTM D-1662.

Figure 7: Properties of S-EP additives

The very basic properties of S-EP can be shown in the Fig. 7. Those are just very basic information, the key important thing is how you formulate the oil for machining, and the majority of the blenders around the world are not afford to buy a four-ball machine. Therefore, you need to understand the machining process and chemical structures of additives to take advantage of the synergistic effect of them for the optimized products for real test in your customers workshops.

III. DARK SULFURIZED EP ADDITIVE AND ITS APPLICATION

In principle, the molecules contains many chromophoric functional groups will enhance the color intensity; therefore, the colors will be darker. As you can see in Fig. 5, Dark S-EP always contains the chromophoric groups in its chemical structure. These structure are not chemically stable since its activity is very high.

The S-EP is the cheapest ones in S-EP additive because of the available raw materials and its less complicated synthesis process. There are 3 types of dark S-EP: S-olefin, S-ester, and S-triglyceride (vegetable or lard oil). You can see the basic classification of DIC S-EP products in Figure 8.

Figure 8: Classification of DIC S-EP Additive

Dark S-EP additives normally are applied in the low-tier cutting and forming applications where the customers can accept its smell and dark colors with a reasonable price and medium performance. 

HERE ARE SOME BASIC PROPERTIES OF THE DARK S-EP:

- Anti-oxidant (AO): Dark S-EP has lower anti-oxidant performance because there are many unsaturated groups in the structure shown in Fig. 7. Light-colored products manufactured with high-pressure hydrogen sulfide processes or by mercaptan oxidation, so it does not maintained the unsaturated double bonds left in the structures ==> they show better oxidation stability.

- Lubricity: Please take a look at Fig. 7. Sulfurized triglyceride provide the best lubricity in both inactive and active type, the second one is ester, and the last one is S-olefin. Lubricity depends on its chemical type. There is nothing to deal with dark and light color. However, at the same chemical structure, the higher MW of dark S-EP may provide the better EP/AW performance.

- Polymerization: Triglyceride type (i.e., lard oil, soybean oil) do polymerize and form solid (e.g., rubberlike products). Because olefins consist of few double bonds and some process can reduce the structure to make only one double bond structure, the polymerization can be controlled. Esters are quite similar to olefins, but due to its natural chemical structure varying amounts of multiple unsaturated compounds, polymerization also can take place. Dark S-EP products will also resume polymerization after the production process is finished.

- Solubility and Polarity: The more polarity, the less solubility in oil. S-EP solubility > S-Ester > S-triglyceride.

- Storage stability: Depending on the raw materials, its chemical structures, and sulfurization process plus technique, some S-EP will continue to polymerize during storage, especially dark S-EP triglyceride type.

Watching Part II: https://phugiadaunhot.blogspot.com/2020/10/sulfurized-ep-additive-series-part-ii.html

Written by Steven Nguyen.