19 Additives for Crankcase Lubricant Applications Ewa A. Bardasz and Gordon D. Lamb CONTENTS 19.1 Introduction. 19.2 Detergents 19.2.1 Introduction 19.2.2 Sulfonates 19.2.3 Phenates, Sulfurized Phenates, and Salicylates 19.24 Other Detergents: Phosphates, Thiophosphates, Phosphonates, and Thiophosphonates 19.2.5 Performance in Lubricants 19.3 Dispersants... 193.1 Introduction 19.3.2. Dispersant Structute.. 19.33. Polyisobutene Synthesis 19.34 Dispersant Basicity 193.5 Succinate Ester Dispersants 19.3.6 Mannich Dispersants. 19.37 Soot Contamination in Diesel Engine Oils 19.38 Soot-Thickening Tests 1939 Seal Testing 19.3.10 Corrosion 193.11 Sludge. 19,3.12 Sludge Engine Tests 194 Antiwear 19.41 Introduction... 19.4.2 Wear Mechanisms 19.4.3 ZDDP Preparation. 19.44 ZDDP Degradation Mechanisms 194.5 Sequential Alkyl Transfers (Primary ZDDP) 19.4.6 Antiwear Tests 1947 Other Antiwear Agents 195 Antioxidants 19.5.1 Introduction 19.5.2 Mechanism of Oxidation of Lubricating Oils 1952.1 Initiation... 1952.2 Propagation. 1952.3 Peroxide Decomposition, . 195.24 Termination (Self and Chain Breaking) 1952.5 Radical Formation 1952.6 Decomposition and Rearrangement 458 498 458 460 461 462 462 463 463 64 466 on A66 466 467 467 468 469 469 470 an 4 an 4a 4B 4am 495 476 4am 477 47 478 478 478 419 479 479 479 457458 Lubricant Additives: Chemistry and Applications 19.53 Oxidation Inhibitors 480 19.54. Hindered Phenols and Arylamines....... sen 80. 19.5.5 Sulfur and Phosphorus Containing Antioxidants, 482 19.5.6 Sulfur Compounds sennnnnnnnnnnnnnnnnnnnnee ABS 19.57 Phosphorus Compounds 483 19.58 Sulfur-Phosphorus Compounds. 483 19.59 Antioxidant Selection, Synergism, and Testing 484 19.6 Viscosity Modifiers... so 436 19.6.1 Introduction 486 19.6.2 Viscosity Modifier Types ss 486 19.6.3 Dispersant Viscosity Modifiers 488 19.64 Shear Stability of Engine Oils son so ABB. 19.65 Viscosity Grade 488 19.6.6 Viscosity Modifier Requirements. 439 197 Pour Point Depressants. 489 19.8 Foam Inhibitors/Antifoams son sn 490 References, 490 19.1 INTRODUCTION Engine oil lubricants make up nearly one-half of the lubricant market and therefore attract a lot of interest, The principal function of the engine oil lubricant is to extend the life of moving parts operating under different conditions of speed, temperature, and pressure. At low temperature, the lubricant is expected to flow sufficiently in order that moving parts are not starved of oil. At higher temperatures, they are expected to keep the moving parts apart to minimize wear. The lubricant does this by reducing friction and removing heat from moving parts. Contaminants pose an additional problem, as they accumulate in the engine during operation. The contaminants may be wear debris, sludges, soot particles, acids, or peroxides. An important function of the lubricant is to prevent these contaminants from causing any damage. To function effectively, the lubricant needs chemical additives as well as base oils. Depending on the application, various combinations of additives are used to meet the required performance level; the most important ones are listed as follows: + Detergents + Dispersants + Antiwear + Antioxidants + Viscosity modifiers + Pour point depressants + Foam inhibitors In addition to these additives, there are several other additives for anticorrosion, antirust, seal swelling, biocide, and demulsability. 19.2. DETERGENTS 19.2.1 INrRopucTion Detergents play an essential role in protecting various metallic components of internal combustion engines by neutralizing acidic compounds formed during combustion processes [1-3]. Gasoline and. diesel engine oils account for more than 75% of the total detergent consumption. Detergent treat- ment in engine lubricant can reach 6-10 wt%, with marine diesel engine lubricants containing theAdditives for Crankcase Lubricant Applications 459 highest concentration levels due to combustion of high-sulfur fuel, which leads to the formation of inorganic acidic combustion products such as sulfuric acid. ‘The purpose of detergents in crankcase oils is 1, To suspendidisperse oil- products 2. To neutralize combustion products (inorganic acids) 3. To neutralize organic acid products of oil degradation processes, 4, To control rust, corrosion, and deposit-forming resinous species [4] soluble combustion products such as sludge or soot and oxidation Why are these specific functions critical to engine durability? Coke and varnish-like deposits can restrict the free movement of the piston rings, allowing a portion of the combustion gases to pass into the crankcase or combustion chamber, leading to heavy contamination of the oil, impacting engine out emissions and even causing piston seizure if the engine operates at high loads [5]. Heavy sludge can plug oil filters, leading to oil starvation and thus to catastrophic wear especially during cold temperature start-ups [6]. Acidic fuel combustion products can cause corrosion. Detergents can react with hydroxyacids, deposit precursors, formed during the oxidation of the oil. Deposit precursors are attracted to detergent micelles and trapped within them and, thus, cannot settle onto metal surfaces and form resinous deposits. The cleaning action of detergent additives is attributed to chemisorption processes and formation of metal salts. To satisfy the abovementioned requirements, practically all detergent additives contain + Polar head. Hydrophilic, acidic groups (¢.g., sulfonate, hydroxyl, mercapton, carboxylic, or carbonamide groups) thal react with metal oxides or hydroxides + Hydrocarbon tail, Oleophilic aliphatic, cycloaliphatic, or alkyaromatic hydrocarbon radicals that provide oil solubility + One or several metal ions Idcalized representation of the detergent structures is shown in Figure 19.1 Although several metals have been incorporated into detergents, only three metal cations are now commonly used—calcium, magnesium, and sodium. Heavy metals such as barium are no longer used. Detergents are described chemically in terms of their metal ratio, soap content, percent sulfate ash, degree of overbasing or conversion, and total base number (TBN) [2]. The metal ratio is defined, as total equivalents of metal per equivalent of sulfonate acid. Soap content refers to the amount of neutral salt and reflects the detergent’s cleansing ability or detergency. The percent sulfate ash is the ash obtained after treating the detergent with sulfuric acid and complete combustion. The degree of overbasing (conversion) describes the ratio of equivalents of the metal base to equivalents of the acid substrate and is usually expressed as conversion. Conversion provides the amount of inor- ganic material relative to that of the organic material and is expressed as number of equivalents of base per equivalent of acid times 100. The overbased part of detergent is needed to neutralize acid b~~~~ oy : FIGURE 19.1 Idealized representations of neutral and overbased detergents