Chemistry and Technology of Lubricants (eBook)

Preface 5
References 10
Contents 11
Part I Base Oils 15
1 Base Oils from Petroleum 16
1.1 Introduction 16
1.2 Base Oil Composition 17
1.2.1 Components of Crude Oil 17
1.2.2 Characteristics of the Hydrocarbons for Lubricant Performance 19
1.2.3 Crude Oil Selection for Base Oil Manufacture 20
1.3 Products and Specifications 21
1.3.1 Introduction 21
1.3.2 Physical Properties -- Viscosity 22
1.3.3 Chemical Properties -- Oxidation 25
1.3.4 Base Oil Categories: Paraffinics 26
1.3.5 Safety of Petroleum Base Oils 28
1.4 Conventional Base Oil Manufacturing Methods 28
1.4.1 Historic Methods 28
1.4.2 Base Oil Manufacture in a Modern Refinery 29
1.4.3 Base Oil Production Economics 30
1.4.4 Distillation 31
1.4.5 De-asphalting 33
1.4.6 Solvent Extraction 34
1.4.7 Solvent De-waxing 36
1.4.8 Finishing 38
1.5 Modern Catalytic Processes 38
1.5.1 Severe Hydrotreatment 40
1.5.2 Special Base Oils from Hydrocracking 41
1.5.3 Special Base Oils by Wax Isomerisation 42
1.5.4 Catalytic De-waxing 43
1.5.5 Iso-de-waxing 44
1.6 Categorisation of Base Oils 44
References 45
2 Synthetic Base Fluids 47
2.1 Introduction 47
2.2 Polyalphaolefins 48
2.2.1 Free Radical Oligomerisation 48
2.2.2 Ziegler-Catalysed Oligomerisation 49
2.2.3 Friedel--Crafts-Catalysed Oligomerisation 49
2.2.4 Properties and Applications 52
2.3 Base Oils from Natural Gas Using Gas-to-Liquids Technology, GTL 53
2.3.1 Introduction 53
2.3.2 Gas-to-Liquids Technology 54
2.3.3 Product Properties 56
2.4 Alkylated Aromatics 56
2.4.1 Introduction 57
2.4.2 Production and General Properties 57
2.4.3 Applications 58
2.5 Polybutenes 58
2.5.1 Introduction 58
2.5.2 Production 58
2.5.3 Markets 60
2.5.4 Properties 60
2.5.5 Lubricant Applications 60
2.5.6 Conclusions and Future 65
2.6 Synthetic Esters 65
2.6.1 Introduction 66
2.6.2 Ester Types 66
2.6.3 Manufacture of Esters 66
2.6.4 Physicochemical Properties of Ester Lubricants 68
2.6.5 Application Areas 73
2.6.6 Future Trends 75
2.7 Polyalkylene Glycols 75
2.7.1 Introduction 75
2.7.2 Production 75
2.7.3 Chemistry 76
2.7.4 Key properties 77
2.7.5 Applications 78
2.8 Phosphate Esters 81
2.8.1 Introduction 81
2.8.2 Manufacture 81
2.8.3 Physical and Chemical Properties 82
2.8.4 Applications 83
2.9 Synthetic Base Oil Categorisation 84
References 84
Part II Additives 87
3 Friction, Wear and the Role of Additives in Controlling Them 88
3.1 Introduction to the Mechanisms of Friction 88
3.2 Mechanisms of Wear 89
3.2.1 Adhesive Wear 90
3.2.2 Abrasive Wear 90
3.2.3 Contact Fatigue 91
3.2.4 Corrosive Wear 91
3.3 Boundary Lubrication 92
3.3.1 Mechanisms of Film Formation 93
3.3.2 Conclusion 95
3.4 Physical Chemical Processes for the Formation of Surface Films 96
3.4.1 Formation of Surface Films 96
3.4.2 Influence of Basestock 97
3.4.3 Influence of Metal Surfaces 97
3.4.4 Corrosive/Adhesive Balance 98
3.5 Control of Friction and Wear by Various Classes of Compounds 99
3.5.1 Organic Oxygen Compounds 100
3.5.2 Sulphur and Sulphur/Nitrogen Compounds 102
3.5.3 Organophosphorus Esters 104
3.5.4 Molybdenum--Sulphur Compounds 105
3.5.5 Metal--Phosphorus--Sulphur Additives -- the ZDDPs 106
3.5.5.1 The Influence of Neutral and Overbased Detergents 109
3.5.5.2 Influence of Dispersants 110
3.5.5.3 Influence of Antioxidants 111
3.5.5.4 Influence of Combustion Products on Wear Protection by ZDDPs 112
3.5.5.5 Oxy Acids of Nitrogen and NOx 112
3.5.5.6 Effect of Soot on Wear Protection by ZDDPs 113
3.6 Overall Summary 113
References 114
4 Oxidative Degradation and Stabilisation of Mineral Oil-Based Lubricants 117
4.1 Introduction 117
4.2 Autoxidation of Hydrocarbons 118
4.2.1 Oxidation of Hydrocarbons at Low Temperature (30120C) 118
4.2.2 Oxidation of Hydrocarbons at High Temperature (120C) 123
4.2.3 Metal-Catalysed Autoxidation of Hydrocarbons 125
4.3 Oxidation Stability of Base Oils 127
4.4 Inhibition of Oxidative Degradation of Lubricants 128
4.4.1 Radical Scavengers 128
4.4.2 Hydroperoxide Decomposers 136
4.4.3 Multifunctional Additives 139
4.4.4 Synergism Between Antioxidants 143
4.5 Application of Antioxidants 143
4.5.1 Industrial Lubricants 144
4.5.2 Engine Oils -- Requirements 149
4.5.2.1 Antioxidant technology for passenger car engine oils 150
4.5.3 Antioxidant Technology for Heavy-Duty Diesel Engine Oils 156
4.6 Future Antioxidant Technology 157
4.6.1 Antioxidants for Industrial Lubricants 158
4.6.2 Antioxidants for Engine Oils 158
References 159
5 Viscosity Index Improvers and Thickeners 163
5.1 Introduction 163
5.2 An Overview of VI Improver Chemistry 164
5.3 Chemistry and Manufacture of Commercial VI Improvers 165
5.3.1 Polymethacrylates -- Chemistry 166
5.3.2 Olefin Copolymers: Chemistry 167
5.3.3 Hydrogenated Styrene--Diene Copolymers and Radial Isoprene: Chemistry 171
5.3.4 Styrene Polyester: Chemistry 173
5.3.5 Concentrate-Compatible PMA/OCP Blends -- Chemistry 173
5.4 Function and Properties 174
5.4.1 Solution Properties 174
5.4.2 Mechanism of Function 176
5.4.3 Shear Stability: Permanent Viscosity Loss 178
5.4.4 Thermal--Oxidative Stability 185
5.5 Performance 187
5.5.1 Introduction 187
5.5.2 Low-Temperature Viscosity 188
5.5.3 High-Temperature Viscosity 189
5.5.4 Deposits: Diesel Piston Deposits 191
5.6 Prognosis for Future Developments 192
References 193
6 Miscellaneous Additives and Vegetable Oils 198
6.1 Organic Friction Modifiers 198
6.1.1 Introduction 198
6.1.2 Friction and Lubricating Regimes 199
6.1.3 Chemical Aspects of Friction Modifiers 202
6.1.4 Antagonisms Between Friction Modifiers and Other Additives 204
6.1.5 Lubricity Additives in Diesel Fuel 205
6.2 Pour Point Depressants 205
6.2.1 Introduction 205
6.2.2 Low-Temperature Operation 205
6.2.3 Mechanism of Pour Point Depressants 206
6.2.4 Pour Point Depressant Additives 207
6.3 Demulsifiers and Antifoams 208
6.3.1 Introduction 208
6.3.2 Emulsion Stabilisation 208
6.3.3 Demulsification 209
6.3.4 Demulsifiers 209
6.3.5 Foam Stability 209
6.3.6 Antifoams 210
6.3.7 Foam Studies 210
6.4 Corrosion Inhibitors 211
6.4.1 Introduction 211
6.4.2 The Process of Corrosion 211
6.4.3 Corrosion Inhibitors 212
6.4.4 Corrosion Testing 213
6.5 Vegetable Oils 213
6.5.1 Introduction 213
6.5.2 Chemical and Physical Properties 214
6.5.3 Extraction and Processing 217
6.5.4 Uses of Vegetable Oils 218
References 220
7 Detergents and Dispersants 221
7.1 Introduction 221
7.2 Detergents 222
7.2.1 Introduction to Detergents 222
7.2.2 The Fundamentals of Detergent Composition 223
7.2.3 General Chemistry 223
7.2.4 Overbasing Description 225
7.2.5 Detergent -- Chemical Definition 227
7.2.6 Substrates 228
7.2.7 Performance in Lubricants 231
7.2.8 Summary 232
7.3 Dispersants 233
7.3.1 Introduction to Dispersants 233
7.3.2 Dispersant Mode of Action 233
7.3.3 Synthesis of Dispersants 236
7.3.4 Effects of Dispersants in Engine Oil Formulations 239
7.3.5 Dispersant Use in Other Fuel and Lubricant Applications 240
7.3.6 Summary 242
References 242
Part III Applications 245
8 Industrial Lubricants 246
8.1 Introduction 246
8.1.1 General Aspects of Industrial Lubricants 246
8.1.2 Classification of Industrial Lubricants 248
8.1.3 A New Systems Analysis Approach to Modelling Industrial Lubricants 250
8.1.4 A New Approach to Heterogeneous Catalysis Combined with Tribochemistry 252
8.2 Bearing Lubricants 254
8.2.1 Bearings 254
8.2.2 Gaseous Lubricants 258
8.2.3 Liquid Lubricants 258
8.2.4 Greases 263
8.2.5 Solid Lubricants 264
8.3 Compressor Lubricants 267
8.3.1 General Description 268
8.3.2 Lubricants for Gas Compressors 268
8.3.3 Lubricants for Refrigerators 270
8.3.4 Vacuum Pump Lubricants 271
8.4 Hydraulic Lubricants (Fluids) 271
8.4.1 General Description 271
8.4.2 Mineral Oil-Based Hydraulic Lubricants 273
8.4.3 Synthetic Hydraulic Lubricants 274
8.4.4 Emulsions and Water-Based Fluids 274
8.4.5 Biodegradable Hydraulic Fluids 275
8.5 Industrial Gear Lubricants 275
8.5.1 General Description 275
8.5.2 Lubricants 276
8.6 Turbine Lubricants 279
8.6.1 General Description 279
8.6.2 Industrial Turbine Lubricants 279
8.7 Metalworking Lubricants 281
8.7.1 General Description of Metalworking Processes 282
8.7.2 Lubricant Types for Metal Forming Processes 284
8.7.3 General Lubricant Types for Metal Cutting Processes 287
8.8 Speciality Lubricants 292
8.8.1 Process Oils 292
8.8.2 Textile Oils 292
8.8.3 Food-Grade Lubricants 293
8.8.4 Slideway Oils 293
8.8.5 Cylinder Oils 293
8.8.6 Wire Rope Lubricants 294
8.8.7 Other Lubricants and Related Products 294
References 295
9 Formulation of Automotive Lubricants 300
9.1 Introduction 300
9.2 Passenger Car Engine Oils 300
9.2.1 Passenger Car Engine Types 300
9.2.2 Passenger Car Trends and Emission Legislation 301
9.2.3 Formulation and Functions of a Passenger Car Engine Oil (PCEO) 305
9.2.4 Lubricant Formulation Trends 307
9.2.5 Passenger Car Lubricant Specifications and Evaluating Lubricant Performance 310
9.3 Heavy-Duty Diesel Engine Oils 314
9.3.1 Introduction 314
9.3.2 Heavy-Duty Trends and Emission Legislation 314
9.3.3 Heavy-Duty Engine Strategies Applied to Reduce Exhaust Emissions 316
9.4 Motorcycles and Small Engines 324
9.4.1 Introduction 325
9.4.2 Overview of Two-Stroke Lubricants 325
9.4.3 Two-Stroke Specifications 325
9.4.4 Four-Stroke Motorcycle Lubricants -- Overview 328
9.4.5 Four-Stroke Motorcycle Specifications 329
9.4.6 Lubricant Composition and Impact on Clutch Performance 330
9.4.7 Emissions and the Future 331
10 Driveline Fundamentals and Lubrication 332
10.1 Introduction to Transmission Systems 332
10.2 Gear Types 332
10.3 Transmissions 334
10.3.1 Manual Transmissions 334
10.3.2 Synchromesh Systems 335
10.3.3 Automatic Transmissions 336
10.3.4 Axles and Differentials 337
10.4 Industry Specifications for Gear Oils 339
10.4.1 Introduction 340
10.4.2 API Service Designations in Current Use 341
10.4.3 API Service Designations NOT in Current Use 342
10.5 Automatic Transmission Fluids, ATFs 342
10.6 Agricultural and Off-Highway Fluids 342
10.7 Generic Formulation of Driveline Fluids 343
10.7.1 Introduction 343
10.7.2 Automatic Transmission Fluids 345
10.7.3 Manual Transmission Fluids 347
10.8 Main Functions of an Axle Lubricant 348
10.8.1 Introduction 348
10.8.2 Axle Additive Packs 349
10.9 General Trends and Emerging Technologies 349
10.9.1 Transmission Types 350
10.9.2 Current Situation 351
11 Aviation Lubricants 352
11.1 Introduction 352
11.2 Piston Engine Lubricants 354
11.2.1 Lubrication of Rotary Engines 354
11.2.2 Lubrication of Conventional Aircraft Piston Engines 355
11.3 Aviation Gas Turbine Lubricants 358
11.3.1 Introduction 359
11.3.2 Base Oil Technology 361
11.3.3 Anti-oxidant Additives 364
11.3.4 Anti-wear and Load-Carrying Additives 365
11.3.5 Corrosion Inhibitor Additives 366
11.3.6 Anti-foam Additives 366
11.3.7 Specifications 367
11.4 Aircraft Hydraulic Fluids 371
11.4.1 Introduction 371
11.4.2 Hydrocarbon-Based Hydraulic Fluids 371
11.4.3 Phosphate Ester-Based Hydraulic Fluids 373
11.5 Aircraft Greases 374
11.6 Helicopter Transmission Lubricants 377
Bibliography 378
References 378
12 Liquid Lubricants for Spacecraft Applications 381
12.1 Introduction 381
12.2 Types of Liquid Lubricants 382
12.2.1 Introduction 382
12.2.2 Mineral (Hydrocarbon) Oils 384
12.2.3 Synthetic Oils 384
12.3 Specifications 386
12.3.1 Temperature Range of Operation 386
12.3.2 Vapour Pressure 387
12.3.3 VCM Properties 388
12.3.4 Creep Rate 388
12.3.5 Effects of the Space Environment 388
12.3.6 Storage 389
12.3.7 Chemical Inertness/Rust Prevention 389
12.3.8 Table of Comparative Data 389
12.4 Some Limitations of Space Oils 389
12.4.1 Approximate Lives of PFPEs and Ways of Improvement 389
12.4.2 Effect of PTFE Filler on Bearing Torque 391
12.4.3 Testing and Acceleration Factors 392
12.5 Conclusions 392
References 392
13 Marine Lubricants 394
13.1 Introduction 394
13.2 Marine Diesel Engines 395
13.2.1 Classification by Engine Speed 395
13.2.2 Slow-Speed Engines 395
13.2.3 Medium-Speed Engines 396
13.3 Fuel Oil 396
13.4 Base Oils 399
13.5 Additives 402
13.5.1 Main Additive Types 402
13.5.2 Alkaline Detergents 402
13.5.3 Dispersants 403
13.5.4 Antioxidants 403
13.5.5 Corrosion Inhibitors 403
13.5.6 Anti-Wear, Load-Carrying and Extreme Pressure Additives 404
13.5.7 Pour-Point Depressants 404
13.5.8 Anti-Foam Additives 404
13.6 Properties and Formulation of Marine Lubricants 404
13.7 System Oils 405
13.7.1 Introduction 405
13.7.2 Demulsibility 406
13.7.3 Rust and Corrosion Protection 406
13.7.4 Oxidation and Thermal Stability 406
13.7.5 Load Carrying 407
13.8 Cylinder Oils 407
13.8.1 Introduction 407
13.8.2 Colloidal Stability 407
13.8.3 Acid Neutralisation 407
13.8.4 Spreadability 408
13.8.5 Engine Tests 408
13.8.6 Field Tests 409
13.9 Trunk Piston Engine Oils 409
13.9.1 Introduction 409
13.9.2 Filterability 410
13.9.3 Heavy Fuel Engine Tests 410
13.10 Analysis of In-Service Oils 411
13.10.1 Introduction 411
13.10.2 Density 411
13.10.3 Viscosity 412
13.10.4 Flash Point 412
13.10.5 Insolubles 412
13.10.6 Base Number 412
13.10.7 Water Content 413
13.10.8 Wear Metals 413
References 413
14 Lubricating Grease 415
14.1 Introduction to Lubricating Grease 415
14.2 Structure and Rheological Properties 417
14.2.1 Structure of Grease 417
14.2.2 The Rheology of Grease 419
14.3 The Chemistry of Grease 421
14.3.1 Introduction 422
14.3.2 Base Fluids in Grease 422
14.3.3 Grease Thickeners 424
14.3.4 Grease Manufacturing 428
14.4 Applications 429
14.4.1 Introduction 429
14.4.2 Grease as a Lubricant 430
14.4.3 Grease as a Sealant 431
14.4.4 Grease as a Matrix 431
14.4.5 Grease as a Corrosion Inhibitor 431
14.4.6 Benefits of Grease 431
14.5 Future Trends 432
14.6 Conclusions 435
References 435
Bibliography 435
Part IV Performance 437
15 Lubricants and Their Environmental Impact 438
15.1 Introduction 438
15.1.1 A New Regulatory Framework 438
15.1.2 Introduction to Lubricants in the Environment 440
15.2 Collection of Waste Lubricant 441
15.2.1 Introduction to EU Legislation 441
15.2.2 Used Industrial Lubricants 442
15.2.3 Used Automotive Lubricants 442
15.3 Treatment of Collected Lubricant 442
15.3.1 Introduction to Used Lubricant Treatment 443
15.3.2 Reclamation of Lubricating Oils 443
15.3.3 Production of Re-Refined Lubricant Base Oils 443
15.4 Re-Refined Base Oil Quality 445
15.4.1 Introduction 445
15.4.2 Possible Contaminants in Re-Refined Base Oils 445
15.5 Health and Safety Aspects of Re-Refined Base Oils 446
15.6 Environmental Considerations of Waste Lubricant 447
15.6.1 Disposal of Waste Lubricant as a Fuel 447
15.6.2 Disposal as a Waste 449
15.6.3 Re-Refining Energy Balances 450
15.6.4 Use of Re-Refined Base Oils 450
15.7 Environmental Impact of Consumed Lubricant 451
15.7.1 Constant, Low-Level Inputs 451
15.7.2 Large-Scale 'Catastrophic Inputs' 452
15.8 Biodegradation Tests for Oils 453
15.8.1 Terminology: Biodegradation 451
15.8.2 Current Test Method Variations 454
15.8.3 Problems with Lubricants 456
15.8.4 Current Status and Applicability 456
15.9 Performance 458
15.10 Future Trends 458
References 460
16 Oil Analysis and Condition Monitoring 461
16.1 Introduction 461
16.1.1 Performance Monitoring Testing 461
16.1.2 Condition Monitoring 463
16.2 Oil Failure Modes 463
16.2.1 Introduction 463
16.2.2 Water Contamination 464
16.2.3 Fuel Dilution 465
16.2.4 Glycol Contamination 465
16.2.5 Dirt (Sand) Contamination 465
16.2.6 Wrong Oil Contamination 466
16.2.7 Metal Particulates Contamination 466
16.2.8 Soot Contamination 467
16.2.9 Petroleum Oil Degradation 467
16.2.10 Polyol Ester Oil Degradation 468
16.2.11 Additive Depletion 468
16.3 Oil Test Methods 468
16.3.1 Introduction to Oil Test Methods 468
16.3.2 Infrared (IR) Spectroscopy 469
16.3.3 Electronic Particle Counting 481
16.3.4 Elemental (Metals) Measurement 483
16.3.5 Viscosity Analysis 486
16.3.6 Supplemental Oil Tests 487
16.4 Condition Data Management 488
16.4.1 Introduction to Managing Condition Data 488
16.4.2 Maintenance and Storage of Data 489
16.4.3 Data Interpretation 489
16.4.4 Data Interpretation Procedure 490
16.4.5 Condition Indicators 493
16.5 Conclusion 496
References 496
17 Automotive Lubricant Specification and Testing 498
17.1 Introduction 498
17.1.1 Prior to 1940 498
17.1.2 The Influence of Military Lubricant Standards 500
17.1.3 Special Lubricant Requirements or Universal Application? 500
17.1.4 Single Tests, Many Engines or Many Tests, Single Engine? 502
17.1.5 'Accelerated Testing' 503
17.1.6 Who Sets the Standards? 503
17.1.7 A Summary of Attitudes and Philosophies 504
17.1.8 Testing Organisations, Their Roles and Engine Tests 504
17.1.9 General Principles 505
17.1.10 Specific Light Vehicle Engine Test Objectives 505
17.1.11 Specific Heavy Duty (Diesel) Vehicle Engine Tests 505
17.1.12 The API, ACEA and ILSAC Lubricant Specification Systems 505
17.2 The United States/North America Tripartite System 507
17.2.1 The Society of Automotive Engineers (SAE) Viscosity Classification 507
17.2.2 Performance Classifications and the 'Tripartite' 509
17.2.3 The US Military and the SAE Lubricants Review Institute (LRI) 510
17.2.4 Changes in the 1980s 510
17.2.5 American Chemistry Council, ACC, 'Code of Practice' 511
17.2.6 EOLCS -- The API Engine Oil Licensing and Certification System 513
17.2.7 Laboratory Petrol/Gasoline Engine Test Development 514
17.2.8 The API 'M' Series of Lubricants 515
17.2.9 Evolution of the API --SX/CX-- -- Standard Series 516
17.2.10 Achievements of the Tripartite System 517
17.2.11 API C-(Series) Specifications for Heavy Duty Diesel Engines, Through to API CJ-4 518
17.2.12 The API CJ-4 Heavy Duty Diesel Engine Specification 519
17.2.13 The Passenger Car Engine Test Category for API SM 525
17.2.14 Future Specifications 525
17.3 ACEA European Lubricant Specifications and Approvals 528
17.3.1 Individual Manufacturers 528
17.3.2 CCMC, Now ACEA 529
17.3.3 Differences Between CCMC/ACEA Categories and API Test Sequences 529
17.3.4 CEC 530
17.3.5 Changes in the European Automotive Industry 531
17.3.6 The ACEA 'A/B' and 'C' Gasoline/Diesel Light Vehicle Lubricants 532
17.3.7 The ACEA 'E' Sequence Heavy Duty Diesel Lubricant Specification System 539
17.4 The International Scene ISO, ILSAC and Other Countries 545
17.4.1 The International Organization for Standardization (ISO) 545
17.4.2 ILSAC -- International Lubricant Standardization and Approval Committee 545
17.4.3 Japan 546
17.4.4 Other Countries 546
17.5 Other Automotive Specifications 550
17.5.1 Super Tractor Universal Oils 550
17.5.2 Marine Diesel Engines 551
17.6 Future Developments in Lubricant Specification and Performance Testing 551
Bibliography 553
References 553
Index 554