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Extreme pressure additive
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Extreme pressure additives, or EP additives, are additives for lubricants with a role to decrease wear of the parts of the gears exposed to very high pressures. They are also added to cutting fluids for machining of metals.[1]
Extreme pressure additives are usually used in applications such as gearboxes, while antiwear additives are used with lighter load applications such as hydraulic and automotive engines.
Extreme pressure gear oils perform well over a range of temperatures, speeds and gear sizes to help prevent damage to the gears during starting and stopping of the engine. Unlike antiwear additives, extreme pressure additives are rarely used in motor oils. The sulfur or chlorine compounds contained in them can react with water and combustion byproducts, forming acids that facilitate corrosion of the engine parts and bearings.[2]
Extreme pressure additives typically contain organic sulfur, phosphorus or chlorine compounds, including sulfur-phosphorus and sulfur-phosphorus-boron compounds, which chemically react with the metal surface under high pressure conditions. Under such conditions, small irregularities on the sliding surfaces cause localized flashes of high temperature (300-1000 °C), without significant increase of the average surface temperature. The chemical reaction between the additives and the surface is confined to this area.
The early extreme pressure additives were based on lead salts of fatty acids ("lead soaps"), "active sulfur" compounds (e.g. thiols and elementary sulfur), and chlorinated compounds. During the 1950s the use of lead soaps was eliminated and replaced by zinc and phosphorus compounds such as zinc dithiophosphate.[3]
Some of the EP additives are:
- Dark inactive sulfurized fat
- Dark active sulfurized fat
- Dark active sulfur hydrocarbon
- Short and medium chain chlorinated alkanes (see chlorinated hydrocarbons and chlorinated paraffins)
- Esters of chlorendic acid
- Polymer esters
- Polysulfides
- Molybdenum compounds
Aliphatic chlorinated hydrocarbons (chlorinated paraffins) are cheap and efficient, however they persist in environment and have strong tendency for bioaccumulation. Therefore, they are being replaced with alternatives. In cutting fluids, their role is largely confined to formulations for forming complex stainless steel parts. [1]
The activity of halogenated hydrocarbons increases with decreasing stability of the carbon-halogen bond. At local contact temperatures ranging between 305-330 °C, the additive thermally decomposes and the reactive halogen atoms form a surface layer of iron halides on the part surface. Eventual failure of the contact point comes when the contact temperature exceeds the melting point of the iron halide layer. Under such conditions, small particles of carbon are generated as well. Some compounds used in lubricant additives are chloroalkanes, trichloromethyl phosphine acids, organic esters of a-acetoxy-b,b,b-trichloroethyl phosphonic acid, trichloromethyl esters of phosphoric acid, trichloromethyl derivates of sulfur, trichloroacetoxy compounds, esters or amine salts of chlorendic acid, 1,2,3,4,7,7-hexachloro-5-dimethylbicyclo[2.2.1]-2-heptene, etc.
Oil-soluble organophosphates, with or without zinc, have excellent high-pressure and antiwear properties, and provide corrosion protection especially in presence of chlorinated hydrocarbons. Zinc dialkyldithiophosphates (ZDDP) start decomposing at 130-170 °C, while the activation temperature of tricresyl phosphate (TCP) typically exceeds 200 °C. Their reaction products form a chemically bonded lubricating film on the surfaces.
Polysulfides serve as carriers of inactive and active sulfur.[4]
Molybdenum compounds decompose under high pressure to form an in-situ deposited layer of molybdenum disulfide. Molybdenum dithiocarbamates are used as additives for greases.
Sulfur containing extreme pressure additives can cause corrosion problems in gears with parts made of bronze, brass and other copper alloy when high temperature environments are encountered.
References
[edit]- ^ a b Theo Mang; Jürgen Braun; Wilfried Dresel; Jürgen Omeis (2011). "Lubricants, 2. Components". Ullmanns Encyclopedia of Industrial Chemistry. Wiley-VCH. doi:10.1002/14356007.o15_o04. ISBN 978-3-527-30673-2.
- ^ pecuniary.com FAQ Archived July 15, 2011, at the Wayback Machine
- ^ Shugarman, Arnold. "Monitoring Active Sulfur in EP Gear Oils - And Other Options for Monitoring EP Additive Depletion". Retrieved 7 October 2012.
- ^ Liu, Zulong; Liu, Sheng; Chen, Jun; Ren, Xuemei; Zhang, Chi; Jiao, Yu; Liu, Shuchen; Zhu, Xiaodong; Yan, Yichao; Lei, Tianyu; Chen, Dongjiang; Hu, Yin; Chen, Wei. "Dynamic Reconstruction of Polysulfides to Elemental Sulfur Enabling High-Performance Ah-Level Lithium-Sulfur Pouch Cells". Advanced Functional Materials. n/a (n/a) e25861. doi:10.1002/adfm.202525861. ISSN 1616-3028.
See also
[edit]Extreme pressure additive
View on Grokipediafrom Grokipedia
Fundamentals
Definition and Purpose
Extreme pressure (EP) additives are chemical compounds incorporated into lubricants to prevent direct metal-to-metal contact and subsequent seizing or welding of surfaces in boundary lubrication regimes, where the lubricating film's hydrodynamic action fails to separate contacting asperities.[5] These additives function by reacting with metal surfaces under severe conditions to form protective films that mitigate adhesive wear.[6] The primary purpose of EP additives is to reduce wear, friction, and scoring in high-load applications, such as gears, cams, and bearings, where contact pressures often exceed 1000 MPa and hydrodynamic lubrication is insufficient.[5] By enabling continued operation under these extreme pressures—typically ranging from 400 to 1400 MPa—they protect components from failure modes like scuffing and galling.[7] Unlike base oils, which rely on viscosity to maintain a physical separating film under moderate conditions, EP additives remain dormant in the lubricant until activated by high temperatures and pressures associated with boundary lubrication, at which point they chemically bond to the surfaces.[6] This targeted reactivity distinguishes them from general lubricant components, ensuring minimal interference with normal operation while providing robust protection when needed.[5] In practical applications, such as gear oils for industrial machinery, EP additives significantly enhance durability; for instance, phosphorus-based variants have been shown to increase pitting fatigue life by 2.6 times compared to base oils alone under high-load testing.Role in Tribology
Extreme pressure (EP) additives play a critical role in tribological systems by addressing wear mechanisms such as adhesive wear, scuffing, and pitting that occur in sliding or rolling contacts under high loads where elastohydrodynamic lubrication (EHL) fails to maintain separation between surfaces.[2] In boundary lubrication regimes, where direct metal-to-metal contact predominates due to insufficient oil film thickness, these additives form protective layers on contact surfaces to prevent catastrophic failure modes like welding or severe abrasion.[2] By integrating into lubricant formulations, EP additives significantly enhance system performance, particularly in load-bearing applications such as gears and bearings, where they increase the capacity to withstand extreme pressures without breakdown. They reduce the coefficient of friction in high-pressure tests from typical values of 0.1-0.2 to below 0.05, thereby minimizing energy losses and extending component life.[9] This improvement is essential for maintaining operational efficiency in industrial machinery operating under severe conditions. EP additives interact synergistically with other lubricant components, such as viscosity modifiers, by dominating performance in mixed and boundary lubrication regimes where viscosity alone cannot prevent asperity contact. Viscosity modifiers help sustain film thickness in hydrodynamic conditions, but EP additives provide the necessary protection when loads push the system into regimes of thinner films, ensuring comprehensive tribological coverage without compromising overall fluid stability.[10] Key performance metrics underscore their effectiveness; for instance, in four-ball weld load tests, base greases without EP additives often fail at around 100-200 kgf, whereas incorporating 1-5% EP additive can elevate the weld load to over 300 kgf, and up to 400 kgf in optimized formulations, demonstrating substantial enhancements in load-carrying capacity.[11]Chemical Composition
Key Elements and Compounds
Extreme pressure (EP) additives primarily rely on core elements including sulfur, which forms protective metal sulfide films on surfaces under extreme conditions; phosphorus, which generates phosphate layers; and chlorine, which produces chloride compounds to mitigate wear.[12][2] Combinations of phosphorus and sulfur exhibit synergies, enhancing overall film stability and anti-wear performance in hybrid formulations.[13] Representative compounds encompass sulfur-based options like dibenzyldisulfide, which provides effective boundary lubrication through its disulfide linkage; phosphorus-sulfur hybrids such as zinc dialkyldithiophosphate (ZDDP), valued for its dual reactivity; and chlorine-based chlorinated paraffins, which deliver robust EP properties via halogenation.[14][13][15] Structurally, these additives incorporate polar groups, such as ester or carboxyl functionalities, that promote adsorption to metal substrates, alongside reactive sites centered on the heteroatoms (sulfur, phosphorus, or chlorine) to facilitate tribochemical decomposition and film formation during high-heat and pressure exposure.[16][12] In lubricant formulations, EP additives are generally used at concentrations of 0.5-5% by weight to balance efficacy and compatibility, with good solubility in both mineral and synthetic base oils.[17][18]Formulation Considerations
Formulating lubricants with extreme pressure (EP) additives requires careful balancing with other components to mitigate antagonistic interactions that could compromise performance. For instance, EP additives often conflict with dispersants and detergents, potentially leading to the formation of insoluble contaminants or reduced efficacy through competitive adsorption on metal surfaces.[19] Similarly, interactions between sulfur-based EP additives and phosphorus-based antiwear agents, such as zinc dialkyldithiophosphate (ZDDP), can diminish film-forming capabilities if not properly managed, necessitating formulation adjustments like sequential addition or compatibilizers.[10] Viscosity index improvers, typically polymethacrylates or olefin copolymers, must also be selected to avoid shear-induced instability in EP-enriched blends, ensuring sustained viscosity under high loads.[20] Compatibility with base stocks is a primary concern, as EP additives vary in solubility across different oil types. In polyalphaolefin (PAO) base stocks, solubility is often limited due to their nonpolar nature, requiring the addition of polar co-base stocks like esters or alkylated naphthalenes to enhance dissolution and prevent phase separation.[21] Esters, such as polyol esters, generally offer better solubility for polar EP additives but may introduce hydrolytic instability in moist environments. Thermal stability up to 200°C is essential for EP additives like aryl ZDDPs or sulfurized olefins, which decompose to form protective films without excessive volatility or breakdown.[20] To prevent corrosion in non-ferrous metals, such as copper or brass, formulations incorporate metal deactivators or passivators, particularly for reactive sulfur carriers that can generate corrosive sulfides.[20] Optimization of EP additive dosage relies on standardized testing, such as ASTM D2783, which evaluates four-ball extreme pressure properties by measuring weld load and load wear index to determine effective concentrations for specific applications. Typical dosages start at 0.5-2% for milder conditions but are adjusted upward based on test results to achieve weld loads exceeding 250 kg. Synergies with antioxidants, including hindered phenols or aromatic amines, are leveraged to inhibit oxidative depletion of EP additives, extending their reactive lifespan in high-temperature environments.[20][21] Key challenges in EP formulation include controlling volatility to minimize oil loss and maintaining oxidation stability against radical-induced degradation. Low-volatility PAOs help retain EP additives during use, while oxidation-resistant base stocks like alkylated naphthalenes complement antioxidant synergies to preserve efficacy. Treat rates are tailored to end-use demands, typically 1-5% in industrial gear lubricants but elevated to 5-12% in hypoid gear oils to withstand severe sliding and shock loading.[21][20]Types
Sulfur-Based Additives
Sulfur-based extreme pressure (EP) additives primarily consist of organic sulfur compounds, such as polysulfides, sulfurized olefins, and thiophosphates, which are synthesized by reacting elemental sulfur with hydrocarbons, esters, or triglycerides.[22] These additives feature sulfur atoms bound to carbon chains or additional sulfur atoms, enabling controlled release of reactive sulfur species under mechanical stress and elevated temperatures.[22] Under boundary lubrication conditions in steel-on-steel contacts, these additives exhibit high reactivity, decomposing at temperatures between 250°C and 275°C to release sulfur that reacts with iron surfaces, forming protective iron sulfide (FeS) films.[23] This tribochemical reaction enhances load-carrying capacity, with four-ball weld load tests showing improvements up to 400 kgf at low treat rates of 2-3%.[11] However, active sulfur variants can promote corrosion of copper and other yellow metals by forming copper sulfides, necessitating careful formulation to mitigate this risk.[24] Sulfur-based additives offer advantages including cost-effectiveness and thermal stability, making them suitable for demanding applications.[11] They are commonly incorporated into industrial gear oils to provide robust EP protection under high loads.[22] Limitations include inherent odor from sulfurization processes, which can be reduced in lighter-colored variants, and potential environmental concerns related to sulfur emissions during lubricant disposal or use.[22]Phosphorus-Based Additives
Phosphorus-based extreme pressure (EP) additives primarily function through the formation of protective phosphate films on metal surfaces under tribological stress, offering both antiwear and EP properties in lubricants. These additives typically contain phosphorus in organophosphorus compounds that decompose under heat and pressure to react with iron or other metals, creating durable tribofilms. Common examples include zinc dialkyldithiophosphate (ZDDP) and tricresyl phosphate (TCP). ZDDP, a metal dialkyldithiophosphate, features a structure with zinc bound to two dithiophosphate groups (each containing phosphorus, sulfur, and alkyl chains), enabling it to serve as a multifunctional additive. TCP, an aryl phosphate ester, consists of a central phosphorus atom esterified with three cresyl groups, making it suitable for high-temperature applications such as aviation lubricants.[25][26][27] The reactivity of these additives involves thermal and tribochemical decomposition at temperatures between 100°C and 200°C, where they form zinc or iron phosphate layers that adhere to steel surfaces, preventing direct metal-to-metal contact. For ZDDP, this process yields polyphosphate glasses and mixed Zn/Fe phosphates, providing robust boundary lubrication in mixed regimes where hydrodynamic films are insufficient. TCP similarly decomposes to generate iron phosphate films, particularly effective under high-pressure conditions with the aid of oxygen and moisture. This dual antiwear/EP mechanism has been shown to significantly reduce wear scars in pin-on-disk tests compared to base oils without additives, demonstrating significant protection in sliding contacts. These films are particularly effective in mixed lubrication scenarios, such as gear meshing or engine components, where loads cause partial elastohydrodynamic film breakdown.[26][25][28] Phosphorus-based additives offer advantages including lower toxicity relative to chlorinated EP agents, which can release harmful hydrochloric acid, and multifunctionality that includes oxidation inhibition through radical scavenging. ZDDP, for instance, not only forms protective films but also neutralizes acidic byproducts and prevents base oil degradation, enhancing overall lubricant stability. However, these additives are ash-forming, contributing to sulfated ash content that can lead to deposit accumulation in engines and potential catalyst poisoning in exhaust aftertreatment systems. Additionally, modern emissions standards impose strict phosphorus limits, such as less than 800 ppm in API SN engine oils, to protect catalytic converters from deactivation, necessitating careful formulation to balance performance and compliance.[26][25][29]Other Variants
Chlorine-based extreme pressure additives, such as chlorinated paraffins, olefins, and esters, function by decomposing under high pressure and temperature to form protective metal chloride films on contacting surfaces, thereby preventing direct metal-to-metal contact in demanding applications like metalworking.[30][1][12] These additives are particularly reactive, offering superior performance in boundary lubrication scenarios compared to less reactive sulfur types.[12] However, their use has been largely phased out due to environmental and health concerns, including the generation of hydrochloric acid (HCl) under moist conditions, which can cause corrosion, and the persistent, bioaccumulative, and toxic nature of short-chain chlorinated paraffins (SCCPs).[31][32][33] Hybrid and alternative EP additives include boron compounds, which enhance antiwear and extreme pressure properties by forming durable borate films, often used in low-sulfur formulations to maintain performance without relying on traditional sulfur carriers.[34][35] Overbased sulfonates serve as temperature-independent EP agents, creating thin carbonate-based barrier layers through interaction with metal surfaces, making them suitable for eco-conscious, low-sulfur lubricant designs.[36][37] Molybdenum-based additives, such as organic molybdenum dithiocarbamates and molybdenum disulfide (MoS₂), provide solid-film lubrication by depositing low-shear lamellar layers on metal surfaces, improving EP performance in greases and high-load applications.[11][1] Graphite, another solid lubricant, forms similar protective films through its layered structure, offering temperature-independent EP protection in formulations where liquid additives are insufficient.[1] Emerging options like ionic liquids act as next-generation additives, providing enhanced tribological performance with up to twice the load-bearing film strength of conventional base oils through strong adsorption and tribochemical film formation.[38][39] In niche applications, chlorine-based additives in cutting fluids significantly extend tool life—often by reacting with iron to form protective layers during machining of ferrous metals—though their toxicity limits broader adoption.[40] Ashless phosphorus compounds offer an eco-friendly alternative for gear lubricants, delivering effective EP protection without metallic residues that contribute to ash formation or environmental pollution.[41][42] Post-2000s environmental regulations, including EU restrictions on SCCPs under REACH and the 2017 Stockholm Convention listing, have driven a shift toward non-halogenated EP additives to mitigate risks of persistence and bioaccumulation.[33][43]Mechanisms of Action
Boundary Lubrication Principles
In tribology, lubrication regimes describe the interaction between contacting surfaces under the influence of a lubricant, with boundary lubrication emerging as a critical condition where extreme pressure (EP) additives become essential. Hydrodynamic lubrication maintains full separation of surfaces through a thick fluid film generated by relative motion, effectively supporting the load without asperity contact. Conversely, boundary lubrication occurs when the lubricant film thins to less than 1 μm, allowing direct contact between surface asperities, which bear the majority of the load. This regime is characterized by a lambda ratio (λ) less than 1, where λ is the ratio of the lubricant film thickness to the combined root-mean-square surface roughness of the mating surfaces, indicating insufficient film to prevent solid-solid interactions.[44][45][46] Boundary lubrication is triggered under operating conditions that compromise the stability of the lubricant film, such as high Hertzian contact pressures exceeding 1 GPa, low sliding or entrainment speeds below 1 m/s, and elevated temperatures above 100°C. These factors reduce film thickness by increasing viscous shear, promoting thermal thinning, or overwhelming the elastohydrodynamic pressure buildup needed for film sustenance. In such scenarios, the transition from mixed to full boundary conditions heightens the risk of severe wear mechanisms like scuffing and galling, where localized welding and material transfer occur due to adhesive asperity contacts. The Stribeck curve illustrates this vulnerability, plotting friction coefficient against a dimensionless parameter (lubricant viscosity times speed divided by load); in boundary regimes, EP additives lower the friction coefficient on the Stribeck curve, extending the operable low-speed range and mitigating wear through chemical reactions that form protective tribofilms, enhancing load-carrying capacity.[47][48][49][50] The underlying physics of boundary lubrication involves asperity interactions and the collapse of elastohydrodynamic films. Surface asperities, typically on the scale of nanometers to micrometers, deform elastically or plastically under load, leading to localized stress concentrations that exceed the lubricant's shear strength. Elastohydrodynamic lubrication (EHL) initially forms a thin, pressurized film in non-conformal contacts, but under severe conditions, this film collapses as inlet shear fails to replenish it, exposing asperities to direct interaction and potential adhesion. This collapse is exacerbated by high pressures that elevate lubricant viscosity yet fail to sustain separation at low speeds, necessitating protective measures to limit wear propagation.[51][52]Film Formation and Reactivity
Extreme pressure (EP) additives function through tribochemical processes that establish protective films on metal surfaces under boundary lubrication conditions. The formation begins with the adsorption of additive molecules onto the metal substrate, initially via physical adsorption followed by chemisorption of polar groups to the surface.[36][53] This is succeeded by thermal decomposition of the additive, where bonds such as S-S linkages in sulfur-based compounds cleave, releasing reactive species. These species then react with iron or iron oxides on the surface, forming inorganic films such as iron sulfide (FeS) in the case of sulfur additives, typically 10-100 nm thick.[7][54][7] The reactivity of EP additives is triggered by localized flash temperatures induced by shear, reaching 500-1000°C at asperity contacts without elevating the bulk lubricant temperature significantly. Reaction rates adhere to Arrhenius kinetics, accelerating exponentially with these transient high temperatures to enable rapid film formation.[53][55] These tribofilms exhibit low shear strength, typically 0.1-0.5 GPa, which is substantially lower than that of the underlying metal, allowing the film to shear preferentially under load. Their sacrificial nature ensures that the film deforms or wears to prevent direct metal-to-metal contact and welding, thereby mitigating severe wear.[7][1][53] The effectiveness of these films is validated through tests such as the Timken OK load, where values exceeding 45 lbs indicate robust EP performance and successful film formation under extreme loads.[56][57]Applications
Industrial and Gear Lubricants
Extreme pressure (EP) additives are essential in lubricants for heavy-duty industrial gear systems, particularly enclosed hypoid and worm gears used in mills and mining operations, where high loads and shock conditions prevail. These additives, often sulfur-phosphorus compounds, react with metal surfaces to form protective films that prevent scuffing and welding, enabling reliable operation under extreme pressures. In mining applications, such as those specified for Joy Mining Machinery, EP gear oils provide robust protection for worm drives and hypoid gears, maintaining performance in harsh environments with dust and water contamination.[58][59] Typical formulations for these applications include mineral or synthetic base oils in ISO VG 220 to 680 viscosities, incorporating 2-5% EP additives to achieve AGMA EP service classifications suitable for high-load stages equivalent to 10-12 in standardized testing. For instance, Phillips 66 Extra Duty Gear Oils in these grades use advanced EP packages to handle heavily loaded enclosed gears, meeting or exceeding AGMA 9005-E02 specifications for industrial applications. These oils demonstrate superior load-carrying capacity, with FZG scuffing test (A/8.3/90) results exceeding 12 stages, indicating failure-free performance through advanced load increments and confirming their suitability for demanding gear systems.[60][17][61] In wind turbine gearboxes, sulfur-phosphorus EP blends have proven effective in reducing failure rates by enhancing wear protection and micropitting resistance under variable loads. Synthetic EP formulations, such as those with polyalphaolefin bases, improve film strength. This aligns with the additives' role in boundary lubrication, briefly referencing film formation mechanisms to sustain efficiency over extended cycles.[62][63] As of 2025, sustainable options like bio-based sulfurized EP additives derived from algae oil and ISCC PLUS-certified sulfur carriers are gaining adoption in gear and metalworking applications to meet environmental regulations while maintaining performance.[64][65]Metalworking and Automotive Uses
In metalworking applications, extreme pressure (EP) additives are incorporated into soluble oils at concentrations typically ranging from 2 to 10% to support demanding machining processes such as tapping and drilling. These additives react under high loads to form durable boundary films on tool and workpiece surfaces, significantly reducing friction and preventing metal-to-metal contact that leads to galling or seizure. By absorbing cutting forces and minimizing heat buildup, EP-enhanced soluble oils extend tool life by factors of 2 to 5 times compared to base fluids without such additives, enabling higher throughput and better surface finishes in operations involving ferrous and non-ferrous metals.[3][66][67][68] A key benefit in metalworking is the reduction of scoring on soft materials like aluminum alloys, where sulfur- or phosphorus-based EP agents create sacrificial layers that inhibit adhesive wear during deformation-intensive tasks such as stamping or extrusion. For instance, sulfurized EP additives are particularly effective in processing aluminum, preventing surface defects while maintaining lubricity in emulsifiable formulations. Performance in these scenarios is often assessed via the Falex pin-and-vee block test, which demonstrates low wear rates under extreme loads for well-formulated EP lubricants, typically achieving scar dimensions below 0.1 mm after prolonged exposure.[67][69] In automotive uses, EP additives play a critical role in engine oils, where zinc dialkyldithiophosphate (ZDDP) is formulated at approximately 1000 ppm to safeguard high-pressure contacts like camshaft lobes and lifters against scuffing and fatigue. This concentration provides sufficient anti-wear protection for flat-tappet valvetrains without exceeding levels that could promote long-term oxidation or deposit formation. Transmission fluids similarly rely on EP components, such as phosphorus- or sulfur-based agents, to ensure robust film strength in wet clutch systems, balancing load-carrying capacity with controlled friction to prevent slippage during engagement.[70][71][72][73] For electric vehicle (EV) drivetrains, low-phosphorus EP variants are increasingly adopted to meet compatibility requirements with sensitive electrical insulation and manufacturing processes, including electrocoating (e-coating) for corrosion protection on components. These ashless or reduced-phosphorus formulations, often ionic liquid-based, maintain EP efficacy while minimizing conductivity risks and residue interference in e-coating baths, supporting the shift toward electrified powertrains. As in industrial gear applications, EP additives in automotive contexts enhance durability under varying loads, though formulations are tailored for mobility and thermal cycling.[74][75][76]Performance and Considerations
Advantages and Testing
Extreme pressure (EP) additives provide significant benefits in high-load lubrication applications by forming protective chemical films on metal surfaces, thereby reducing friction and preventing metal-to-metal contact under severe conditions.[1] These additives can achieve substantial wear reduction in gear systems compared to non-EP formulations, particularly in boundary lubrication regimes where loads exceed the base oil's capacity.[77] In gear applications, EP additives enable extended drain intervals by minimizing degradation and contamination buildup.[78] This leads to cost savings through reduced maintenance frequency and downtime, as equipment operates longer without failure; for instance, high-performance EP formulations have been shown to reduce unplanned outages in industrial settings.[79] The efficacy of EP additives is evaluated using standardized tests that simulate extreme loading conditions. The Four-Ball EP test (ASTM D2783) measures load-carrying capacity by rotating a steel ball against three stationary balls submerged in the lubricant, determining the weld point—the load at which the balls seize together; values exceeding 250 kg indicate excellent EP performance suitable for demanding applications.[80][81] The Timken test (ASTM D2782) assesses the ok load, the maximum non-scoring load a lubricant can support between a rotating cup and stationary block, providing insight into EP film's ability to prevent abrasion under sliding contact.[82] Complementing these, the FZG gear test (DIN 51354) evaluates scuffing resistance in a gear rig by incrementally increasing torque until pitting or failure occurs, with pass levels (e.g., stage 12 or higher) confirming suitability for industrial gears.[83] Compared to anti-wear (AW) additives, which protect against moderate friction through milder boundary films, EP additives offer substantially higher load capacity in EP-specific tests—making them essential for shock-loaded or hypoid gear systems where AW alone would fail.[84] This enhanced performance stems from EP's reactive chemistry, which activates under higher pressures to form durable sacrificial layers.[85] The global market for EP additives reflects their critical role in manufacturing and automotive sectors, driven by rising demand for durable lubricants amid industrial growth.Environmental and Health Impacts
Extreme pressure (EP) additives, particularly zinc dialkyldithiophosphate (ZDDP), pose health risks primarily through inhalation and skin contact during handling and manufacturing. ZDDP exhibits low acute oral toxicity with an LD50 greater than 2,000 mg/kg in rats, but inhalation can cause respiratory irritation, coughing, and throat discomfort due to its dust or vapor form.[86] Chlorinated EP additives, such as short-chain chlorinated paraffins (SCCPs), are classified as possible human carcinogens (IARC Group 2B) based on animal studies showing liver and thyroid tumors, prompting OSHA to enforce a de minimis concentration limit of 0.1% for known or suspected carcinogens in workplace mixtures to minimize exposure risks.[87][88] Environmentally, sulfur- and phosphorus-based EP additives contribute to aquatic toxicity via runoff from industrial discharges or lubricant leaks. ZDDP and its degradation products, including zinc and phosphate ions, are harmful to aquatic organisms, with ecotoxicological data indicating toxicity to daphnids, fish, and algae at low concentrations and potential for long-lasting effects in water bodies.[89] Sulfur compounds can exacerbate acidification, while phosphorus promotes eutrophication, leading to algal blooms and oxygen depletion in affected ecosystems. Regulatory responses include EU REACH Annex XVII restrictions prohibiting SCCPs in mixtures at concentrations equal to or above 0.15% by weight since 2009, targeting their use in lubricants to curb persistent organic pollutant releases.[90] To address these impacts, bio-based EP alternatives derived from vegetable oils or esters have emerged, offering reduction in volatile organic compounds (VOCs) compared to traditional formulations while maintaining performance.[91] Lubricant recycling processes, however, often result in significant depletion of EP additives like ZDDP due to filtration, distillation, and chemical treatments, necessitating replenishment and potentially increasing overall environmental footprint if not managed efficiently.[92] Evolving standards, such as ILSAC GF-6 introduced in 2020, limit phosphorus content to 600-800 ppm in passenger car motor oils to protect catalytic converters from poisoning while balancing wear protection needs.[93]Developments
Historical Evolution
The development of extreme pressure (EP) additives began in the early 20th century with simple metal-based compounds to address wear in high-load mechanical systems. In the 1930s, lead soaps, such as lead salts of fatty acids, emerged as one of the first EP agents, providing basic protection by forming soft metal films on contact surfaces under pressure, though limited to low-speed and low-load conditions.[36] These early formulations were derived from animal fats and basic sulfur compounds, marking the initial shift from plain mineral oils to chemically enhanced lubricants for industrial gears.[94] During the 1940s, the demands of World War II accelerated innovation in EP additives for military equipment, particularly gears in vehicles and machinery subjected to extreme conditions. Sulfurized olefins were developed as reactive sulfur compounds that form protective sulfide layers on metal surfaces at high temperatures and loads, proving essential for reliable performance in wartime applications like tank and aircraft transmissions.[23] Concurrently, zinc dialkyldithiophosphate (ZDDP) was patented in 1941 by Lubrizol Corporation (U.S. Patent 2,261,047), initially as an antioxidant but soon recognized for its dual antiwear and EP properties through tribochemical reactions forming zinc/iron phosphate films.[95] This breakthrough enabled broader adoption in engine and gear oils, reducing metal-to-metal contact in boundary lubrication regimes.[96] In the 1950s, standardization efforts formalized EP additive performance, with the American Petroleum Institute (API) introducing the GL-5 specification around 1958 specifically for hypoid gears in automotive axles, requiring high EP protection against shock loading and high speeds.[97] This category emphasized additives like sulfur-phosphorus combinations to prevent scoring and welding, driving industry-wide adoption in heavy-duty applications. By the 1960s, the Society of Tribologists and Lubrication Engineers (STLE), founded in 1944, advanced understanding through research on tribochemistry—the chemical reactions induced by friction—pioneering studies on how EP additives decompose under shear to form sacrificial films.[98] The 1970s saw environmental pressures influence EP additive evolution, with chlorinated compounds like chlorinated paraffins facing early phase-out due to concerns over persistence and toxicity, aligned with emerging regulations on halogenated organics.[99] This shift prompted development of ashless alternatives, such as phosphorus-sulfur systems, to maintain performance without environmental drawbacks. Industry adoption grew steadily, fueled by rising demand in automotive and industrial sectors.Recent Innovations and Trends
Since 2010, innovations in extreme pressure (EP) additives have focused on nanocomposite materials to enhance load-bearing capabilities under severe conditions. For instance, ultrathin MoS₂ nanosheets incorporated at 1 wt% into liquid paraffin base oil have demonstrated a highest non-seizure load of ≥2000 N at 120°C, representing a more than threefold increase compared to traditional additives like molybdenum dialkyldithiocarbamate (MoDDP) at 600 N.[100] Hybrid nanocomposites, such as those combining Al₂O₃ and graphene nanoplatelets at optimal concentrations of 0.8 wt% and 0.2 wt%, have further improved extreme pressure performance by enhancing weld points and reducing wear volume by up to 98% in steel-bronze tribopairs under high loads.[101] Ashless phosphorus-organic additives have emerged as key innovations for electric vehicle (EV) applications, addressing compatibility with sensitive battery interfaces and electrification demands. These additives, such as Duraphos® 178, provide metal-free anti-wear and EP protection equivalent to zinc dialkyldithiophosphate (ZDDP) while offering superior copper corrosion resistance and low ash content, making them suitable for EV drivelines and engine oils.[102] Similarly, CYPHOS® ionic liquids deliver high thermal stability and tunable EP benefits without ash or phosphorus residues that could interfere with EV electrical systems.[74] Recent trends include the development of bio-derived alternatives to traditional sulfur-based EP agents, driven by sustainability goals. Patents from the 2020s highlight sulfonated lignin as a biobased EP additive derived from renewable sources like Kraft lignin, achieving weld loads up to 620 kgf in lithium-complex greases at 5 wt% concentration while maintaining low sulfur (<10 ppm) and enhancing anti-wear with scar diameters below 0.50 mm.[103] AI-optimized formulations represent another trend, leveraging machine learning models like artificial neural networks to refine EP additive blends, thereby improving efficiency and reducing overall additive usage through precise viscosity and friction predictions.[104] Market drivers for these advancements include projections estimating the global EP additives market at approximately $2.5 billion by 2025 (as of 2024), fueled by stringent environmental regulations and the rise of electrification requiring low-phosphorus formulations for battery-compatible lubricants.[105] Ongoing research emphasizes integrating friction modifiers with EP additives to minimize energy losses in gear systems, with potential reductions in power consumption through optimized boundary lubrication in industrial gears.[106] As of 2025, further advancements include EU REACH updates limiting phosphorus in lubricants and expanded bio-based EP options for EV drivetrains.[107]References
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