The present invention relates to a method for lubricating moving surfaces of a mechanical device comprising the steps of vaporizing an lubricant additive, depositing the vaporized lubricant additive on the surface of the mechanical device to prepare an additive coated device, and contacting the surface of the additive coated device with a lubricant. It further relates to a method for preparing the additive coated device comprising the step of vaporizing the lubricant additive, and depositing the lubricant additive on the surface of the mechanical device to prepare the additive coated device. Combinations of preferred embodiments with other preferred embodiments are within the scope of the present invention.

The traditional way of applying lubricant additives to mechanical devices is mixing lubricant additives with the base oil, and then applying the formulated lubricant to the moving surfaces. Object was to find new ways of applying known lubricant additives for lubricating mechanical devices, and to further improve methods for lubricating mechanical devices.

The object was achieved by a method for lubricating moving surfaces of a mechanical device comprising the steps of a) vaporizing an lubricant additive, b) depositing the vaporized lubricant additive on the surface of the mechanical device to prepare an additive coated device, and c) contacting the surface of the additive coated device with a lubricant.

The object was also achieved by a method for preparing the additive coated device comprising the step of a) vaporizing the lubricant additive, and b) depositing the lubricant additive on the surface of the mechanical device to prepare the additive coated device.

The object was also achieved by the additive coated device wherin a surface of the mechanical device is coated with a coating consisting of the lubricant additive and where the coating has a thickness of up to 10 pm.

The lubricant additive can be an organic or inorganic lubricant additive. Typically, the organic lubricant additive is an organic compound which comprises carbon-hydrogen bonds. For example, the organic lubricant additive is an organic compound which comprises aliphatic and/or aromatic groups. The lubricant additive has usually melting point below 200 °C, 150 °C, 100 °C, or 50 °C. The melting point is usually determined at normal pressure.

Suitable lubricant additives may be selected from viscosity index improvers, polymeric thickeners, corrosion inhibitors, detergents, dispersants, anti-foam agents, dyes, wear protection additives, extreme pressure additives, anti-wear additives, friction modifiers, metal deactivators, antioxidants, pour point depressants.

Preferably, the lubricant additive comprises an antiwear additive, an friction modifier, or an antioxidant. In another preferred form, the lubricant additive comprises an organic antiwear additive, an organic friction modifier, or an organic antioxidant.

The lubricant additive can be a friction modifier, preferably an organic friction modifier. Various friction modifiers are commercially and known to an expert.

Suitable organic friction modifier are fatty acids derivatives (such as fatty amines, fatty acid amides, fatty acid epoxides, alkoxylated fatty amines, alkoxylated fatty amides, metal salts of fatty acids, fatty acid imidazolines), fatty alcohols, or alkoxylated fatty alcohols.

Preferably, the lubricant additive is an organic friction modifier selected from fatty amines, fatty acid amides, fatty acid epoxides, alkoxylated fatty amines, alkoxylated fatty amides, metal salts of fatty acids, fatty acid imidazolines, fatty alcohols, or alkoxylated fatty alcohols.

The fatty acids may contain 6 to 24, or 8 to 18 carbon atoms. The fatty acids may be branched or straight-chain, saturated or unsaturated. Suitable acids include 2-ethylhexanoic, decanoic, oleic, stearic, isostearic, palmitic, myristic, palmitoleic, linoleic, lauric, and linolenic acids, and the acids from the natural products tallow, palm oil, olive oil, peanut oil, corn oil, and Neat's foot oil.

When in the form of a metal salt, typically the metal includes zinc or calcium.

Preferably, the organic friction modifier is a fatty acid derivative, such as a C6-C24 fatty acid derivative.

In another preferred form the organic friction modifier is selected from fatty amines, fatty acid amides, fatty acid epoxides, alkoxylated fatty amines, metal salts of fatty acids, fatty acid imidazolines, where the fatty acid is preferably a C6-C24 (more preferably a C8-C18) fatty acid. In particular the organic friction modifier is selected from alkoxylated fatty amines and alkoxlated fatty amides, such as reaction products of fatty acids with di(C2-8 alkanol)amine and C2-C6 alkylene oxides.

Further suitable friction modifier includes fatty amines, borated glycerol esters, fatty acid amides, non-borated fatty epoxides, borated fatty epoxides, alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty imidazolines, metal salts of alkyl salicylates (may also be referred to as a detergent), metal salts of sulphonates (may also be referred to as a detergent), condensation products of carboxylic acids or polyalkylenepolyamines, or amides of hydroxyalkyl compounds.

In one embodiment the friction modifier includes a secondary or tertiary amine being represented by the formula RaR NRc, wherein Ra and R are each independently an alkyl group of at least 6 carbon atoms and Rc is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group.

In one embodiment the friction modifier includes those formed by the condensation of the hydroxyalkyl compound with an acylating agent or an amine. Another suitable friction modifier includes an amide represented by the formula RdRdN-C(0)Rf, wherein Rd and Re are each independently hydrocarbyl groups of at least 6 carbon atoms and Rf is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by the condensation of said hydroxyalkyl group, through a hydroxyl group thereof, with an acylating agent. In one embodiment the amide of a hydroxylalkyl compound is prepared by reacting glycolic acid, that is, hydroxyacetic acid, HO-CH2-COOH with an amine.

In one embodiment the friction modifier includes a reaction product of a di-cocoalkyl amine (or di-cocoamine) with glycolic acid.

In one embodiment the friction modifier includes those derived from the reaction product of a carboxylic acid or a reactive equivalent thereof with an aminoalcohol, wherein the friction modifier contains at least two hydrocarbyl groups, each containing at least 6 carbon atoms. An example of such a friction modifier includes the reaction product of isostearic acid or an alkyl succinic anhydride with tris-hydroxymethylaminomethane.

In one embodiment the friction modifier includes an alkoxylated amine e.g. alkoxylated fatty amines known by the trademark "ETHOMEEN" and available from Akzo Nobel. Representative examples of these ETHOMEEN™ materials is ETHOMEEN™ C/12 (bis[2-hydroxyethyl]-coco- amine); ETHOMEEN™ C/20 (polyoxyethylene cocoamine); ETHOMEEN™ S/12 (bis[2- hydroxyethyl]- soyamine); ETHOMEEN™ T/12 (bis[2-hydroxyethyl]-tallow-amine);

ETHOMEEN™ T/15 (polyoxyethylene-tallowamine); ETHOMEEN™ 0/12 (bis[2- hydroxyethyl]oleyl-amine); ETHOMEEN™ 18/12 (bis[2 — hydroxyethyl]octadecylamine); and ETHOMEEN™ 18/25 (polyoxyethylene octadecylamine).

In one embodiment the friction modifier includes an alkylphosphonate mono- or di- ester, e.g. sold commercially by Rhodia under the trademark Duraphos® DMODP.

In one embodiment the friction modifier includes a borated fatty epoxide or alkylene oxide. These oil-soluble boron-containing compositions may be prepared by reacting, at a temperature of 80 °C to 250 °C, boric acid or boron trioxide with at least one fatty epoxide or alkylene oxide. The fatty epoxide or alkylene oxide typically contains at least 8 carbon atoms in the fatty groups of the epoxide (or the alkylene groups of the alkylene oxide).

Suitable inorganic friction modifiers are molybdenum disulfide or graphite.

The lubricant additive can be a anti-wear additive, preferably an organic anti-wear additive. Various anti-wear additives are commercially and known to an expert. Suitable organic antiwear additives are phosphorus-containing organic antiwear agents and sulfur- containing organic antiwear agent.

Suitable phosphorus-containing organic antiwear agents include organo phosphites (such as dialkyl, trialkyl, and triaryl phosphites), dialkyldithiophosphates, dialkylphosphates (typically a zinc or amine dialkylphosphate), diaryl dithiophosphates, or phosphosulfurized hydrocarbons.

Examples of a dialkyldithiophosphate include zinc, molybdenum or ammine salts of di-(2- methylpropyl) dithiophosphate/di-(amyl)dithiophosphate, di-(1 ,3-dimethylbutyl) dithiophosphate, di-(heptyl)dithiophosphate, di-(octyl) dithiophosphate, di-(2-ethylhexyl) dithiophosphate, di- (nonyl) dithiophosphate, di-(decyl) dithiophosphate, di-(dodecyl) dithiophosphate, di- (dodecylphenyl) dithiophosphate, di-(heptylphenyl) dithiophosphate, or mixtures thereof.

Examples of a dialkylphosphate include zinc or amine salts of di-Ci-18-alkylphosphate, such as di-(2- methylpropyl) phosphate, di-(amyl) phosphate, di-(l,3-dimethylbutyl) phosphate, di-(heptyl) phosphate, di-(octyl) phosphate, di-(2- ethylhexyl) phosphate, di-(nonyl) phosphate, di-(decyl) phosphate, di-(dodecyl) phosphate, di-(dodecylphenyl) phosphate, di- (heptylphenyl) phosphate, or mixtures thereof. Suitable sulfur-containing organic antiwear agents are sulfurized sperm oil, sulfurized terpenes, zinc dialkyldithiocarbamate, molybdeum dialkyl dithiocarbamates (e.g. molybdenum di-n- butyldithiocarbamate, molybdenum bis-diethylhexyl dithio-carbamate), antimony tris(dialkyldithiocarbamate), methylene bis(dibutyldithiocarbamate).

Preferably, the phosphorus-containing organic antiwear agents include organo phosphites, dialkyldithiophosphates, dialkylphosphates, diaryl dithiophosphates, or phosphosulfurized hydrocarbons.

Preferably, the sulfur-containing organic antiwear agents are sulfurized sperm oil, sulfurized terpenes, dialkyldithiocarbamates (e.g. of zinc or molybdenum), antimony tris(dialkyldithiocarbamate), methylene bis(dibutyldithiocarbamate).

Preferably, the lubricant additive is an an phosphorus-containing organic antiwear agents selected from organo phosphites, dialkyldithiophosphates, dialkylphosphates, diaryl dithiophosphates, or phosphosulfurized hydrocarbons; or a sulfur-containing organic antiwear agents selected from sulfurized sperm oil, sulfurized terpenes, dialkyldithiocarbamates, antimony tris(dialkyldithiocarbamate), methylene bis(dibutyldithiocarbamate).

In particular preferred form of the lubricant additive the dialkyldithiophosphate is propanoic acid 3-bis(2-methylpropoxy)phosphinothioylthio-2-methyl-.

In particular preferred form the lubricant additive the dialkylphosphate is an amine salt of di-Ci . -alkylphosphate.

Suitable viscosity index improvers include high molecular weight polymers that increase the relative viscosity of an oil at high temperatures more than they do at low temperatures. Viscosity index improvers include polyacrylates, polymethacrylates, alkylmethacrylates, vinylpyrrolidone/meth-acrylate copolymers, poly vinylpyrrolidones, polybutenes, olefin copolymers such as an ethylene-propylene copolymer or a styrene-butadiene copolymer or polyalkene such as PIB, styrene/acrylate copolymers and polyethers, and combinations thereof. The most common VI improvers are methacrylate polymers and copolymers, acrylate polymers, olefin polymers and copolymers, and styrenebutadiene copolymers. Other examples of the viscosity index improver include polymethacrylate, polyisobutylene, alpha-olefin polymers, alpha-olefin copolymers (e.g., an ethylenepropylene copolymer), polyalkylstyrene, phenol condensates, naphthalene condensates, a styrenebutadiene copolymer and the like. Of these, polymethacrylate having a number average molecular weight of 10000 to 300000, and alphaolefin polymers or alpha-olefin copolymers having a number average molecular weight of 1000 to 30000, particularly ethylene- alpha-olefin copolymers having a number average molecular weight of 1000 to 10000 are preferred.

Suitable (polymeric) thickeners include, but are not limited to, polyisobutenes (PIB), oligomeric co-polymers (OCPs), polymethacrylates (PMAs), copolymers of styrene and butadiene, or high viscosity esters (complex esters).

Corrosion inhibitors may include various oxygen-, nitrogen-, sulfur-, and phosphorus- containing materials. Corrosion inhibitors may include, but are not limited to, additive types such as, for example, hydrocarbyl-, aryl-, alkyl-, arylalkyl-, and alkylaryl- versions of detergents (neutral, overbased), sulfonates, phenates, salicylates, alcoholates, carboxylates, salixarates, phosphites, phosphates, thiophosphates, amines, amine salts, amine phosphoric acid salts, amine sulfonic acid salts, alkoxylated amines, etheramines, polyetheramines, amides, imides, azoles, diazoles, triazoles, benzotriazoles, benzothiadoles, mercaptobenzothiazoles, tolyltriazoles (TTZ-type), heterocyclic amines, heterocyclic sulfides, thiazoles, thiadiazoles, mercaptothiadiazoles, dimercaptothiadiazoles (DMTD-type), imidazoles, benzimidazoles, dithiobenzimidazoles, imidazolines, oxazolines, Mannich reactions products, glycidyl ethers, anhydrides, carbamates, thiocarbamates, dithiocarbamates, polyglycols, etc., or mixtures thereof.

Detergents include cleaning agents that adhere to dirt particles, preventing them from attaching to critical surfaces. Detergents may also adhere to the metal surface itself to keep it clean and prevent corrosion from occurring. Detergents include calcium alkylsalicylates, calcium alkylphenates and calcium alkarylsulfonates with alternate metal ions used such as magnesium, barium, or sodium. Examples of the cleaning and dispersing agents which can be used include metal-based detergents such as the neutral and basic alkaline earth metal sulphonates, alkaline earth metal phenates and alkaline earth metal salicylates alkenylsuccinimide and alkenylsuccinimide esters and their borohydrides, phenates, salienius complex detergents and ashless dispersing agents which have been modified with sulphur compounds.

Dispersants are lubricant additives that help to prevent sludge, varnish and other deposits from forming on critical surfaces. The dispersant may be a succinimide dispersant (for example N-substituted long chain alkenyl succinimides), a Mannich dispersant, an ester-containing dispersant, a condensation product of a fatty hydrocarbyl monocarboxylic acylating agent with an amine or ammonia, an alkyl amino phenol dispersant, a hydrocarbyl-amine dispersant, a polyether dispersant or a polyetheramine dispersant. In one embodiment, the succinimide dispersant includes a polyisobutylene-substituted succinimide, wherein the polyisobutylene from which the dispersant is derived may have a number average molecular weight of about 400 to about 5000, or of about 950 to about 1600. In one embodiment, the dispersant includes a borated dispersant. Typically, the borated dispersant includes a succinimide dispersant including a polyisobutylene succinimide, wherein the polyisobutylene from which the dispersant is derived may have a number average molecular weight of about 400 to about 5000. Borated dispersants are described in more detail above within the extreme pressure agent description.

Anti-foam agents may be selected from silicones or polyacrylates.

Suitable organic extreme pressure agent is a sulfur-containing compound. In one embodiment, the sulfur-containing compound may be a sulfurised olefin. Examples of the sulfurised olefin include a sulfurised olefin derived from propylene, isobutylene, pentene; an organic sulfide and/or polysulfide including benzyldisulfide; bis-(chlorobenzyl) disulfide; dibutyl tetrasulfide; di-tertiary butyl polysulfide; and sulfurised methyl ester of oleic acid, a sulfurised alkylphenol, a sulfurised dipentene, a sulfurised terpene, a sulfurised Diels-Alder adduct, an alkyl sulphenyl N'N- dialkyl dithiocarbamates; or mixtures thereof. In one embodiment, the sulfurised olefin includes a sulfurised olefin derived from propylene, isobutylene, pentene or mixtures thereof. In one embodiment the extreme pressure additive sulfur-containing compound includes a dimercaptothiadiazole or derivative, or mixtures thereof. Examples of the dimercaptothiadiazole include compounds such as 2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof. The oligomers of hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole typically form by forming a sulfur-sulfur bond between 2,5-dimercapto-1 ,3,4-thiadiazole units to form derivatives or oligomers of two or more of said thiadiazole units. Suitable 2,5-dimercapto-1 ,3,4-thiadiazole derived compounds include for example 2,5-bis(tert-nonyldithio)-1 ,3,4-thiadiazole or 2-tert-nonyldithio-5-mercapto- 1 ,3,4-thiadiazole. The number of carbon atoms on the hydrocarbyl substituents of the hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole typically include 1 to 30, or 2 to 20, or 3 to 16. Suitable inorganic extreme pressure agents are polysulfide.

The lubricant additive can be an antioxidant, preferably an organic antioxidant, such as a phenolic antioxidant, an aminic antioxidant, or a further antioxidant, where phenolic antioxidants are preferred.

Preferably, the lubricant additive is an antioxidant selected from phenolic antioxidants or aminic antioxidants.

In a preferred form the lubricant additive is an ester of (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with polyhydric alcohols. Examples of phenolic antioxidants are:

1.1. Alkylated monophenols: 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di- tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6- dicyclopentyl-4-methylphenol, 2-(alpha -methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl- 4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear nonylphenols or nonylphenols branched in the side chain, such as, for example, 2,6-dinonyl-4- methylphenol, 2,4-dimethyl-6-(1 '-methyl-undec-1 '-yl)-phenol, 2,4-dimethyl-6-(1 '-methyl heptadec- 1'-yl)-phenol, 2,4-dimethyl-6-(1'-methyltridec-T-yl)-phenol and mixtures thereof;

1.2. Alkylthiomethylphenols: 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6- methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;

1.3. Hydroquinones and alkylated hydroquinones: 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert- butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di- tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate;

1.4. Tocopherols: alpha -, beta -, gamma -, or delta-tocopherol and mixtures thereof (vitamin E);

1.5. Hydroxylated thiodiphenyl ethers: 2,2'-thio-bis(6-tert-butyl-4-methylphenol), 2,2'-thio-bis(4- octylphenol), 4,4'-thio-bis(6-tert-butyl-3-methylphenol), 4,4'-thio-bis(6-tert-butyl-2-methylphenol), 4,4'-thio-bis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxy-phenyl)disulfide;

1.6. Alkylidene bisphenols: 2,2'-methylene-bis(6-tert-butyl-4-methylphenol), 2,2'-methylene- bis(6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis[4-methyl-6-(alpha -methylcyclohexyl)phenol], 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(6-nonyl-4-methylphenol), 2,2'-methylene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethyl- idene-bis(6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis[6-(alpha -methylbenzyl)-4-nonyl- phenol], 2,2'-methylene-bis[6-(alpha, alpha -dimethyl-benzyl)-4-nonylphenol], 4,4'-methylene- bis(2,6-di-tert-butylphenol), 4,4'-methylene-bis(6-tert-butyl-2-methylphenol), 1 , 1 -bis(5-tert-butyl- 4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methyl- phenol, 1 ,1 ,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1 ,1-bis(5-tert-butyl-4-hydroxy-2- methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydro- xyphenyl)-butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert- butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphen yl]terephthalate, 1 , 1 -bis(3,5-di- methyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-propane, 2,2-bis(5- tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobuta ne, 1 , 1 ,5,5-tetra(5-tert-butyl-4- hydroxy-2-methylphenyl)pentane; 1.7. O-. N- and S-benzyl compounds: 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-di methyl benzyl-mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert- butylben-zyl-mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3- hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate;

1.8. Hydroxybenzylated malonates: dioctadecyl-2, 2-bis(3,5-di-tert-butyl-2-hydroxybenzyl) ma- lonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonat e, didodecyl- mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di [4-( 1 ,1,3,3- tetramethylbutyl)-phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydrox ybenzyl)malonate;

1.9. Hydroxybenzyl aromatic compounds: 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6- trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrameth ylbenzene, 2,4,6- tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol;

1.10. Triazine compounds: 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino) -1 ,3,5- triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)- 1 ,3, 5-triazi ne, 2-octyl- mercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4- hydroxyphenoxy)-1 ,2, 3-triazine, 1 ,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1 ,3,5- tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxy- phenylethyl)-1 , 3, 5-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahyd ro-

1 ,3, 5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate;

1.11. Acylaminophenols: 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, N-(3,5-di- tert-butyl-4-hydroxyphenyl)-carbamic acid octyl ester;

1.12. Esters of beta -(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid: with polyhydric alcohols, e.g. with 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- trioxabicyclo[2.2.2]octane;

1.13. Esters of beta -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, gamma-(3,5- dicyclohexyl-4-hydroxyphenyl) propionic acid, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid: with mono- or polyhydric alcohols, e.g., with methanol, ethanol, n-octanol, isooctanol, octade-canol, 1 ,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thi- odiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis-hydroxyethyl oxalic acid diamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- trioxabicyclo[2.2.2]octane;

1.14. Amides of beta -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid: N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

Examples of aminic antioxidants are: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl- p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N, N'-bis(1 -ethyl-3- methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N.N'dicyclo- hexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di(naphth-2-yl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)-N'-phenyl- p-phenylenediamine, N-(1 -methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'- phenyl-p-phenylenediamine, 4-(p-toluenesulfonamido)-diphenylamine, N,N'-dimethyl-N,N'-di- sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy- diphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4- dodecanoylaminophenol, 4-octadecanoylaminophenol, di(4-methoxyphenyl)amine, 2,6-di-tert- butyl-4-dimethylaminomethyl phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodi- phenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di[(2-methyl- phenyl)amino]-ethane, 1,2-di(phenylamino)propane, (o-tolyl)biguanide, di[4-(1',3'-dimethyl- butyl)phenyl]amine, tert-octylated N-phenyl-1 -naphthylamine, mixture of mono- and di-alkylated tert-butyl/tert-octyl-diphenylamines, mixture of mono- and di-alkylated nonyidiphenylamines, mixture of mono- and di-alkylated dodecyldiphenylamines, mixture of mono- and di-alkylated isopro-pyl/isohexyl-diphenylamines, mixtures of mono- and di-alkylated tert-butyldiphenyl- amines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and di-alkylated tert-butyl/tert-octyl-phenothiazines, mixtures of mono- and di-alkylated tertoctylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N- bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4- yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

Examples of further antioxidants are: aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid or salts of dithiocarbamic acid, 2,2,12,12-tetramethyl- 5,9-dihydroxy-3,7,11-trithiamidecane and 2,2,15,15-tetramethyl-5,12-dihydroxy-3,7, 10,14- tetrathiahexa-decane. The steps a) and b) are often included in a physical vapor deposition (also known as PVD). Suitable apparatuses for PVD are commercially available. The steps a) and b) are usually made in a vacuum chamber. The vacuum chamber has typically a temperature from 5 to 80 °C, preferably 10 to 40 °C, such as room temperature. The mechanical device has usually the same temperature as the vacuum chamber.

Step a) is vaporizing the lubricant additive. The vaporizing of the the lubricant additive is usually made in a vacuum of below 500, 300, 200, 100, 80, 60, 50, 40, 30, 20,10, 1, 0.1, 0.01, or 0.001 mbar.

The vaporizing of the lubricant additive is usually assisted by heating the lubricant additive, e.g. to above the boiling point under the applied vacuum. The vaporizing of the lubricant additive is usually assisted by heating the lubricant additive to at least 30, 50, 100, 150, or 200 °C.

Step b) is depositing the vaporized lubricant additive on the surface of the mechanical device to prepare an additive coated device. The depositing of the vaporized lubricant additive usually happens by a physical process such as condensation of the lubricant additive on the surface. The mechanical device is usually not heated. The deposition usually happens at a temperature from 5 to 80 °C, preferably 10 to 40 °C, such as room temperature.

The additive coated device usually has a coating comprising the lubricant additive on at least a part of the surface of the mechnical device.

The surface of the additive coated device is at least partially coated with the lubricant additive. Preferably, at least the surfaces of the mechanical device which come in contact with the lubricant are coated.

Typically, the surface of the mechanical device on which the vaporized lubricant additive is deposited is free of a lubricant.

The coating may have a thickness of up to 10, 5, 4, 3, 2 or 1 pm. The coating may have a thickness of at least 0.01 , 0.05, 0.1 or 0.3 pm.

The coating is usually free of other compounds beside the lubricant additives. The coating is usually consists of the lubricant additive.

In another form the additive coated device is heated prior to contacting it with a lubricant in step c), for example it is heated to at least 40, 50, 60, 70, 80, 100, 150, or 200 °C. The additive coated device can be heated for at least 0.1 , 0.5, 1 , 3, 5, 8, or 12 hours. The heating of the additive coated device is also known as chemical vapor deposition (CVD).

The surface of the mechanical device can be a metal or non-metal surface. Suitable surfaces are selected from metals, metal alloys, non-metals, non-metal alloys, mixed carbon-metal composites and alloys, mixed carbon-nonmetal composites and alloys, ferrous metals, ferrous composites and alloys, non-ferrous metals, non-ferrous composites and alloys, titanium, titanium composites and alloys, aluminum, aluminum composites and alloys, magnesium, magnesium composites and alloys, ion-implanted metals and alloys, plasma modified surfaces; surface modified materials; coatings; mono-layer, multi-layer, and gradient layered coatings; honed surfaces; polished surfaces; etched surfaces; textured surfaces; micro and nano structures on textured surfaces; super-finished surfaces; diamond-like carbon (DLC), DLC with high-hydrogen content, DLC with moderate hydrogen content, DLC with low-hydrogen content, DLC with near- zero hydrogen content, DLC composites, DLC-metal compositions and composites, DLC- nonmetal compositions and composites; ceramics, ceramic oxides, ceramic nitrides, FeN, CrN, ceramic carbides, mixed ceramic compositions, cermets, and the like; polymers, thermoplastic polymers, engineered polymers, polymer blends, polymer alloys, polymer composites; materials compositions and composites containing dry lubricants, that include, for example, graphite, carbon, molybdenum, molybdenum disulfide, polytetrafluoroethylene, polyperfiuoropropylene, polyperfluoroalkylethers, and the like; super hydrophobic surfaces; super hydrophilic surfaces; self-healing surfaces; surfaces derived from 3-D printing or additive manufacturing techniques, which may be additionally used as -manufactured, or used with post-printing surface finishing, or used with post-printing surface coating.

Preferrably, the surface is a metal surface, such as surfaces which are metals, metal alloys, mixed carbon-metal composites and alloys, ferrous metals, ferrous composites and alloys, nonferrous metals, titanium, titanium composites and alloys, aluminum, aluminum composites and alloys, magnesium, magnesium composites and alloys, ion-implanted metals and alloys.

In another preferred form the surface is a polymer surface, preferably a thermopolastic polymer, such as polyaryletherketone (PAEK), especially polyether ether ketone (PEEK).

The surface may be pretreated with an organic solvent (e.g. hydrocarbons, acetone, alcohols) or with plasma. In a preferred form the surface is pretreated with plasma. In another preferred form the surface is pretreated with organic solvent.

The mechanical device may be a mechanism consisting of a device that works on mechanical principles. The mechanical device may by a part of powertrains, drivelines, transmissions, I differentials, gears, gear trains, gear sets, gear boxes, bearings, bushings, axles, turbines, compressors, pumps, hydraulic systems, batteries, capacitors, electric motors, drive motors, generators, AC/DC converters, alternators, transformers, kinetic energy converters, kinetic energy recovery systems. In one form the mechanical device is part of a vehicle. The term “vehicle” refers to any mobile or stationary platform, wherein mobile platforms are preferred. In particular vehicles are selected from a passenger vehicle, a light-duty or heavy-duty truck, a utility vehicle, an agricultural vehicle, an industrial or warehouse vehicle, or a recreational offroad vehicle.

Stepc c) is contacting the surfaces of the additive coated device with a lubricant. The contacting of the surface with the lubricant can be achieved by applying, spraying, dropping, or dipping into the lubricant. Step c) is usually made after step b). The steps a), b) and c) are typically made in the given alphabetic order.

The term lubricant usually refers to compositions which are capable of reducing friction and/or reducing wear between surfaces (preferably metal surfaces), such as surfaces of mechanical devices. The lubricant is usually a lubricating liquid, lubricating oil or lubricating grease.

The lubricant usually comprises

- a base oil selected from mineral oils, polyalphaolefins, polymerized and interpolymerized olefins, alkyl naphthalenes, alkylene oxide polymers, silicone oils, phosphate ester, carboxylic acid esters; and/or

- optionally a further lubricant additive beside the lubricant additive. The further lubricant additive may be selected from the organic lubricant additives or from the inorganic lubricant additives.

The base oil may selected from the group consisting of mineral oils (Group I, II or III oils), polyalphaolefins (Group IV oils), polymerized and interpolymerized olefins, alkyl naphthalenes, alkylene oxide polymers, silicone oils, phosphate esters and carboxylic acid esters (Group V oils). Preferably, the base oil is selected from Group I, Group II, Group III base oils according to the definition of the API, or mixtures thereof. Definitions for the base oils are the same as those found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. Said publication categorizes base oils as follows: a) Group I base oils contain less than 90 percent saturates (ASTM D 2007) and/or greater than 0.03 percent sulfur (ASTM D 2622) and have a viscosity index (ASTM D 2270) greater than or equal to 80 and less than 120. b) Group II base oils contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120. c) Group III base oils contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 120. d) Group IV base oils contain polyalphaolefins. Polyalphaolefins (PAG) include known PAO materials which typically comprise relatively low molecular weight hydrogenated polymers or oligomers of alphaolefins which include but are not limited to C2 to about C32 alphaolefins with the C8 to about C16 alphaolefins, such as 1 -octene, 1 -decene, 1-dode- cene and the like being preferred. The preferred polyalphaolefins are poly-1 -octene, poly-1 - decene, and poly-1 -dodecene. e) Group V base oils contain any base oils not described by Groups I to IV. Examples of Group V base oils include alkyl naphthalenes, alkylene oxide polymers, silicone oils, and phosphate esters.

Synthetic base oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as pol-ymerized and interpolymerized olefins (e.g., polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1 -hexenes), poly(1 -octenes), poly(1 -decenes)); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2- ethylhexyl)benzenes); poly-phenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivative, analogs and homologs thereof.

Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic base oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having a molecular weight of 1000 or diphenyl ether of polyethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycar-boxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters and C13 oxo acid diester of tetraethylene glycol.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and sili-cate oils comprise another useful class of synthetic base oils; such base oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2- ethylhexyl)silicate, tetra-(4-methyl-2-ethyl- hexyl) silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl) siloxanes and poly(methylphenyl)siloxanes. Other synthetic base oils include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

The method according to the invention allows for lubricating moving surfaces of the mechanical device. Preferably, the method for lubrication reduces the friction and/or reduces the wear between moving surfaces of the mechanical device.

The friction may be determined by measuring the friction coefficient at 25% slide roll ratio (SRR) using mini-traction machine (MTM) measurements at 70 °C and 1 GPa.

The wear may be determined as described in the Examples.

The present invention further relates to a method for preparing the additive coated device as comprising the steps of a) vaporizing the lubricant additive, and b) depositing the vaporized lubricant additive on the surface of the mechanical device to prepare the additive coated device.

The present invention further relates the additive coated device wherein the surface of a mechanical device is coated with a coating consisting of an lubricant additive and where the coating has a thickness of up to 10 pm.

The present invention further relates the additive coated device wherein the surface of a mechanical device is coated with a coating consisting of an organic lubricant additive and where the coating has a thickness of up to 10 pm. Preferably, the additive coated device is obtainable by a method comprising the steps of a) vaporizing the lubricant additive, and b) depositing the vaporized lubricant additive on the surface of the mechanical device to prepare the additive coated device. Examples

Irgalube® FE1: Organic friction modifier, CAS 1000817-22-0, Fatty acids, C8-18 and C18- unsatd., reaction products with diethanolamine and propylene oxide; liquid at room temperature, melting point 2 °C, thermal decomposition around 135 °C (DSC, DIN 51007), thus boiling point not determined. Content (W/W): > 80 %, commercially available from BASF SE..

Irgalube® 353: extreme pressure I antiwear additive, CAS 268567-32-4, Propanoic acid 3- bis(2-methylpropoxy)phosphinothioylthio-2-methyl-. Clear liquid at room temperature, boiling point above 175 °C at 101.3 kPa, contains up to 20 wt% of a paraffinic hydrocarbon fluid, commercially available from BASF SE.

Irgalube® F10A: multifunctional lubricant antioxidant additive for thermooxidative stability of engine oil, CAS 179986-09-5, coconut oil, reaction products with glycerol esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid. Yellow liquid, melting point below -5°C, commercially available from BASF SE.

Irgalube® 349: multifuntional lubricant additive with extreme pressure, antiwear and antirust activity, CAS 80939-62-4, Amines, C11-14-branched alkyl, monohexyl and dihexyl phosphates. Viscous liquid at room temperature, , commercially available from BASF SE.

Example 1: Vaporization and Deposition

A MTM standard metal test block with 19,05 mm diameter was coated with Irgalube® 353 or Irgalube® FE1 as follows:

The test block was either cleaned with first ethanol followed by acetone (“solvent pretreated”) or the surface was activated by plasma pretreatment for 10 min under argon at 300 W (“plasma pretreated”). In a vaporization chamber the additive mixture (30 pl in an open container) was put under a vacuum of 5 10' ⁵ mbar at room temperature and the open container was heated by a current until the container was empty (1-2 min). The test block and the vaporization chamber were not heated. WO 2022/038011 _A _, PCT/EP2021/072362

17

The progress of the vapor deposition on the test block was followed by analyzing the thickness of the coating with a thin film deposition controller (Inficon XTC/3S). In addition, a hazy film was observed on the test block.

Example 2: Heat T reatment of coated device

The physical vapor deposition of the organic additives on the test block as described in Example 1 was followed by heating the coated test block for 18 hours at 80 °C at normal pressure. The effects were analyzed in the following Examples.

Example 3: MTM friction coefficient with metal test block

The friction coefficient [p] vs speed [mm/s] was determined by the MTM test on a MTM machine from PCS Instruments with a steel ball of 19.05 mm diameter and a test disk with 50 mm diameter, contact pressure 1 GPa, SRR 50%, test temperature 60 °C, test time 3 sec, velocity of first run 3000 mm/s, increment between 3000-1000 mm/s was 200 mm/s, increment between 1000-0 mm/s was 20 mm/s. The contact friction is measured by a torque converter, which is firmly mounted between the drive shaft and the test ball. The frictional force is determined perpendicular to the direction of loading. During the Stribeck test the average speed between test disc and ball are kept constant and the frictional force is applied in two directions measured. During the first measurement (TF1) the disc has a higher speed than the ball, in the second measurement (TF2) is the speed of the ball is greater. The coefficient of friction was thus calculated .

The lubricant was a group II mineral oil, viscosity grade VG 20, which contained for the comparative test 100 ppm Irgalube 353 and 100 ppm Irgalube FE1.

Figure 1 shows the friction coefficient [p] vs speed [mm/s] of the following tests, which were made with a lubricant of group II mineral oil, viscosity grade VG 20, which contained no additives.

- The doted line with diamonds shows the data of the comparative uncoated test block.

The normal line with the squares shows the data of the plasma pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 353, and heat treated as described in Example 2, and then coated with Irgalube FE1 as decribed in Example 1. - The dashed line with the triangles shows the data of the test block was used in previous run b), then flushed with group II mineral oil (viscosity grade VG 20) and tested a second time.

The results demonstrated that the friction coefficient of the coated test block was reduced compared to the uncoated test block. The results also demonstrated that the coating was stable even after cleaning the test block.

Figure 2 shows the friction coefficient [p] vs speed [mm/s] of the following tests, which were made with a lubricant of group II mineral oil, viscosity grade VG 20, which contained 100 ppm Irgalube 353 and 100 ppm Irgalube FE1.

- The doted line with diamonds shows the data of the comparative uncoated test block.

- The normal line with the squares shows the data of the solvent pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 353, and then coated with Irgalube FE1 as decribed in Example 1.

- The dashed line with the triangels shows the data of the plasma pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 353, and then coated with Irgalube FE1 as decribed in Example 1.

The results demonstrated that the friction coefficient of the coated test block was reduced compared to the uncoated test block. The results also demonstrated that such improvement was even achived when the additives were also present in the oil.

Example 4: Scattering in the first state of motion

The MTM test method of example 3 was used to determine the scattering in the first state of motion. To determine the standard deviation the tests were repeated 20 times.

In Table 1 the tests were made with a lubricant was a group II mineral oil, viscosity grade VG 20, which contained no additives. The uncoated comparative test block was compared to a plasma pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 353, and heat treated as described in Example 2, and then coated with Irgalube FE1 as decribed in Example 1.

The results show that the standard deviation in the first state of motion is reduced, which corresponds to a higher stability in this state.

Table 1

In Table 2 the tests were made with a lubricant was a group II mineral oil, viscosity grade VG

20, which contained 100 ppm Irgalube 353 and 100 ppm Irgalube FE1. The uncoated comparative test block was compared to

- a solvent pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 353, and then coated with Irgalube FE1 as decribed in Example 1.

- a plasma pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 353, and then coated with Irgalube FE1 as decribed in Example 1.

The results show that the standard deviation in the first state of motion is reduced, which corresponds to a higher stability in this state.

Table 2

Example 5: MTM friction coefficient with polymer test block

The MTM friction coefficient was determined as described in Example 3, except that instead of a metal test block now a high performance thermoplastic polymer (polyetheretherketone PEEK; obtainable by dialkylation of bisphenolate salts) test block was used. The results are summarized in Figure 3. Figure 3 shows the friction coefficient [p] vs speed [mm/s] of the following tests, which were made with a lubricant of group II mineral oil, viscosity grade VG 20, which contained no additives.

- The doted line with diamonds shows the data of the comparative uncoated test block.

- The dashed line with the triangles shows the data of the solvent pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 349, and then coated with Irgalube 353 as decribed in Example 1.

- The normal line with the squares shows the data of the plasma pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 353, and then treated as in Example 2, then coated with Irgalube 349 as decribed in Example 1.

- The dotted line with the circles shows the data of the plasma pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 353, and then treated as in Example 2, then coated with Irgalube 349 as decribed in Example 1.

The results demonstrated that the friction coefficient of the coated polymer test block was reduced compared to the uncoated polymer test block.

Example 6: MTM friction coefficient

The MTM friction coefficient was determined as described in Example 3 and the results are shown in Figure 4. Figure 4 shows the friction coefficient [p] vs speed [mm/s] of the following tests, which were made with a lubricant of group II mineral oil, viscosity grade VG 20, which contained 100 ppm Irgalube 349 and 100 ppm Irgalube F10A.

- The doted line with diamonds shows the data of the comparative uncoated test block.

The normal line with the squares shows the data of the solvent pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 349, and then treated as in Example 2, then coated with Irgalube F10A as decribed in Example 1. - The dashed line with the trianlge shows the data of the plasma pre-treated test block, which was first coated as decribed in Example 1 with Irgalube 349, and then treated as in Example 2, then coated with Irgalube F10A as decribed in Example 1. The results demonstrated that the friction coefficient of the coated polymer test block was reduced compared to the uncoated polymer test block