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Publication numberUS3277001 A
Publication typeGrant
Publication dateOct 4, 1966
Filing dateJul 6, 1965
Priority dateJul 6, 1965
Publication numberUS 3277001 A, US 3277001A, US-A-3277001, US3277001 A, US3277001A
InventorsFischer Paul W, Maly George P
Original AssigneeUnion Oil Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Aqueous lubricant
US 3277001 A
Abstract  available in
Images(12)
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,277,001 AQUEOUS LUBRICANT Paul W. Fischer, Whittier, and George P. Maly, Newport Beach, Calif., assignors to Union Oil Company of California, Los Angeles, Calif., a corporation of California No Drawing. Filed July 6, 1965, Ser. No. 469,910 20 Claims. '(Cl. 252-325) This application is a continuation-impart of our copending applications, Serial Numbers 121,832 and 398,112, now abandoned.

This invention relates to a method for lubricating surfaces in frictional contact with an aqueous media; to the aqueous media and to a concentrate for preparing said media; and in a specific adaptation this invention relates to aqueous hydraulic fluids.

Heretofore, the art of lubrication has centered about methods of preparing lubricants or greases and thereafter applying the lubricant so prepared to the point of wear or friction. Innumerable and complex lubricating compositions have been prepared, generally comprising a hydrocarbon oil, a bodying or gelling ingredient, fillers, extreme pressure lubricants and other ingredients to modify the lubricant. The complexity of these compositions is equalled only by methods and apparatus used to apply these lubricants to the points of frictional contact in suflicient quantities to reduce and control the wear.

This approach to the problem of wear has several serious disadvantages. Mechanical lubricating systems must be built into practically all present machines. Because the grease or lubricant is preformed, e.g., in a kettle, a compromise must often be made in its formulation. The lubricant must be suflficiently pliable so as to readily extrude through the lubrication passageways and reach the points of wear. At the point .of wear, however, extrusion of the grease results in its rapid loss. The grease is also rapidly decomposed by the extremely high temperatures generated at the contact. Thus prior art lubrication techniques have not utilized the frictional heat generated to aid lubrication, but rather, commonly fail because of frictional heat. In contrast, our invention utilizes a large portion of the frictional heat to manufacture grease in situ and thus reduces the amount of heat available for decomposition of the grease.

A specific application of our invention is in the field of hydraulic fluids. Oil base fluids are commonly used; however, because these fluids are inflammable they are not well suited for use in the oil industry. This limitation has curtailed the use of hydraulic pumps in oil wells. Some limited use of hydraulic pumps has occurred in the past several decades and a detailed description of this type of hydraulic pump and its operation is given at pages 2894 et seq., of the 1957 edition of the Composite Catalog of Oil Field Equipment and Services. Briefly, the hydraulic pump is positioned in the well base beneath the earths surface and powered by a hydraulic fluid. The hydraulic fluid is usually supplied to the well from a central source which, through a network of piping on the earths surface, supplies one or all the wells in the area. Crude oil, freed of silt and brine, is almost universally employed under pressures often in excess of 5000 p.s.i.

To eliminate the fire hazard, various silicone, polyester and halogenated hydrocarbon synthetic oils have 3,277,001 Patented Oct. 4, 1966 "ice been developed to provide uninflammable hydraulic fluids. Because these synthetic oils are expensive they must be employed in relatively fluid-tight recirculating systems. It has also been suggested that various cutting oils can be added to water, but the low viscosity and consequently high loss of the water greatly reduces the operating efiiciency of the pump. Additionally, cutting oils are unstable in brines and must be employed in relatively high concentrations (greater than about 1 percent). Attempts have also been made to employ oil field brine or other available water directly as the hydraulic fluid; however, heretofore these attempts have not been successful because of the corrosivity and poor lubricity of water and the high fluid loss experienced with low viscosity water. A high fluid loss is objectionable not only because it reduces the efliciency of the pump but also because it erodes the pump bearing surfaces, requiring frequent repair and maintenance.

It is an object of this invention to provide a simplified method for lubricating surfaces in friction.

It is an object of this invention to simplify the mechanical design of machinery by providing a lubricating method which requires very simple lubricating means.

It is also an object of this invention to simplify the construction of machinery by providing a lubricating composition which effectively lubricates and seals mating surfaces in friction which have loose fits, thereby eliminating the need for costly machining and finishing operations.

It is also an object of this invention to provide a lubricating method which is temperature responsive and in which there is an automatic supply or replenishment of lubricant to surfaces in friction as a direct function of the frictional heat generated by said surfaces.

A specific object of this invention is to provide an aqueous hydraulic fluid suitable for oil field use. A related object is to provide a concentrate for addition to water for the preparation of said aqueous hydraulic fluid.

Other and related objects will be apparent from the following description of our invention.

We have found that the aforementioned objectives can be secured by a method comprising the steps of supplying an aqueous medium containing reactive ingredients tothe surfaces in frictional contact and moving the surfaces to generate suflicient frictional heat release to initiate the reaction of the reactants and to deposit a lubrieating film on the surfaces. This deposit forms a plastic film or layer on the surfaces which fills and effectively seals the clearances against fluid passage. The formation of a high viscosity deposit from a lubricant is in marked contrast to the lubricating art which teaches that conventional grease and oil lubricants can form undesirable sludge and that the sludge or deposit precursors must be refined out of the lubricant.

The difficulty with the prior art has been its failure to control the nature of the sludge and the location of its deposition. Generally the prior art sludges have a high coefiicient of friction, low heat conductivity, high emulsification tendency and absorbency to acids. Additionally the sludges readily polymerize and carb onize. F requently the sludges plug the lubricant ports and passageways and prevent an adequate supply of lubricant.

The deposit formed with our lubricant, however, is designed to have a low coeflicient of friction and sufficient adhesion to maintain a fihn on the surfaces under dynamic conditions. Additionally, our lubricants are 3 heat sensitive so as to form only on the surfaces where needed, i.e., on surfaces in friction, and thereby avoid plugging ports and fluid passageways.

As employed in our method, the aqueous medium comprises a major proportion of water with minor to minute proportions of reactive ingredients and in this form is well suited for use as an aqueous hydraulic fluid. The reactive organic ingredients employed are efiective at extremely low concentrations, e.g., the preferred ingredients effectively seal, lubricate and inhibit corrosion of the surfaces at concentrations as low as 0.005 weight percent in water. In general, these reactive organic ingredients are employed in concentrations from 0.005 to 5.0 weight percent. The invention can also be practiced by dispersing to users the reactive ingredients in concentrates which can be diluted with water to f r-m the aqueous lubricant. I

The reactive ingredients employed in our method compise organic anions which are reactive with alkaline earth metal ions in the water. Typical of such reactive organic anions are the aliphatic carboxylates which can be supplied as the acids or the alkali metal or ammonium salts thereof; as well as the anions of organic phosphorous acids as described hereafter in greater detail. Generally these reactive organic anions have aliphatic chains containing from 8 to about carbons to ensure water insolubility of their alkaline earth metal salts and to ensure that the deposit so formed will have the desired lubricity.

Alkaline earth metal ions, preferably calcium, are em ployed in our lubricants to react with the aforementioned organic anions and thereby form a grease-like deposit which serves to seal the tolerances between the moving surfaces and to lubricate these surfaces. This deposit has been found to have a fibrous structure possessing a high degree of lubricity. Because of its high water insolubility the deposit is also quite stable. Conveniently hard water, i.e., tap water or brine can be used to prepare our dilute lubricants since a sufiicient amount of alkaline earth metalion content is naturally present in these waters. In general, at least about 10 ppm. of the precipitant, the alkaline earth metal ion, is desired. As mentioned hereafter, various other metal cations can also be used as precipitants to modify the properties of the deposit, e.g., to impart extreme pressure lubrication to the deposit. The nature of the lubricant can be widely varied and controlled by the judicious choice of modifiers that can be incorporated in the aqueous fluid. Typical of modifiers include various plasticizers which modify the hardness of the deposit, solvents which control the sealing characteristics of the deposit, tackifiers which control the adhesiveness of the deposit to the metal surfaces, extreme pressure agents which extend the surface life of the equipment as well as the necessary amounts of an emulsifier to prevent the various components of the fluid from precipitating prior to use. In addition, corrosion inhibitors and various coupling agents can be employed when desired, the latter being useful to enhance the emulsification of the concentrates of our invention in the aqueous medium and to impart a high degree of stability of the emulsion.

From the preceding description of the method, it is apparent that the proper functioning of the lubricating deposit depends on its reaction with the alkaline earth metal cation and resultant precipitation of the alkaline earth metal salt on the wearing surfaces. It was quite unexpected to discover that this reaction occurred at the surfaces in frictional contact and investigation revealed that it depended to some extent on the heat generated by the frictional engagement of the surfaces. Also unexpected was the fact that the nature of this deposit could be varied at will be judicious choice of modifying agents, particularly in view of the requirements that the modifying agent must also be incorporated in the deposit in a sufficient amount to modify the latter.

Referring now in greater detail to the components of the aqueous lubricants and hydraulic fluids which are useful as bodying agents to react with the alkaline earth metal precipitant any of the following can be used:

Aliphatic carboxylic acids having from 8 to about 25 carbons, i.e., saturated fatty or unsaturated fatty acids, alkali metal or ammonium salts thereof can be used.

Examples of suitable acids include the following: caprylic,

pelargonic, undecylic, lauric, tridecylic, myristic, pentadecylic, palmitic, datoric, capric, stearic, nondecylic, The satu arachidic, medullic, benhenic, carnaubic, etc. rated acids can be obtained from various animal and hydrogenated vegetable oils such as palm oil, beef tallow, lard oil, sperm oil, hydrogenated cottonseed oil, coconut oil, etc., in the manner well known in the art.

A suitable source of saturated acids also includes ox-.

idized wax acids obtained by oxidation of petroleum wax, e.g., Sunaptic acids commercially available from Sun Oil Company.

The nature of the deposit depends somewhat on the choice of acid employed; saturated acids tend to form more rigid and hard solids than unsaturated acids. When a pliable solid or oil external phase emulsion is desired, we prefer to employ unsaturated fatty acids or polymers are: oleic, linoleic, myristoleic, palmitoleic, dodecenoic,

pantadecenoic, etc. The oligomers or lower polymers of these acids, i.e., dimers, trirners, tetramers, etc., can also be used. These oligomers are available commercially or can be prepared simply by heating the unsaturated acid to between about 250 and 400 C. in the presence of 1 to 5% water which prevents decarboxylation. Further information on the polymerization of acids is set forth in Patent Number 2,482,761. Examples of such oligomers are linoleic dimer, oleic dimer, tall oil fatty acid dimers, palmitoleic trimer, etc.

As used herein, the term aliphatic carboxylic acid is also intended to include those acids which contain various substituents such as sulfur, e.g., sulfides, sulfates and sulfonates; halides, e.g., chloride, fluoride, bromide and iodide; hydroxyl; etc. Some of these acids are actually preferred because not only do they function as bodying agents but also contribute extreme pressure lubricity to the deposit.

Typical of a preferred class are the sulfided unsaturated fatty acids. These acids are commonly known in the art as sulfurized fatty acids and are sulfided and polysulfided unsaturated fatty acids and dimers thereof wherein sulfur has been added to the unsaturate double bonded carbons. In the dimer acids the sulfur crosslinks the acids to form diacid thioethers. These sulfided acids are simply prepared by heating a mixture of sulfur and any of an alkali metal bisulfite to the unsaturated double,

bond at mild conditions, e.g., to C. in an aqueous or aqueous alcoholic solvent can also be used.

Preparation of the halogenated fatty acids, as apparent to those skilled in the art, can be simply achieved by the direct addition of the halogen or addition of a hydrogen halide to the unsaturated carbons of any of the aforementioned unsaturated fatty acids or dimers thereof.

The unsat- As previously mentioned, another class of organic anions which are reactive @with alkaline earth metal cations to seal the tolerances between the moving surfaces are those of organic .phosphorus acids. These correspond to the following structure:

wherein:

X is hydrogen, alkali metal or ammonium R is alkyl, alkoxy, alkenyl or alkenoxy containing from 8 to about 18 carbons; and

R" is hydrogen, hydroxy, alkyl, alkoxy, alkenyl or alkenoxy having from 1 to about 18 carbons.

The aforementioned organic phosphorus compounds are of the phosphoric acid series, e.g., alkyl and dialkyl phosphoric acids corresponding to (RO) POOH; the phosphonic acid series, e.g., alkyl phosphonic acid, dialkylphosphonic acid and alkyl alkylphosphouic acid corresponding to RROPOOH; or the phosphinic acids, e.g., alkylphosphinic acid and dialkylphosphinic acid corresponding to R POOH. I

Typical of the phosphoric acids are: octyl phosphoric acid, oleyl phosphoric acid, linoleyl phosphoric acid, lauryl phosphoric acid, ethyl lauryl phosphoric acid, propyl decyl phosphoric acid, butyl pentadecyl phosphoric acid, amyl oleyl phosphoric acid, isohexyl tridecyl phosphoric acid, heptyl isodecyl phosphoric acid, dioctyl phosphoric acid, nonyl octyl phosphoric acid, isodecyl lauryl phosphoric acid, undecyl hexadecenyl phosphoric acid, d.i lauryl phosphoric acid, isotridecyl decyl phosphoric acid, tetradecyl oleyl phosphoric acid, pentadecyl Z-ethylhexyl phosphoric acid, etc. Any of the preceding acids can be prepared simply by reacting the proper alkanol or alkenol with orthophosphoric acid to add the desired alkoxy or alkenoxy group at temperatures from about 25 to 125 C.

Typical of the aforementioned phosphonic acids are: octyl phosphonic acid, decylphosphonic acid, dodecyl ethylphosphonic acid, oleyl phosphonic acid, linoleyl isopropylphosphonic acid, etc. The alkylphosphonic acids can be prepared by the oxidation of primary aliphatic phosphines or alkylphosphinic acids with strong oxidizing agents such as nitric acid or dichromate or permanganate salts in aqueous media at temperatures from about 25 to 175 C. The esterification of the *alkylphosphonic acid with an equal molar quantity of a suitable alkanol or alkenol in turn produces the alkyl or alkenyl alkylphosphonic acid.

Typical of the phosphinic acids are: didodecylphosphinic acid; decylphosphinic acid; 910 octadecenylphosphinic acid; ethyl, decylphosphinic acid, etc. These acids can be prepared by oxidation of primary and secondary aliphatic phosphines, e.g., by direct air oxidation can be used to prepare the phosphinic acids under mild conditions of 25 to 125 C. in a suitable aqueous solvent.

While the preceding materials are operative to provide an approved lubricity and sealing characteristic to the hydraulic fluids, we prefer to also use optional ingredients that greatly improve the functioning of the deposit and permit flexibility for various environments. Typical of materials which can be added to modify the deposit formed include plasticizers or softening agents, solvents, tackifiers, extreme pressure agents, corrosion inhibitors, and various additives serving one or more of the aforementioned functions.

Plasticizers or softening agents can be employed to vary the nature of the deposit and to control its hardness and brittleness. These plasticizers are particularly advantageous when a large proportion of the bodying agent previously described is a saturated fatty acid. Since the alkaline earth metal salts of saturated fatty acids are generally hard and brittle, it frequently becomes desirable to include agents in the reactive ingredients to soften the deposits. Examples of such optional materials which can be included in amounts up to about Weight percent of the reactive ingredients are described in the following paragraphs.

Sulfated and sulfonated fatty oils or their alkali metal or heterocyclic amine soaps thereof can be employed as a plasticizer. The preparation of these materials is well known in the art and briefly comprises the reaction of concentrated sulfuric acid with the fat or oil. Various sulfated and sulfonated fats and oils are commercially available and useful in our compositions. Examples of these materials are: sulfonated sperm oil, sulfonated coconut oil, sulfonated castor oil, sulfonated olive oil, etc.

Naphthenic acids can also be employed to soften and plasticize the soap in lieu of all or a portion of the previously described plasticizer. Naphthenic acids are obtained from middle distillates of mineral oils in a manner well known in the art. As with the other reactants the acids can be used directly or the alkali metal naphthanates can be used.

As previously mentioned, sulfonated mahogany acids can also be employed as an alternative or additional plasticizing agent in our hydraulic fluid. These acids are commercially available and their preparation is well known in the art. In one method, lubricating oil fractions are treated with concentrated sulfuric acid. The mahogany acids dissolve in the oil phase and are recovered therefrom by treatment of the oil with an alkali metal hydroxide, e.g., sodium hydroxide to produce the alkali metal sulfonates which can be recovered from the oil by extraction with alcohol. The extracted alkali metal sulfonate canbe used directly or acidulated to the acid form, The molecular weight of suitable sulfonate mahogany acids can be from about 320 to about 800 units.

Polymerized alkyl phenol sulfides such as described in US. Patent 2,139,321 are also useful reactive plasticizing agents. These materials are prepared by reacting ortho or para secondary and tertiary alkyl phenols, e.g., tertiary amyl phenol with sulfur monochlon'de or dichloride to produce a mixture of alkyl phenol sulfides and thioether polymers. In general, products having between about 2 and 10 alkyl phenol sulfide monomers per molecule are satisfactory.

Often the deposit must be used in environments where contrary characteristics are desired. Thus an effective bodying action is desired at the pump surfaces to seal tolerances between the surfaces in frictional contact. When the material which achieves the maximum sealing is employed in an oil well hydraulic pump, however, too effective of a bodying action will clog the reciprocating valve mechanism that controls the distribution of the power fluid supply to the hydraulic pump. This, in turn, results in decreased efliciency of the pump. To avoid this decreased efficiency it is desirable to include up to about weight percent of a suitable solvent. Various materials set forth in the following paragraphs in greater detail can be employed as solvents such as mineral oils, fatty oils, esters, alcohols and glycols, etc. Aromatic solvents, chlorinated hydrocarbons, etc. To insure that the lubricanfTa a suflicient pliable or fluid state, we prefer to employ a weight ratio of solvent to bodying agent up to about 5:1; preferably from about 1:10 to about 2:1.

Various organic compounds that have a solubility for calcium fatty acid soaps can be used. Preferably these solvents have atmospheric boiling points of at least F. and most preferably at least about 200 F. Examples of some of these compounds are:

Hydrocarbons such as aliphatic, alicyclic and aromatic hydrocarbons having from about 6 to about 25 carbons, e.g., cyclohexane, cyclohept ene, heptane, octane, nonane, isononane, decane, tridecane, pentadecane, hexadecane,

heptadecene, octadecane, eicosane, docosane, pentacosane, toluene, benzene, xylene, cumene, ethylbenzene, 1, 4-dimethylnaphthalene, ethylnaphthalene, l-methylnaphthalene, tetralin, decalin, pseudocumene, etc. The aforementioned hydrocarbons are commonly found in admixture as mineral oil distillates and are useful in this form. Examples of various distillates include those having a boiling point range between about 200 and 750 F., e.g., heavy naphtha, kersosene, light and heavy gas oils, lubricating oil distillates that preferably have been dewaxed, etc., so [that their melting point and preferably their cloud point is below about 32 F.

Also useful are various halogenated hydrocarbons including halogenated homologs of all the aforementioned such as chlorobenzene, dichlorobenzene, chloroheptane, chloronaphthalene, l-bromonaphthalene, etc., as well as halogenate derivatives of lower boiling hydrocarbons such as trichloroethane, tetrachloroethane, ethylene bromide, trichloroporpane, chloro-1,2-benzyl bromide, 1, 3-chlorobromobenzene, chlorobromoethane, chlorodibromoethane, dichloropentane, etc.

Esters can also be used such as propyl acetate, butyl acetate, ethyl butyrate, amyl acetate, monomethylglycol acetate (methyl-Cellosolve acetate), ethyl lactate, amyl propionate, cyclohexyl acetate, diethyl oxalate, glycol diacetate, amyl valerate, methyl benzoate, diethyl malonate, ethyl benzoate, methyl salicylate, diethyl maleate, propyl benzoate, dibutyl oxalate, butyl benzoate, amyl benzoate, diethyl phthalate, dibutyl phthalate, dihexyl glycolate, etc.

Esters of low molecular weight alcohols having from 2 to about 10 carbon atoms and fatty acids having from about 12 to about 25 carbon atoms can be used such as methyl laurate, propyl oleate, methyl stearate, amyl linoleate, isopropyl palmitoleate, butyl oleate, cyclohexyl laurate, etc.

Aliphatic, alicyclic and aromatic alcohols and glycols having from to about 25 carbons can also be used as the solvent such as allyl alcohol, pentanol, heptanol, hexanol, octanol, phenol, benzyl alcohol, decanol, lauryl alcohol, cresol, xylenol, oleyl alcohol, lino-leyl alcohol, stearyl alcohol, butyl phenol, etc., glycols such as ethyene glycol, triethylene glycol, diethylene glycol, ethylene and propylene oxide condensates with such glycols or alcohols having from 2 to about 12 alkylene oxide units, e.g., phenol poly(oxyethylene) glycol, ethylene glycol, poly (oxyethylene)ether, triethylene glycol, poly(oxypropy-lene) ether, etc. Ethers such as propylene glycol monomethyl ether, ethylene glycol diethyl ether (diethyl Cellosolve), ethylene glycol monomethy-l ether (methyl Cellosolve), ethylene glycol monoisopropyl ether, methyl-o-tolyl ether, di-iso-amyl ether, diet-hylene glycol diethyl ether, ethyl benzyl ether, tetraethylene glycol dimethyl ether, etc.

Various natural oil and fats can also be used such as almond oil, beechnut oil, black mustard oil, castor oil, coconut oil, cod liver oil, maize oil, cottonseed oil, hazel nut oil, lard oil, neats-f-oot oil, olive oil, palm oil, peach kernel oil, peanut oil, pumpkin seed oil, rape seed oil, seal oil, sesame oil, soya bean oil, whale oil, white mustard seed oil, wool fat, etc. The sulfurized fatty oils can also be employed as solvents. These oils are sulfided derivatives of the unsaturated fatty oil wherein sulfur is added to the unsaturate double bonded carbons to prepare sulfides and thioethers. Any of the aforementioned unsaturated fatty oils can be sulfied by heating to about 250-350 F. with sulfur for 1 to 3 hours.

As apparent from the preceding discussion of the method of the invention, the deposit is subjected to considerable mechanical shearing action and consequently a high adhesive characteristic is desired. We have found that the adhesion of the deposit to the metal surfaces can be greatly improved by the use of up to about 50 Weight percent of a rosin derivative, e.g., abietic acid or abietyl alcohol. Rosin acids which comprise 90% or more of the various wood and gum resins can be employed. Abiatic acid comprises the major portion of these rosins, however, various other acids such as pumeric, d-pumeric acid, suphenic acid, etc., are also present and useful in our invention. Rosin acids impart a tackiness and adhesiveness to the soap deposits. Additionally, since the alkaline earth metal salts of rosin acids are water insoluble, they also contribute to the volume .of the soap deposit and aid in sealing the tolerances between the moving surfaces.

The aforementioned rosin acids contribute substantially .to the adhesion of the lubricant on the metal surfaces.

In some instances, it is desirable to prevent solidification of this deposit and retain the precipitate as a semi-solid,

or oil-external phase emulsion. As previously mentioned, this is achieved in accordance with our present invention by incorporating various amounts of solvents, hereinafter set forth, in the composition. Accordingly, when solidification is undesired, the rosin acid can be eliminated from the composition, or all or a portion of the aforementioned rosin acid can be replaced with abietyl alcohol.

A convenient source of rosin acids as well as various unsaturated fatty acids useful as reactive modifying agents are crude tall oil and various distilled products of tall oil. Tall oil is a byproduct of the sulfate industry where it is found in the sulfide liquor that has been used to digest wood., The oil is a crude product containing various unsaturated fatty acids, chiefly oleic and linoleic, rosin acids and some unsaponifiable ma-.

terials. The crude tall oil can be employed as such in our invention, however, more suitably, various refined or distilled products of the crude oil are employed. Examples of these are the tall oil distillate that contains only slight amounts of rosin acids and from about unsaturated fatty acids. Other products are distilled tall oil having 25-35% rosin acids and 60-75%.

fatty acids. The tall oil pitch from the distillation has from'about 20-25% rosin acids and 30-40% unsaturated fatty acids, the balance being unsaponifiable material.

The lubricity of the grease-like deposit, its adhesion:

to the metal surfaces and its stability can also be enhanced by including in the aqueous lubricant one, or more water dispersible compounds of a polyvalent metal selected from the group consisting of the oxides or salts of zinc, cadmium, arsenic, lead, iron, cobalt, nickel and mixtures thereof. As used herein, the term water dispersible includes water'soluble as well as Water emulsifiable... The grease-like deposit formed from the aqueous lubricant incorporates these polyvalent metal ions in some unknown combination. The presence of these combined metals in the lubricant deposit greatly improves its lubricity and reduces wear. While .WC-dO not wish .to be bound by any theory for the role of these combined metals in the lubricating deposit, we believe.

they serve as extreme pressure or temperature lubricants and extend the useful temperature range of the lubricant past that obtainable with only organic ingredients.

The preferred metals to be combined in the lubricating deposit are zinc and lead and combinations thereof. In general we have found that the best results are obtainable with weight ratios of zinc to lead (calculated as oxides) between about 2:1 and 6:1.

The metal ions can also be added to the aqueous lubricating fluid in an amount of at least about 10 parts per million as water soluble salts such as the nitrate, acetate, sulfate, chloride, etc.; or by incorporating the salt into the concentrate. The metal soaps of organic fatty acids are water emulsifiable with an oil-in-water emulsifying agent and, therefore, these soaps can also be used. In a preferred embodiment, the desired metals as oxides or salts, e.g., zinc oxide and lead oxide, are added to all or a portion of the reactive organic ingredients of the concentrate and the resultant mixture heated to about to 400 F. for several minutes to several hours to saponify a portion of the reactive ingredients and form soaps with the 9 polyvalent metal ions. We prefer that no more than about 90 percent of the reactive organic ingredients of the concentrate be thus saponified with the polyvalent metals and, in particular, prefer that between about 15 and 80 percent be so saponified. In general, the amount of polyvalent metal so added corresponds to between about 1 and about 10 parts per 100 parts organic acids. The balance of the reactive organic ingredients are thus free to react with the alkaline earth metal ions and form the lubricating deposits at the points of wear.

Various corrosion inhibitors can optionally be added if desired. In general, we have found that the aqueous lubricants are not corrosive; however, under severe conditions of time, temperature or high salt contents, some corrosion may be encountered. This can readily be avoided by use of various corrosion inhibitors such as the polyalkylene polyamides of long chain fatty acids which are described in US. Patent 2,598,213 which are prepared by reacting a polyalkylene polyamine with a C to C fatty acid in an amount insufficient to react with all the amino groups, thereby leaving at least one free amino group per molecule. The inhibitors can be used in amounts from to weight percent of the reactive organic ingredients.

Also useful as an optional corrosion inhibitor are the piperazino alkylamides of polybasic carboxylic acids and glycollic acid salts thereof which are described in U.S. Patent 3,167,554. The amides are prepared by reaction of piperazine or aminoalkyl substituted piperazines, at temperatures from 100 to 300 F., with dicarboxylic fatty acids, in particular, dimerized linoleic acid, itself commercially available from Emery Industries, Inc., as Emery 30798. The remaining free amino group can then be reacted with glycollic acid to prepare the water soluble acid salt of the complex amide.

From the preceding discussion it is apparent that some additives can be employed which will impart more than a single desired characteristic to the deposit. Examples of such dual function additives are sulfurized oils which will serve both as lubricants under extreme pressure conditions and as solvents. Additional examples are sulfurized fatty acids which serve both as high lubricity components as well as bodying agents which form the deposit and seal the wearing surfaces.

Various emulsifying agents can be employed to disperse the reactive ingredients of our concentrate in the aqueous media. Preferably, about 1 to about 10 parts of an oilin-water emulsifier per 100 parts of said reactive ingredients is employed. The nature of this emulsifier is not critical to the invention as it does not enter into the lubricant forming reaction at the wearing metal surfaces. As apparent to those skilled in the art, a host of suitable emulsifiers are available, a few of which are listed as follows:

Anionic compounds obtained by sulfonation of fatty derivatives such as sulfonated tallow, sulfonated vegetable oils, sulfonated marine animal oils. Commercially available emulsifiers of this group are: Tallosan RC, a sulfonated tallow of the General Dyestulf Corp; Garnafon K, highly sulfonated fatty acids of coconut oil and Finish WFS, a sulfonated sperm oil.

Various sulfonated fatty acid esters of mono and polyvalent alcohols are also suitable such as: Nopco 2272R, sulfonated butyl ester of a fatty acid; Mekal N3, tri (2- ethylbutyl)sulfotricarboxylate; and Nopco 1471, sulfonated oleoglyceride.

Sulfated and sulfonated fatty alcohols are also useful as the additional emulsifier of our concentrate. Typical of this class of anionic agents are: Duponal ME, sodium lauryl sulfate; Duponal L 142, sodium cetyl sulfate; Duponal LS, sodium oleyl sulfate; Tergitol 4, sodium tetradecyl sulfonate; Tergital 7, sodium heptadecyl sulfonate; etc.

Nonionic oil-in-water emulsifiers can also be employed to enhance the dispersion of our concentrate in water and this class of emulsifiers is preferred when the hydraulic fluid is to be prepared from brine. Among the various nonionic agents are various ethylene oxide condensation products with fatty acids, alcohols and glycerides, phenolic compounds, fatty amides, amines and fatty acid partial esters of hexitans.

Examples of ethylene oxide condensation products with fatty acids are the following: Nonisol 100, ethylene oxide condensation product with lauric acid; Nonisol 200, ethylene oxide condensation product of oleic acid; Nonisol 300, ethylene oxide condensation product of stearic acid; etc.

Examples of ethylene oxide condensation products with fatty and rosin alcohols are: Brij 30, polyoxyethylene lauryl ether; Synthetics D-37, ethylene oxide condensate of hydroabietyl alcohol; etc.

Examples of ethylene oxide condensation products with alkyl and alkenyl phenols are: Igepal W, Igepa l C, Antarox A-200, ethylene oxide condensation products of n-dodecyl and isododecyl phenol; Triton TX45, octyl phenoxy polyethoxy ethanol; etc.

Examples of ethylene oxide condensation products with fatty amines and amides are the Ethoamides prepared by condensation of ethylene oxide with fatty acid amides having from 8 to 18 carbons.

Ethylene oxide condensation products of fatty acid partial esters of hexitans are suitable emulsifying agents in our invention. These agents are commercially available as the various Span and Tween products which are polyoxyethylene derivatives of sorbitan monolaurate, sorbitan monopahnitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, etc.

As will be apparent to those skilled in the art, various agents can be added to the concentrate (or to the hydraulic fluid) to clarify the emulsion. These agents are known as bridging or coupling agents and can be used in amounts from about 0.01 to about 5 parts per hundred parts of reactive ingredients. Examples of such are diethylene glycol, pentanediol, butyl Cellosolve as well as pH controlling agents such as oleic acid. If desired, a sequestering agent such as ethylenediamine tetraacetic acid or its alkali metal salt can also be added.

Various heterocyclic amines having between about 4 and 9 carbon atoms can also be employed to enhance the water dispersibility of our concentrate. These amines can be employed in amounts between about 5 and 50 parts per hundred parts of reactive ingredient. The preferred concentrate of our invent-ion contains morpholine, in amounts between about 15 and '20 par-ts per 100 parts of reactive ingredients. Examples of other suitable heterocyclic amines are: pyridine, pyrnole, pipetridine, pyrrolidine, piperazone, pynroline, pyrrolidone, etc. The addition of these amines to our concentrates greatly increases their water dispersibility, reducing, and in some instances, eliminating, the need for mixing of the concentrate after it has been added to the aqueous media.

The following will illustrate the use of the aqueous I lubricants of our invention as hydraulic fluids:

EXAMPLE 1 To evaluate the sealing properties of our hydraulic fluids, a standard air pressure actuated positive displacement pump was modified by removal of the pump check valves. A hydraulic fluid supply from a nitrogen pressured reservoir was connected to the pump side of the modified pump to provide a pressure drop across the pump piston of 500 to 3000 poundsper square inch. The air pressure supply to the pump was controlled to reciprocate the pump piston against the hydraulic fluid pressure at frequencies from 30 to 300 strokes per minute. The cylinder of the pump Was grooved on the low pressure side of the piston to provide a collector for hydraulic fluid which escaped through the pump tolerances and provision was made to measure the amount of fluid so collected.

1 l V The piston had a diameter of 0.625 inch and a stroke of 1.3 inches. A portion of the cylinder Wall was enlarged to reduce the length of'mating surface with the piston to The fluid loss was measured initially and at six-hour increments throughout the test duration. The following fluid losses in milliliters per minute were measured with the indicated organic additives:

Zinc soap of K0 acids Surfactol 365 I Tall oil distillate 0K0 acids 0K0 acids A...

Calcium soap of acids. Surfactol 365 e 5 Tall oil distillate 0K0 acids 8 Lead soap of acids. 2 Surfactol 365 v 40 6.---.. Tall oil distillate 158 1, 250 790 850 16' Lead soap of acids 2 Surfactol 365 0 40 7 Tall oil fatty acids 0 20 1,400 20 6 Nil Tallow fatty acids d 20 Lead soap of acids- 72 Zinc soap of acids 52 Surfaetol 365 8--- Monooleyl dihydrogen phos- 250 500 190 phate. Suriactol 365 a 0K0 acids is a commercially available mixture of unsaturated fatty acids, chiefly oleic acid and its dimer, obtained by the distillation of vegetable fatty acids. It has an average molecular weight of 336 and an acid number of about 167.

b Tall oil distillate is a mixture of resin acids 29.0 percent, oleic acid and linolcic acid 67.2 percent, saturated fatty acid 2.5 percent.

6 Tall oil fatty acids is a mixture of linoleic acid 39.0 percent, linolinic acid 7 percent, oleic acid 52.0 percent, saturated fatty acid 2.0 percent.

d Tallow fa tty acids is a mixture of stearic acid 2.9 percent, palmitic acid 11.0percent, myristic acid 1.7 percent, oleic acid 48.8 percent, linolineic 34.0 percent.

B Nonionic emulsifier comprising the ethylene oxide condensate of caster oil fatty acid.

1 inch. The tolerance between the piston and mating cylinder surface was about 0.002 inch.

The pump was initially supplied with oil field brine having the following composition for runs 1 through 7.

Component: Concentration Ca p.p.m 500 Mg p.p.m 6 Na p.p.m 12,000 HCO p.p.m 1,700 CO ..p.p.m N11 Cl p.p.m 14,000 80.; p.p.m 6 Organic additive p.p.m 200 pH 7.8

Potable water of the following composition was used EXAMPLE 2 The testing system of Example 1 was used on hydraulic fluids which contained a limited amount of .various of the aforementioned solvents with the reactive organic components. The organic components were added inan amount comprising 300 parts per million with the following approximate composition:

Component: Weight percent Zinc and lead fatty 'acid soaps 20-30 Unsaponified fatty acids 10-30 Surfia'ctol 365 16.0

Solvent 0-55 The solvents employed and the exact composition of the additives is indicated in the :following Table 2. The

test period extended for at least 48 hours on each composition. T-he fluid loss with water containing no additive was 400 to 450 milliliters per minute.

Run 9 contained rosin acids in an amountcomprisin-g 10 weight percent of the organic components while runs 11 through 24 contained 1 weight percent abietyl alcohol.

The ratio of saturated to unsaturated fatty acid was also varied in the experiments :as indicated. The following Table 2 sets forth the variation in these parameters and the fluid loss in milliliters per minute measured in the tests:

TABLE 2 Fatty acid Unsapon Solvent Metal ified Soaps+ Solvent, Percent Fluid Run Soaps Fatty Acid Soaps+ Unsapon- Loss Remarks Satu- Unsatu- Acid Total Identity Amount Acid ified rated rated 29 16 17 32 61 53 25 Hard plastic. 28 15 16 31 59 4 0. 07 53 3 Hard plastic. 27 14. 7 15. 6 30 57 Chlorothene 8 O. 14 53 25 Soft solid. 27 14.9 15.6 30 57 Cyclohexanol 8 0.14 53 20 Viscous liquid. 27 14.9 15. 6 30 57 Tetrahydroiuran 8 0.14 53 100 Viscous liquid. 27 14.9 15.6 30 57 Isopropano1 0. 6

g. 2 8 0.14 53 1 Soft solid. 4 0 15 13 7. 2 7. 7 15 11 2g 55 1. 96 53 150 Viscousliquid. 2 16 24 13. 4 14. 2 27. 6 1O 1; 16 0.38 53 20 Soft solid. v 1 29 17 32 0 53 7 28 18 18 16 0.29 39 160 26 17 31 16 0.28 53 150 30 20 20 16 0.31 40 130 28. 21 21 0. 31 42 200 15 15 37 1. 05 43 160 18 10 10 28 Fatty oil 42 l. 5 36 8,000 S.S.U. 100

F. viscous oil. 18 30 30 48 .d0 22 0. 22 63 id.

Component Parts by Weight Weight Percent Reactive organic components 100 48-90 Lubricant, e.g., polyvalent metal salts 1-10 0. 5-9. 0 Fmnlsifier 5-50 2 4432, 0 Heterocyclic amine (optional) 5-50 2. 4-32. 0

The aforementioned reactive organic components comprise the sealing or bodying agent which can be an aliphatic carboxylic acid, alkali metal or ammonium salt thereof or an aliphatic phosphoric, phosphonic or phosphinic acid, alkali metal or ammonium salt thereof. The reactive components can, optionally, also com-prise from 0 to 50 percent of the aforementioned rosin derivatives, abietic acid or abietyl alcohol and can also comprise any of the aforementioned plasticizers in amounts from 0 to 95 weight percent, preferably from about 5 to 25 weight percent.

The following will illustrate concentrates containing some of the aforementioned lubricating additives, e.g., polyvalent metals, of our invention which can be added to water to provide aqueous lubricants having organic reactant concentrations of from 0.005 to 5.0 weight percent:

Concentrate 1 Reactive ingredients (100 parts): Parts by weight Caprylic acid 20 Tall oil rosin Pentadecenoic acid 50 Sulfonated sperm oil 50 Cadmium (calculated as CdO) 10 Concentrate 2 Reactive ingredients (100 parts): Parts by weight 1 Sodium tetradecyl sulfonate.

Concentrate 3 Reactive ingredients parts): Parts by weight Capric acid 15 Tall oil rosin 25 Naphthen-ic acid 60 Sulfonated spenn oil 50 Lead (calculated as Pb O 35 Pyrrole 30 Concentrate 4 Reactive ingredients (100 parts): Parts by weight Undecylic acid 35 TAPS 1 V 6 Nonisol 2 45 Zinc (calculated as ZnO) 10 Lead (calculated as =Pb O 2 /2 Pyrrolidine 15 Commercially available polymer of tertiary amyl phenol sulfide, having an average molecular weight of about 500 600 units.

:dEthylene oxide condensation production of 012 to C13 fatty ac s.

Concentrate 5 Reactive ingredients (100 parts): Parts by weight Luric acid 10 Tall oil rosin 20 Palmitoleic acid 70 Nopco 1471 20 Zinc (calculated as ZnO) 16 Piperazine 20 Sulfonated 'oleoglyceride.

C ncentrate 6 Reactive ingredients (100 parts): Parts by weight Tridecylic acid 25 Sulfonated sperm oil 75 Sanfotal 40 Iron (calculated as Fe O 8 Pyridine 22 saponification, the meals such as zinc, lead, arsenic, coblat and nickel are added to the mixture of fatty acids, plasticizer, and optionally, rosin, and the mixture then heated to about 100 to 500 F; preferably 300 to 400 F.; for several minutes to several hours. Thereafter the mixture is cooled to at least about 175 F. and the oil-inwater emulsifier and optional clarifying agent such as the heterocyclic amine added.

The saponification of oadmiumr-and iron with fatty acids-is well known in the art and any suitable method can be used. Briefly, a suit-able preparation is as follows: an aqueous solution of the sodium of alkali'metal fatty acid soap is reacted with a water soluble salt of the desired metal such as iron chloride, cadmium chloride, etc. The solution is preferably heated and the metal soap, e.g,. cadmium oleate, precipitates and is dissolved in an organic solvent such as benzene. Upon evaporation of benzene, the soap is ready for addition to our concentrate; however, in some instances it may be desirable to clarify the benzene extract by filtration prior to evaporation of the benzene.

As thus compounded, the aforementioned concen trates are suitable for use in fresh waters having at least about 10 parts per million of an alkaline earth metal ion. As previously mentioned, the alkaline earth metal, preferably calcium, can be naturally present in the water (hard water) or it can be added as a water soluble salt. When it is necessary to add an alkaline earth metal ion, a water soluble salt of the metal can be added directly to the water or incorporated into the concentrate in amounts between about :1 and 100 parts per 100 parts of the aforedescribed concentrates.

While the aforedescribed concentrates are suitable for use with fresh or potable waters, the following concentrates having nonionic emulsifiers are preferred for use in salt waters and oil field brines which have a high content of sodium, generally greater than about several thousand parts per million.

Concentrate 7 Reactive ingredients (100 parts): Parts by weight Myristic acid Tall oil rosin 15 Linoleic acid 80 Tween 20 Cadmium (calculated as CdO) 18 Lead (calculated as Pb O 3 Morpholine 30 1 Ethylene condensate of fatty acid esters.

Concentrate 8 Reactive ingredients (100 parts): Parts by weight Pentadecylic acid 15 Isodecyl lauryl hydrogen phosphate 85 Brij 30 1 15 Zinc (calculated as ZnO) '10 Pipen'dine 17 1 Polyoxyethylene lauryl ether.

Concentrate 9 Reactive ingredients (100 parts): Parts by weight Palmitic acid 7 Gum rosin 3 Sodium naphthanate 90 Surfactol 365 1 5 Zinc (calculated as ZnO) 10 Lead (calculated as Pb O 5 Morpholine 25 Ethylene acids condensate of caste: oil fatty acids.

Concentrate 10 Reactive ingredients ('100 parts):

Isohexyl tridecyl hydrogen phosphate Linoleic acid 95 Surfactol 365 5 Lead (calculated as Pb O 5. Morpholine 15' Concentrate 11 Reactive ingredients (100 parts): Parts by weight Stearic acid 11 Tall oil rosin 9 Potassium naphthanate Surfactol 365 30 Zinc (calculated as ZnO) .10 Lead (calculated as Pb O 2 Water 25 Concentrate 12 Reactive ingredients (100 parts) Parts by weight Nonadecylic acid 15 Sulfonated mahogany acids Surfactol 365 25 Zinc (calculated as ZnO) .14 Lead (calculated as Pb O 2 Morpholine 25 Concentrate 13 Reactive ingredients parts): Parts by weight Arachidic acid 8 Tall oil rosin 7 Oleic acid 45 Linoleic acid 40 Surfactol 365 15 Zinc (calculated as ZnO) 10 Lead (calculated as Pb O 1 Morpholine '25 Concentrate 14 Reactive ingredients (100 parts): Parts by weight Medullic acid l7 Wood rosin 3 TAPS 80 Surfactol 365 15 Zinc (calculated as ZnO) 5 Lead (calculated as Pb O 10 Morpholine 25 Concentrate 15 Reactive ingredients (100 parts): Parts by. weight .Behenic acid 9 Sodium mahogany acids 85 Surfactol 365 10 Zinc. (calculated as ZnO) 10 Lead (calculated as Pb O 2%. Morpholine 25 The preceding concentrates have been described as mixtures of relatively pure components. As apparent to those skilled in the art, relatively pure fatty acids are not common since the acids occur in animal and vegetable oils as mixtures of homologous members of the fatty series. Thus tallow serves as a convenient source of saturated fatty acids (stearic and palmitic), but also present is generally an equal amount of a mixture of oleic and linoleic acids. As previously mentioned, tall oil rosin is found in crude tall oil and its products, constituting about :30 percent by Weight of these materials. The balance of the oil is a mixture of linoleic andoleic acids. It is preferred to employ the more common sources of the acids and the relatively pure acids are used only to adjust the final con- Parts by weight 17 v centration of the components. These compositions are illustrated as follows:

Concentrate 16 Parts by weight Composition is about: tall oil rosin, 29%; unsaponifiables, 1.3%; oleic acid, 34.3% linoleic acid, 25.8%; saturated fatty acid, 2.5%.

2 Composition is about: stearic'acld, 15% palmitic acid, 33% myristic acid, 2% oleic acid, 48% linoleic acid, 2%.

3 Composition is about: rosin acids, 1.0% unsaponifiables, glyeic acid, 52.0% lineoleic acid, 45% saturated fatty 8.0 a.

Concentrate 17 Parts by weight Coconut oil fatty acids 1 55 Tall oil I 120 Corn oil fatty acids 2 65 Dioctyl hydrogen phosphate 60 Morpholine l Surfactol 3 65 60 Composition is about: capryllc, 9% capric, 5% lauric, 51.0%; myristic, 18%; palmitic, 8%; stearie, 3.0%; oleic, 5.0% linoleic 1.0%.

2 Composition is about: palmitic, 8% stearic, 4%; oleic, 46%, llnoleic, 42%.

As previously mentioned, optional amounts of solvents can be included in our aqueous lubricantsand concentrates in the manner described in ourcopending application, Serial Number 398,112. These solvents modify and soften the lubricating deposit and thus avoid sticking of the valves in. subsurface oil well hydraulic pumps. The typical composition of concentrates containing solvents is set forth in the following table.

SOLVENT CON CENTRA'IES Parts by Weight Component Broad Preferred Bodying agent preferably a fatty acid 5-40 10-18 Optional tackifier, preferably rosin alcohol or acid 0-20 l-5 Solvent, preferably a fatty oil 40-05 77-89 Total Emulsifiable Components- 100 100 Oil-in-water emulsifier 5-50 5-15 Metals present as soaps of bod ferably zinc and lea 1 0-10 1 1-5 Heterocyclic amine 0-50 10-25 1 Calculated as oxides.

In addition, the concentrates have the following properties:

Trace-5.0 5-100 Weight ratio solvent to bodying agent Percent unsaponified bodying agent The following will illustrate concentrates according to our invention that contain slight amounts of various solvents: v p

Concentrate 18 Emulsifiable organic components, (100 parts Concentrate 19 V Emulsifiable organic components, 100 parts):

'Oleic acid parts by weight" 28 Stearic acid do 8 Tall oil rosin d0 2 Chlorobenzene do 68 Sulfonated sperm oil do 50 Zinc (calculated as ZnO) ..do 4 Lead (calculated as Pb O do 1 Morpholine do 25 Water do-.." Solvent to bodying agent ratio 2.33 Percent unsaponified acids. 18

Concentrate 20 Emulsifiable organic components, parts):

, Myristoleic acid "parts by weight-.. 25 Ethylene bromide do' 75 Nopco 1471 do 20 Iron (calculated as Fe O do 3 Piperazine do 20 Water--- do 50 Solvent to bodying agent ratio 3 Percent unsaponified acid 65 -Sulfonated oleoglyceride.

V Concentrate 21 Emulsifiable organic components, (100 parts):

Lauric acid "parts by weight 20 Monomethylglycol acetate do 80 Tween 1 d 20 Nickel (calculated as NiO) do 2 Mohph'oline do 30 Water do 70 Solvent to bodying agent ratio 4 Percent unsaponified acid 46 1 Ethylene oxide condensate of fatty acid esters.

Concentrate 22 Emulsifiable organic components, (100 parts):

Palmitoleic acid "parts by weight 30 Benhenic acid do 5 Butyl acetate do 65 Sanfotal do 48 Cobalt (calculated as C00) do 2 Pyridine do 22 Solvent to bodying agent ratio 1.8 Percent unsaponified acid 59 -Su1fonated tall oil. Concentrate 2 3 Emulsifiable organic'components, (100 parts):

Peanut oil fatty acid parts by weight 35 Butylphenol do 65 Surfactol 365 do 38 Zinc (calculated as ZnO) "do"..- 3 Lead (calculated as PbO) do 1 Water do 26 Solvent to bodying agent ratio '1.9 Percent unsaponified acid 40 1 Linoleic, 2e oleic, 56% palmitic, 8% arachidic, a stearic, 3% behenic, 2.2%.

V Concentrate 24,

Emulsifiable organic components, 100 parts):

Linoleic, 51.2%.; linolinic, 5.4% oleic, 30.2% saturated acids, 13.2%.

Concentrate 25 Emulsifiable organic components, (100 parts):

Eruoic, 57% oleic, 20% linoleic, 15% lignoceric, 3% linolinic, 2% myristie, 2% stearic. 2%.

2 Linoleic, 49% oleic, 25% palmitic, 21.8% stearic, 2.0% myristic, 1.5% arachidic, 1.0%.

Concentrate 26 Emulsifiable organic components, (100 parts):

:Tallow fatty acid parts of weight 23 Corn oil fatty acid 2 do 15 Castor oil do 62 Surfactol 365 do 20 Zinc (calculated as ZnO) do 4 Lead (calculated as PbO) do 1 Water do 30 Solvent to bodying agent ratio 1.8 Percent unsaponified acid 10 1 Stearic, 2.9% palmitic, 11.0% myristie, 1.7% oleic, 40.8% linoleic, 34.0%.

2 Palmitic; stearic, 51% oleic and linoleic acids.

Concentrate 27 Emulsifiable organic components, (100 parts) Sulfurized oleic acid parts by weight 27 Tall oil fatty acids 1 do 20 Neutral lubricating oil do 53 Surfactol 365 do 18 Water do 59 Solvent to bodying agent ratio 1.1 Percent unsaponified acid 100 1 Linoleic, 39% linolinic, 7% oleic, 52% saturated acids, 2%.

Concentrate 28 Emulsifiable organic components, (100 parts):

Tall oil fatty acid 1 parts by Weight 45 Cottonseed oil do 55 Surfactol 365 do 15 Solvent to bodying agent ratio 1.2 Percent unsaponified acid 100 1 See Concentrate 9. 2 See Concentrate 8.

Concentrate 29 Emulsifiable organic components (100 parts):

Chlorinated oleic acid parts by weight 35 Cottonseed oil do 65 Sunfactol 3-65 do 15 Solvent to bodying agent ratio 1.85 Percent unsaponified acid 100 Concentrate 30 Emulsifiable organic components (100 parts):

Sulfurized tall oil fatty acids 1 .parts by weight--. 33

Tall oil fatty acid d 13 Naphthenic oil, 509 SSU at 100 'F. do- 53 Abietyl alcohol 1 Surfactol 365 20 Corrosion inhibitor 2 4 1 Surfurized mixture of rosin acids. 1.0% oleic acid, 52.0% linoleic acid. 450% saturated fatty acid, 1.0%.

dG1yc0ll1c acid salt of bis(piperazinoethyi)amide of dimer aci r To illustrate the application of our invention in the operation of an oil well hydraulic pump, a pump such as described in the aforecited catalog and having a closed I hydraulic circuit was placed in a tank and facilities were provided to supply the power piston of said pump with the aqueous hydraulic fluids of our invention. The pump 20 1 had a reciprocating valve mechanism having clearance between the moving valve parts of about 0.0002 inch.

The pistons of the pump had clearances of about. 0.003

inch and each piston had 14 rings with interference fits.

A back pressure control valve was placed on the discharge of the hydraulic fluid from the motor piston ,of

the pump and the discharge from the pump side was.

passed through a second pressure control valve and returned to the tank. The tank was equipped withan ovenfiow 'With provision to measure the rate of flow therethrough. The amount of the aqueous hydraulic fluid which escaped between the power piston and cylinder and past the reciprocating controlling valve mechanism went into the tank and displaced an equal volume of the contents thereof through the overflow. Measurement of the ovenflow ratei-thus provided a simple and accurate indication of the loss or leakageof the power fluid.

Inlet and outlet pressures and strokes per. minute of the pump were measured to determine the operating efficiency of the pump.

The aforedescribed pump was operated for a test period of about 3 months under varied rates throughout the. design range (about 20 to about strokes per minute with an inlet or head pressure of about 200 to 3500 p.s.i. and net power pistonpressure differential between about 150 to 3200 p.s.i.).

Oil field brine having a pH of'7.8 and the following analysis was used as the power fluid:

Ion: Parts per mil-lion Ca 465-500 Mg++ 6 Na+ 1 2,000 H00 1,700 CO Nil Cl 14,000 SO 0.01 and 0.1 weight percent of Concentrate 16. The

pump efficiency remained above percent throughout the test period in contrast to efiiciencies with oil field brine 1 having no additive wherein the initial efliciency is about 70 percent and decreases to 30 percent within a Week. The fiuid loss throughout the test period varied between 0 and about 10 milliliters per minute.

Upon completion of the test, the pump was dismantled and inspected. No visual signs of wear or corrosion were 1 observed on the piston, cylinder walls, valve mechanism, or other parts of the equipment.

ton ring grooves, etc.).

wet and water repellent surface. The film was very tacky and adhered very strongly to the metal surfaces. white precipitate was observed to be weakly adsorbed on recessed metal surfaces which were not in friction. This precipitatei was soft and was not tacky.

Electron micrographs of the grease-like deposit show that the deposit has a definite rodor lfi'brous crystalline structure with fiber lengths between about 0.5 and .3 microns in length; the majority of the fibers having a length of about 1 micron.

Optical microscope studies of particles of the grease,

like deposit show it to comprise an agglomerated or congealed phase having a sharply defined interface withthe surrounding water phase. Under ultraviolet light, tinorescent areas were obsenved, showing inclusion ofthe polyvalent metals in the deposit.

Emission spectroscopy studies show the grease-like deposit to comprise calcium, lead, 'zinc and iron in moderate to major portions and various elements such as boron, silicon, magnesium, chromium, vanadium, nickel, etc., in trace amounts.

6 1 To the aiforedescri bed oil field brine was added between A solid brown grease-.

like deposit was observed on the metal surfaces of the 1 pump subject to shear and frictional heat (e.g., between the reciprocating mating surfaces of the valve mechanism, between the piston rings and cylinder, in the recessed pis- The deposit appeared as a plastic.

dark brown film which imparted a highly preferential oil A cream Although the fluid was circulated through stationary ports and orifices not subjected to mechanical friction and shear, no problem was encountered due to plugging. The minimum size port was about 0.016 inch.

To illustrate the sealing and lubricating properties of our concentrate, the aforedescribed pump was modified by decreasing the .piston diameter to provide a clearance of 0.0625 inch in lieu' of the original 0.003 inch. The length of the sealing hearings on the connectingrod between the high pressure hydraulic motor andthe pumping piston were reduced to one-third the original length and the ring seals therefor wereomitted. Only two square look piston rings were used to guide the piston rather than the originally supplied fourteen. The fluid loss measured throughout the test period of two days with the modified pump at about 50 strokes'per minute and a pressure drop of about 700 p.s.i. was about 50 milliliters per minute. Hydraulic oil with a :viscosity of about 100 SSU at 100 F. under comparable conditions exhibits fluid loss of about 1300 to 1500 milliliters per minute initially and this loss increases throughout the test period.

In a third test, a sealed model duplicating the stroke lengths, clearances, size and metallurgy of the valve mechanism of the aiforedescribed hydraulic pump was operated on oil field brine containing. 0.03 percent Concentrate 16 for a continuous test period of months. Throughout the test period the fluid loss was below that observed under the same conditions with crude oil. After completion of the test, mechanical and optical measurement of the metal surfaces showed no detectable wear. This was very unexpected since the brine contained about 4 to about parts per million of solids ranging from submicron sized clays to silts of maximum particle dimension of 0.004 inch.

To illustrate the effectiveness of our concentrate in the lubrication of rotating members, a helical screw type pump, the DeLaval IMO single end pump, Was employed to pump an oil field brine containing between 0.0 and 0.1 Weight percent of Concentrate 16. A description of this type of pump is in Bulletin 3200 of The DeLaval Steam Turbine Company, Trenton, New Jersey. The IMO pump was operated for extended periods at about 7 gal- Ions per minute at a discharge pressure of 650 p.s.i. As the valve in the discharge line of the pump was constricted, the discharge pressure rose to about 1100 p.s.i. Further constriction of the valve was not attempted because of the danger of breaking the pump housing. The aforedescribed IMO pump was not designed to handle water. The maximum design operating pressure of this pump was about 400 p.s.i. with viscous fluids. In contrast, We obtained 7 gallons per minute at 600 p.s.i. of an oil field brine which had a viscosity of about to SSU.

The pump was dismantled and visually inspected. No signs of wear were detected. The aforedescribed greaselike film and deposit had formed on all the surfaces of this pump which had been in friction. Some of this grease-like material had extruded out of the pump housing around the main bearing on the rotor shaft. Although this deposit had extruded away from the point of wear, there was at all times an automatic replenishment of this grease which effectively sealed and lubricated the bearing.

It is of course apparent to those skilled in the art that various corrosion inhibitors and scale inhibitors can be added to our aqueous lubricant if needed. Various compatible and water dispersible solid lubricants can also be added, if desired, such as colloidal powders of graphite and molybdenum sulfide.

While the aqueous lubricant of our invention has been described with emphasis on its use as a hydraulic fluid, it is of course apparent that our invention is applicable wherever an aqueous lubricant can be used. Other specific uses contemplated are, for instance, cutting oils, drawing lubricants, steam turbine and cylinder lubricants,

22 lubricating and sealing heat transfer mediums for forced circulation cooling systems, etc.

Having completely described our invention, we therefore claim the following compositions of ingredients or equivalents thereof and method steps or equivalents thereof.

We claim:

1. A method for lubricating surfaces in frictional contact which comprises:

' (1) supplying to said surfaces an aqueous medium containing at least about 10 parts per million of alkaline earth metal ions, from about .001 to 5.0 weight percent of a reactive organic ingreident selected from the class consisting of aliphatic carboxylic acids having from 8 to about 25 carbons, alkali metal and ammonium salts thereof and organic phosphorus acids of the following structure:

wherein:

R is selected from the class consisting of alkyl, alkenyl, alkoxy and alkenoxy having from 8 to 18 carbons R is selected from the class consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkoxy and alkenoxy having from 1 to about 18 carbons; and X is selected from the class consisting of hydro gen, alkali metal and ammonium; and .an oilin-water emulsifier in an amount from 2 to 50 weight percent of said reactive organic ingredient, sufiicient to emulsify said ingredient in said water; and r (2) moving said surfaces in frictional contact to initiate reaction of said ions with said reactive organic in: gredient and form a water insoluble lubricating film on said surfaces.

2. The method of claim 1 wherein said water is brine containing at least about 0.5 weight'percent dissolved-salts and said reactive organic ingredient is selectedfrom the class consisting of aliphatic carboxylic acids, alkali rnet al or ammonium salts thereof.

3.. The method'of claiml wherein said water contains less than 0.5 weight percent dissolved salts and said reactive organic ingredient is an organic phosphate ester.

4. The method of claim 1 wherein said water also contains an organic solvent for said lubricating deposit with the weight ratio of the solvent to said reactive organic ingredient being between about 0.1 and 5.0.

5. The method of claim 1 wherein said water also contains abietyl alcohol in an amount comprising from about 0.1 to about 5 weight percent of said reactive organic ingredient.

6. The method of claim 1 wherein said aqueous medium also contains a metal compound selected from the class consisting of the oxides and salts of zinc, lead, cadmium, aresnic, iron, cobalt, nickel, indium, silver and mixtures thereof.

7. The method of claim 1 wherein said reactive organic ingredient is an oligmer of an 8 to 25 carbon alkenyl carboxylic acid.

8.The method of claim 1 wherein said reactive organic ingredinet is a sulfided unsaturated fatty acid.

9. A concentrate composition useful for addition to water having at least about 10 parts per million of an alkaline earth metal to thereby form an aqueous lubricant, said concentrate consisting essentially of:

(1) from 5 to about 40 weight percent of a reactive organic ingredient selected from the class consisting of an aliphatic carboxylic acid having 8 to about 25 carbons, alkali metal and ammonium salts thereof '23 or organic phosphorus acids of the following structure:

R1 B: OX

wherein:

R is selected from the class consisting of alkyl, alkenyl, alkoxy and alkenoxy having 8 to about 18 carbons;

R is selected from the class consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkoxy and alkenoxy having 1 to about '18 carbons; and

X is selected from the class conisting of hydrogen, alkali metal and ammonium;

(2) between about 40 and about 95 weight percent of an organic solvent for the alkaline earth metal salts of said reactive organic ingredient with a Weight ratio of said solvent to said organic ingredient between about 0.01 and about 5.0; and

(3) from 5 to about 50 parts by weightof an oil-inwater emulsifier per 100 parts of said reactive organic ingredient and said solvent.

10. The concentrate composition of claim 9 wherein said organic reactive ingredient is a fatty carboxylic acid.

11. The concentrate composition of claim 9 wherein said aliphatic fatty acid is a sulfided unsaturated fatty acid.

. 12.,The concentrate composition of claim 9 wherein said emulsifier is a nonionic oil-in-water emulsifying agent.

13., An aqueous medium comprising water having at least about 10 parts per million of an alkaline earth metal ion and between about 0.005 and 5 weight percent of the concentrate of claim 9.

14. The concentrate composition of claim 9 which also contains from 0.1 to 5 weight percent abietyl alcohol.

15. A concentrate composition useful for addition to water containing at least about 10 parts per million of an alkaline earth metal ion to thereby form an aqueous lubricant, said concentrate consisting essentially of: i

(1) from about 48 to about 90 weight percent of a reactive organic ingredient selected from the class consisting of aliphatic carboxylic acids having from about 8 to about 25 carbons, alkali metal and ammonium salts thereof, organic 'phosphorus acids of the following structure:

R1 0 111 \OX wherein:

R is selected from the class consisting of alkyl, alkenyl, alkoxy and alkenoxy having 8 to about 18 carbons; R is selected from the class consisting of hygrogen, hydroxyl, alkyl, alkenyl, alkoxy and alkenoxy having 1 to about 18 carbons; X is selected from the class consisting of hydrogen, alkali metal and ammonium;

(2) a water dispersible compound of a polyvalent: metal in an amount from about 2.4 to about 32 weight percent, said compound selected from the class consisting of the oxides and salts of zinc, cadmium, arsenic, lead, iron, cobalt, nickel and mixtures thereof; and (3) an oil-in-water emulsifier in an amount from about 2.4 to 32 weight percent,,sufficient to emulsify said reactive organic ingredient-in water.

16. The concentrate of claim 15 also containing rosin.

17. The concentrate .of c1aim'15 wherein said metal compound is a mixture of zinc and lead compounds with a weight ratio of zinc to lead between about 2:1 and 6:1, calculated as the oxide.

18. The concentrate of claim 15 useful for addition to water substantially free of alkaline earth metal ions wherein said concentrate also contains between aboutl and parts of a soluble alkaline earth metal salt per. .100 parts of said reactive ingredients.

19. The concentrate of claim 15 also containing between about 2.4 and about 32 weight percent of a heterocyclic amine.

20. The concentrate of claim 15 wherein said organic phosphorus acid is oleyl phosphoric acid.

References Cited by the Examiner UNITED STATES PATENTS 2,285,853 6/1942 Downing et al. 25249.8 X 1 2,285,855 6/1942 Dovmiug et al. 252-32.5 X 2,751,356 6/1956 White ct al. 25276 X 1 3,091,589 5/1963 Bruker 252-j49.3 X.

DANIEL E. WYMAN, Primary Examiner.

C. F. DEES, Assistant Examiner.

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