US2417433A - Lubricating composition - Google Patents

Description

I Patented Mar. 18, 1947 2,417,433 LUBRICATING COMPOSITION Lester W. McLennan,

to Union Oil Angeles, Calif., a

El Cerrito, CaliL, aasignor Company of California, Los corporation of California No Drawing. Application April 23, 1945, Serial No. 589,941

Claims. (Cl. 252-403!) This invention relates to lubricating compositions containing complex basic barium soaps and has special reference to complex barium soap greases.

The object of the invention is to obtain all the benefits of such lubricants and greases as are peculiar to complex barium soaps. Complex barium soaps produce stable greases which have excellent melting point and penetration characteristics, do not require hydration, and have exceptional resistance to deterioration by the action of heat and by the action of moisture. Another object 01' this invention is to provide processes for the manufacture of complex barium soap lubricants.

Complex barium soaps as used herein include products which are substantially neutral or substantially free from readily titratable excess alkalinity, at least beyond a relatively small amount, these products comprising a complex of a normal barium soap with a barium salt. The number of mols of barium salt combined with each moi of barium soap should be greater than 0.1 and, depending upon the particular saponiflable material and upon the characteristics of the mineral oil employed, it is preferred that the number of mols of barium salt per mol of normal barium soap be between about 0.2 and 1.0, but it may be as high as 2.0 or even as high as 3.0

Normal barium soaps as used herein include those products which result when one equivalent of barium hydroxide or other basically reacting barium compound is reacted with one equivalent of a saponifiable material to form a soap, said soap being the normal barium salt of the high molecular weight organic acids present as such or desirable by saponification from the saponifiabie material.

Examples oi saponiiiable materials containing high molecular weight organic acids, present as such or readily derivable therefrom by saponiflcation, include fats such as tallow, lard, oil, hog fat, horse fat, etc., high molecular weight organic acids such as stearic acid, oleic acid, the high molecular weight acids resulting from the oxidation of petroleum fractions (for example, paraffin wax and mineral oil), rosin and related products, high molecular weight naphthenic acids, sulfonic acids, etc., and saponifiabie waxes such as beeswax, sperm oil, degras, etc.

The present invention resides in lubricating compositions, especially greases which contain complex barium soaps which are substantially neutral or substantially free from readily titratable excess alkalinity. While the invention may be extended to freely fluid lubricants, such as Diesel engine lubricating oils containing small proportions of complex basic soaps, it includes more particularly the use of such complex barium soaps in proportions to thicken lubricating oils appreciably for the purpose oi producing liquid greases or solid greases of varying consistencies. More particularly the invention resides in mineral oil lubricants containing thickening proportions of complex barium soaps where the molai ratio of barium salt to normal barium soap is between about 0.2 and 1.0, although it extends to the upper limit above indicated, i. e., 3.0 and may be as low as 0.1. Especially stable complex barium soap greases have been found to have a molal ratio within the range of 0.3 to 0.9. The invention also comprises the method of making such lubricants.

The invention also includes the use of basic soaps to produce lubricants employing high viscosity mineral oils, e. g., 50 or SAE grade or even bright stocks as well as lower viscosity mineral oils, e. g., 10 or 20 SAE grade. These mineral ols can be either of the Pennsylvania type which have a viscosity index of or higher, or

, the Mid-Continent type or even of the naphthenic type which have a viscosity index of 30 or lower. Greases or unusually good water resistance have been prepared from oils containing as much as 25% by weight of asphalt or extracts derived from lubricating oil distillates by treatment witn phenol, furi'urai, etc.

I have discovered that under appropriate conditions it is possible to form a complex having unique solubility characteristics in mineral, lubricating oils by reacting one mol of a normal barium soap with more than about 0.1 mol of a barium salt. By the term barium salt" it is meant to include preferably the simple reaction product resulting from the combination of one equivalent of barium hydroxide with one equivalent of a mineral acid such as sulfuric acid, hydrochloric acid, orthophosphoric acid, pyrophosphoric acid, suifurous acid, carbonic acid, boric acid, thiosulfuric acid or of an organic acid of relatively low molecular weight such as the monocarboxylic and polycarboxylic acids containing less than about 7 carbon atoms per molecule, such as formic, acetic, propionic, valeric, oxalic, malonic, succinic. etc., acids, the low molecular weight alkyl and aryl sulfonic acids. the low molecular weight substituted carboxylic acids such as glyceric, giycoilic, thioglycollic, etc., acids, and the low molecular weight phenolio and thiophenolic compounds such as phenol, cresol, thiophenoi. etc. However, I may also employ acidic or basic salts in which one equivalent of barium hydroxide has been reacted with more or less than one equivalent of a mineral acid or low molecular weight organic acid.

Preferably, the bar um salt should be barium acetate or barium carbonate or a mixture of barium acetate and barium carbonate.

Desirably the complex barium soap is substantially neutral or free from relatively titratable excess alkalinity. By the terms "substantially neutral" or substantially free from readily titratable excess alkalinity" as used in this invention, are meant to include greases having a free acid or free alkali content less than about the equivalent oi 5.0 mg. of KOH per gram of soap present. While it is prelerred that the greases oi. this invention be substantially neutral, under some conditions they may desirably contain a small amount of free acidity or alkalinity. For example, the finished greases may have a free alkali content, calculated as BaiOHlz, as high as about 0.5% by weight of grease or a free acid contentequivalent to about 2.0 mg. KOH per gram oi grease. Greases having a desired free acid or free barium hydroxide content can be produced by controlling the ratio of acidic materials to basically reacting compounds as will be obvious to one skilled in the art.

Free alkalinity is measured in accordance with A. S. T. M. method of test No. D-l28-40, section 18, except that titration is conducted in the cold and the titration is made directly with standard HCl solution rather than by adding an excess of HCl solution and then back titrating with alcoholic potassium hydroxide solution. Free acidity is measured in accordance with A. S. T. M. method 01 test No. D-128-40, section 20. Briefly, the methods of test employed are as iollows:

A 10gram sample of the grease is weighed to the nearest tenth of a gram into a 250 ml. Erlenmeyer flask. To the flask is then added '75 ml. of petroleum ether and 50 ml. of 95% alcohol containing phenolphthalein indicator, the alcohol having been previously made neutral as indicated by the phenolphthalein indicator. The flask is stoppered and shaken vigorously in the cold until the grease has completely disintegrated and no lumps remain. The solution is then allowed to settle and tree alkali or free acid, as observed by the color the alcoholic layer, is titrated carefully in the cold to the phenolphthalein end point with 0.5 normal HCl or alcoholic KOH, as required. Free alkalinity is calculated in terms of Ba(0I-l):; free acidity in terms of oleic acid or acetic acid. Free alkalinity and free acidity may also be expressed in terms of equivalent mg. of KOH per gram of grease.

While I do not wish to be limited by the theories advanced herein, it appears, however. that under the conditions as disclosed in this invention, it is possible for normal barium soap to form an association complex" with a barium salt, this complex acting in many respects as a single chemical component. For example, this complex has a different solubility in lubricating oil than either the normal barium soap or the barium salt oi which it is composed. Further, although a given barium salt when added to a. normal barium soap grease as a filler. may be readily extractable with water, the same barium salt combined with the normal barium soap in the form oi a complex barium soap or the present invention is extractable either only with diihculty or not at all. As another indication of the novelty or my complex barium soap greases, attention should be called to the fact that whereas barium salts are usually relatively insoluble in mineral oils and when added as fillers to conventional normal soap greases, the latter are opaque and the salts can be largely removed by passing through a flne mesh screen, my greases are relatively transparent or translucent in appearance and none of the salt is removable by mechanical means.

It is not meant to intimate that any given barium salt is the full equivalent of any other barium-salt for modifying the characteristics of a dispersion of normal barium soap in lubricating oil. In fact the complexes of various barium salts with a given normal barium soap vary over a wide range as regards their respective solubilities in a given mineral lubricating oil. For example, a normal barium stearate-barium carbonate complex is more soluble in a given mineral oil than is a normal barium stearate-barium formate complex. Likewise, the latter complex appears to be more soluble than one formed from normal barium stearate and barium acetate. Complexes of a given normal barium soap with certain barium salts will possess just the proper characteristics to form with a specific mineral oil a grease of the improved properties described herein. Other complexes of the same normal barium soap with diflerent barium salts will be either too soluble or insufllcientiy soluble to form desirable greases in the given mineral oil. In the latter case it is possible and desirable to form excellent greases coming within the scope of the present invention by mixing a complex which is too soluble in the specific mineral oil with one possessing inadequate solubility. The exact proportions of the two complexes to be used will depend upon the relative solubilities of the two complexes and can be readily determined by one skilled in the greasemaking art.

It has also been noted that even though the final grease is to be substantially anhydrous, a product of improved characteristics can often be obtained by adding a small amount of water, for example, in the range of 0.1 to 3.0% by weight or even as high as 10% by weight of the grease charge at a suitable temperature and subsequently increasing the temperature to eflect substantially complete dehydration. The grease may be at a temperature of about 210 F. or less when such water additions are made, although temperatures as high as 230 F. or even as high as 300 F. or higher may be used, and subsequent dehydration has been accomplished by heating to temperatures in the neighborhood of 250 F. or higher when necessary. With certain saponiflable materials and barium salts the greases produced by the processes or the present invention have a granular appearance, but by employing the hydration-dehydration technique, products of smooth buttery texture are obtained often accompanied by an increase in consistency and melting point. Usually the hydration-dehydration technique to produce a final substantially anhydrous grease is most effective on a slightly acidic complex barium soap grease. Subsequently the grease can be adjusted to the desired acidity or alkalinity by the addition of barium hydroxide or acid, as the case may be. Further improvements in grease texture can likewise usually be obtained by working the grease at temperatures below about 200 F. and preferably below about F. prior to final packaging.

Although preferably the complex barium soap greases or this invention are produced as sub- 6 stantially anhydrous products under some concooled to room temperature, and if a grease, ditions a slight water content such as 0.01% to worked in the cold and drawn into packages. 0.05 or even as high as 0.3% may be desirable Heating is preferably conducted at atmospheric for om p p In p i n f this W r pressure in an open bottle, however, the heating can be accomplished at any of a number O St and reaction may b carried out in a closed kettle in the prepa at on o the grease s will be obvious under superatmospheric pressure. to one skilled in the art. For example, aft r y Another preferred method of forming the comdrating the grease as described above, the subplex barium soap lubricants of this invention sequent d hydr n n e stopped at a poin comprises mixing the saponifiable material, a which will give the water content required in the 10 small amount of mineral oil and the acid finished p oduct or after complete dehydrati n acids, whose barium salt is desired in the complex the desired quantities of water can be added an barium soap. Subsequently, barium hydrate in c porated in the greas an amount equivalent to the saponifiable material In order for t e desired Complex formation and acid is added to the mixture and the matepr ed w h t preferred temperature range, rial heated and agitated to effect reaction and it is usually desirable that at least a small D dehydration. During the dehydration stage addicentage of a polar solvent in the neighborhood Mona] n may be added or n f the remaining of at least 01% by W of the reacting mass oil required may be added subsequent to the debe Present Further appears that eferably hydration stage. The lubricant is finally heated this polar solvent should be water, although unto a temperature f between about 2504350 F.

der some conditions the complex formation proor even as high as F" subsequently cooled to ceeds more readily in the presence of a mixture room temperature and if a grease worked in of water and glycerine, water and glycol or some the cold to give the final product The hydra hydroxy or polyhydmxy Organic Compound Such hon-dehydration technique may be employed at as ethyl alcoholr diethylene glycol Pref any of several stages, as will be obvious to one erably the proportion of polar solvent present Skilled in the art should be "K range of 05% to by W i It is also possible to first form a normal barium of the reacting mass, but under some conditions soap grease and Subsequently add barium hydrate Smaller quantitiesisuch as about 01% and higher followed by an equivalent amount of the acid quantities' Such as about 10% can be used- AS Whose barium salt it is desired to com lex with an indication of the desirability of having at least the normal barium Soap Also it is pbssible to a Small percentage of a polar solvent m- I produce a complex barium soap lubricant by addhave observed that, anhydrous normal banum ing a barium salt dissolved, or at least partially soap when heated with anhydrous barium acetate dissolved) in water or other appropriate polar in the presence of oil at various temperatures 35 solvent as described hereinabove to a normal famed the complex barium f greases barium soap grease and subsequently heat to effect of my invention and in fact the barium acetate formation of the complex barium soap remained undissolved. On the other hand, when The farmatmn of the complex barium Soap the Same mlxtutfle to Whlch had been added 5% lubricants of this invention generally require of Water was i and subsequently heated to moderately high temperatures, preferably in the dehydrate f the i: the barium range of about 225-325 F. However. under some Soap i f f g evldence of conditions it is desirable that the complex any free anum ace m e mshed grease barium soap lubricants of this invention be heated one of preferred 'i of forming the to temperatures as high as 400 F. or even 550 F. complex barium soap lubiicants of the present prim, to cooling and Working in the co In invention is to charge to a kettle equipped with forming the normal barium scans and barium means for heating cooling, and agitation an salts by reacting a saponifiable material or an amount of banum hydrate (BMOHMBHZO) acidic material with a basically reacting comequjvalent to the number of mols of barium pound. the base is added preferably as the hygzg gg zig gg gi g i gzg 2225x2 22: droxide. Bai OH) 2, or as barium hydrate, although barium Salt is desired in the finished grases is in some instances barium oxide or other basically added in an amount equivalent to that desired in iffi g banun g g g be h the complex barium soap. After heating and age may e a e as a pow Ema gran agitating to effect reaction of this acid with the 5 i or as an aqueous or slurry as barium hydroxide the saponifiable material is .Elther normal or 9Omp1ex.banum soap formatlon if: azi -2 22 13 13}; g g gg g izgg wg of the lubr1cating oil to be used in the finished saponifiable material is mixed with between lubricant, although inert low-boiling solvents may about one fom.m and twice its Weight of the be used under pressure and subsequently wa mineral oil to be present in the finished lubricant. Grated to leave a pure complex banPm soap F After the introduction of the saponifiable maf powder can be dispersed terial, heating and agitation is continued to effect mmeral ml to form comPlex barium Soap lubrisaponification and subsequently dehydration of cant of the present mventlonthe complex barium soap. After dehydration has The amolfnt of complex harm-m Soap P be been completed or even during the dehydration corporated in the greases of this invention may step, additional mineral oil may be added. be from about 5% to about although Finally, the lubricant is heated to a temperature Centrations as low as about 2% and as high as of b t about 25 E and 350 or higher to about may be desirable for certain special complete dehydration and obtain the desired Combinations and applicationscharacteristics and then cooled to approximately Complex arium o p may also be used in 200 F. If desired, a small proportion of water relatively sm ll pr ort n t pro ce l quid can be added at this time and subsequently greases and fluid lubricants, such as lubricating moved as described under the hydration-dehyoils for internal combustion engines, especially dration technique. Finally, the lubricant is 75 Diesel engines. The soap concentrations in such applications are usually below about and are normally in the range of 0.2% to about 2.0%.

Materials other than complex barium soaps may also be added to the lubricating compositions of this invention, such as water, alcohols, and other solvents, oxidation inhibitor, fillers, etc.. as desired. Additions of petrolatum and solvent extracts from lubricating oil stocks have been helpful in some instances. Oxidation inhibitors which may be added to the grease include phenyl alpha naphthyiamine. tetramethyl diamino diphenyl methane, benzidine, etc.. and the amount thereof vary from about 0.001% to about 1.0% of the finished grease.

The following examples will serve as illustrations of the present invention:

EXAMILI I The following ingredients were charged to a steam jacketed grease kettle of about i-barrei capacity equipped with means for agitation:

Pounds Tallow fatty acids (saponiflcation number:

208 mg. KOH per gram) 50 Naphthenic type oil (viscosity=350 Saybolt Universal seconds at 100 F.) 25

These materials were heated to approximately 180 F. and mixed to form a homogeneous solution.

Separately. 25 pounds of barium hydrate, 20 pounds of water, and 8 pounds of glacial acetic acid were mixed, then added to the kettle and followed by 27 pounds of barium hydrate the temperature in the kettle being between 180 and 200 F.

The kettle ingredients were continuously agitated and the temperature gradually increased to effect reaction and dehydration. During the latter part of the dehydration operation, '15 pounds of additional naphthenic-type oil was added so that the mixture would not become stiff and difficult to agitate at any time. Approximately 3 hours was required to complete the dehydration and at the end of this time the material in the kettle exhibited a slight acidity. After the dehydration had been completed the kettle contents were heated to a temperature of 300 F. and maintained at this temperature for a period of two hours. The material was then cooled to 200 F'., about one gallon of water added and thoroughly mixed in, and the temperature then increased to 280 F., to effect dehydration. Finally as the complex barium soap grease cooled from 280 F., an additional 100 pounds of naphthenictype oil was graded into the batch and at a temperature of about 200 F., 1.4 pounds of phenylalpha-naphthylamine, an oxidation inhibitor, was mixed in, the grease further cooled to room temperature, worked in the cold. and drawn into packages.

The finished grease had ties:

the following proper- Composition Complex barium soap per cent by weight 1 28.0

0.!5 moi barium acetate per mol of normal barium tailow fatty acid soap.

Physical characteristics A. B. '1'. M. penetration at I? F.--..--..--..-.. 317 Dropping point, "P 300 Resistance to boiling water Excellent. not

affected Appearance --Smooth, transparent, slightly fibrous Exaurur 11 A complex barium soap grease was prepared in a manner similar to that described in Example 1, except that the naphthenic-typ oil employed had a viscosity at F. of 000 Saybolt Universal seconds and one moi of barium acetate was employed for each moi of barium tailow fatty acid soap. Further, the grease was slightly alkaline, so prior to the hydration-dehydration operations, 2 pounds of tailow fatty acids were added and when the dehydration was almost complete, 1.14 pounds of barium hydrate was added in order that the finished product would be substantially neutral.

The properties of this grease were as follows:

1 1 mol barium acetate per mol of normal barium tailow fatty acid soap.

Physical characteristics slightly fibrous Exsurns II! To a steam jacketed grease kettle equipped with means for agitation, 3400 parts by weight of barium hydrate and 650 parts by weight of glacial acetic acid were charged and mixed to effect reaction. A solution of 3000 parts by weight of tailow fatty acids in 1500 parts by weight of a naphthenic-type oil (viscosity at 100 F.==600 Sayboit Universal seconds) was added and while continuing agitation the mixture was heated to eflect reaction and dehydration. During the final stage of the dehydration, an additional 4500 parts by weight of the naphthenic-type oil was added.

The resultant mixture was alkaline so it was cooled to 200 F., 1000 parts by weight of water and 100 parts by weight of tailow fatty acids added and the kettle contents again heated to about 280 F. to effect reaction and dehydration. An additional 9000 parts by weight naphthenictype 011 was then added, the product cooled to room temperature, worked and drawn into packages.

The properties of this complex barium soap grease were as follows:

1 1 mol barium acetate per mol of normal barium tallo'w fatty acid soap.

A. S. T. M. penetration at 77 F 295 Dropping point. F 376 Resistance to boiling water -Excellent, not

affected ExAMrLz IV The following ingredients were weighed into a kettle:

Parts by weight Prime tailow (saponification number=193) 56 Glacial acetic acid 4 Barium hydrate 46 Naphthenic type oil (viscosity=:600 Saybolt Universal seconds at 100 F.) 56

While agitating, the material in the kettle was heated to 390 F. to eiiect reaction and dehydration. Subsequently, an additional 168 parts by weight or naphthenic-type oil was added and the material again heated to 390 F. The contents of the kettle were then cooled to room temperature. and about one part by weight of water added. While con"nuing agitation the grease was again heated to effect partial dehydration, subsequently cooled and worked to give a smooth, translucent product having an A. S. T. M. penetration at 77 F. or 189 and a Ubbehlode dropping point of 295 F.

EXAMPLE V EXAMPLE VI A complex barium soap grease was prepared in manner similar to that described in Example 3, except that only one-half as much glacial acetic acid was employed and the remaining free barium hydroxide was neutralized by passing carbon dioxide through the kettle contents.

The resultant grease contained a complex barium soap comprising normal barium soap in combination with both barium acetate and barium carbonate. This product had an A. S. 'I'. M. penetration at 77 F. of 250. a Ubbehlode dropping point above 400 F., and showed excellent stability and resistance to the effects of boiling water.

EXAMPLE VII A complex barium soap grease was prepared in a manner similar to that described in Example 2. except that oil soluble sulfonic acids, such as are desired as by-products in the preparation of petroleum white oils, were used in place of the tallow fatty acids. This grease was likewise a smooth, translucent product having a dropping point above 350 F. and resistant to the effects of boiling water.

The foregoing description of my invention is not to be taken as limiting my invention but only as illustrative thereof since many variations may be made by those skilled in the art without departing from the scope of the following claims.

I claim:

1. A lubricating composition comprising mineral oil and a. barium soap complex, the latter being an association complex comprising a normal barium soap and a barium salt in which the ratio of equivalents of barium salt to equivalents of normal barium soap is between about 0.1 and 3, said composition being substantially free from readily titratable excess alkalinity.

2. A lubricating composition comprising mineral oil and a barium soap complex, the latter being an association complex comprising a normal barium soap and a barium salt in which the ratio said composition being substantially anhydrous and free from readily titratable excess alkalinity.

3. A lubricating composition according to claim 1, in which the ratio oi equivalents oi barium salt to normal barium soap is between about 0.2 and 2.

4. A lubricating composition according to claim 1, in which the barium salt is a barium salt of a mineral acid.

5. A lubricating composition according to claim 1, in which the barium salt is a barium salt of low molecular weight organic a:id.

6. A lubricating composition according to claim 1, in which the barium salt is barium carbonate.

'7. A lubricating composition according to claim 1, in which the barium salt is barium acetate.

8. A lubricating composition according to claim 1. in which the barium soap complex is made by admixing normal barium soap and a barium salt of mineral acid.

9. A lubricating composition according to claim 1, in which the barium soap complex is made by of a low molecular weight organic acid.

10. A lubricating composition according to claim 1. in which the barium soap complex is made by reacting normal barium soap, basically reacting barium compound and an acid, the amount of acid being sufllcient to neutralize said basically reacting barium compound.

11. A lubricating composition according to claim 1, in which the barium soap complex is made by reacting normal barium soap, basically neutralize said basically reacting compound.

12. A lubricating composition according to claim 1, in which the barium soap complex is made by reacting normal barium soap, basically reacting barium compound and a low molecular weight organic acid, The amount of said acid being sufilcient to neutralize said basically reacting barium compound.

13. A lubricating composition according to claim 1 prepared by reacting approximately equal chemical equivalents of a basically reacting barium compound and a saponifiable material containing high molecular weight organic acids in the presence of mineral oil to yield a. normal barium soap, adding aqueous solution of a barium salt and then heating said mixture to vaporize water therefrom.

14. A lubricating composition according to claim 1 prepared by heating a saponifiable material containing high molecular weight organic acids, low molecular weight organic acids and a basically reacting barium compound in the presence of mineral oil to yield a product containing said barium soap complex and then hydrating and dehydrating the product.

15. A lubricating composition according to claim 1 prepared by heating a low molecular weight organic acid, a basically reacting barium compound and a mineral 011 containing high molecular weight organic acids to yield a product containing said barium soap complex, adding additional mineral oil and then hydrating and dehydrating said product.

16. A lubricating composition according to claim 1, in which the barium soap complex comprises a normal barium soap, a barium salt oi a mineral acid and a barium salt of a low molecular weight organic acid.

17. A lubricating composition according to claim 1, in which the barium soap complex comprises a normal barium soap. barium carbonate and barium acetate.

13. A lubricating composition according to claim 1 containing also a small amount oi an oxidation inhibitor.

19. A lubricating composition according to claim 1 containing also a small amount of phenyl alpha naphthylamine.

20. A method of preparing lubricants comprising reacting a saponiilable material, a basically reacting barium compound and low molecular weight organic acid in the presence of mineral oil to yield a product containing a barium soap complex and then adding additional mineral oil, said barium soap complex having a ratio of equivalents of barium salt of low molecular weight fatty acids to equivalents of barium soap of said saponiflable material between about 0.2 and 2.0 and being substantially free irom readily titratable xcess alkalinity.

LESTER W. M LENNAN.

REFERENCES CITED The following references are of record in the die of this patent:

UNITED STATES PATENTS OTHER REFERENCES MoLennan, Methods 0! Compounding Barium Greases, Their Properties, Uses. and Future, Article in National Petroleum News, Apr. 5, 1944, pages R234, R236, R238, and R239.

Certificate of Correction Patent No. 2 ,417,433.-

March 18, 1947.

LESTER W. McLENNAN It is hereby certified that error appears in the llows:

Letters Patent should be read with this numbered patent requiring correction as f0 desirable read derivable; and that the said correction therein that the same may conform to the record of the case in the Patent rinted specification of the above olumn 1, line 36, for the word Signed and sealed this 8th day of JulyZA. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

16. A lubricating composition according to claim 1, in which the barium soap complex comprises a normal barium soap, a barium salt oi a mineral acid and a barium salt of a low molecular weight organic acid.

17. A lubricating composition according to claim 1, in which the barium soap complex comprises a normal barium soap. barium carbonate and barium acetate.

13. A lubricating composition according to claim 1 containing also a small amount oi an oxidation inhibitor.

19. A lubricating composition according to claim 1 containing also a small amount of phenyl alpha naphthylamine.

20. A method of preparing lubricants comprising reacting a saponiilable material, a basically reacting barium compound and low molecular weight organic acid in the presence of mineral oil to yield a product containing a barium soap complex and then adding additional mineral oil, said barium soap complex having a ratio of equivalents of barium salt of low molecular weight fatty acids to equivalents of barium soap of said saponiflable material between about 0.2 and 2.0 and being substantially free irom readily titratable xcess alkalinity.

LESTER W. M LENNAN.

REFERENCES CITED The following references are of record in the die of this patent:

UNITED STATES PATENTS OTHER REFERENCES MoLennan, Methods 0! Compounding Barium Greases, Their Properties, Uses. and Future, Article in National Petroleum News, Apr. 5, 1944, pages R234, R236, R238, and R239.

Certificate of Correction Patent No. 2 ,417,433.-

March 18, 1947.

LESTER W. McLENNAN It is hereby certified that error appears in the llows:

Letters Patent should be read with this numbered patent requiring correction as f0 desirable read derivable; and that the said correction therein that the same may conform to the record of the case in the Patent rinted specification of the above olumn 1, line 36, for the word Signed and sealed this 8th day of JulyZA. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents.