Patented Nov.

20, 1945
2,389,523

UNITED STATES PATENT OFFICE

2,389,523
BARIUM CALCIUM MAGNESIUM sTEARATE
GREASE
Frank A. Leyda, Berkeley, Calif., assignor, by
mesne assignments, to California Research Cor
poration, San Franciseo, Calif., a corporation
of Delaware
No Drawing. Application November 2, 1943,
Serial No. 508,749
8 Claims. (C. 252-39)
it his invention relates to the preparation of Nos.2,033,148 and 2,154,383 to Thomas F. Ott et al.
lubricating greases and the greases produced Chiefly, such barium base greases include basic
thereby, particularly one which is waterproof, bariuri? soap or a mixture of AOrna and basic
high melting and thermally reversible. bariun soaps with petroleum oils of varying vis
The three most commonly used bases for cosity characteristics. Grease where the soap
greases are soda, lime and aluminum soaps. Each base is largely or entirely normal bariara soap
type of grease inade from these bases has cer have a lower melting point than those in which
talia advantages as well as disadvantages. Soda the Soap is of the basic variety. Fixed bariuri
base greases have high meiting points and are calcium base greases are described in United
ther naiy reversible; i. e., on melting and then 0. States Patent No. 2,070,78 to it, C. Brunstrum
cooling to solidify, a Soda base grease reverts to et al. These are said to be Superior not only to
its original state. It does not break into an oil the line or cacia base greases out also to the
phase and a soap phase upon melting. However, Straight, bariurn base greases, in that they will
due to the Water solubility of the soda soaps, not stiffen upon heating above 250's. The nixed
greases inade from this material as a base lack 5 barium-calciura base greases are preferably used
Waterproof. qualities and will tend to emulsify in conjunction with a partial ester of a poly
with any moisture that may be present. hydric alcohol and a higher fatty acid, such as
line or calcium base greases are waterproof, diglycol stearate. The combined effect of the
but neit at relatively low temperatures, about mixed barium-calcium base and the partial estes
200 s. Under these conditions they lose the 20
is much greater than the effect of the bariuiras
Water which is a minor but essential component calcium base alone. This is particularly true
of this type of grease and break into an oil phase of the anhydrous greases.
and a soap phase. Thus, in addition to being low It is an object of the present invention to pro
melting, which in itself is undesirable, lime base duce a grease having certain characteristics of
greases are not thermally reversible. 25
Altarninuin base greases are waterproof but calcium base greases and which combines Sev
for a rubbery gel at about 200 F. Also, al erai advantages and lacks several disadvantages
though aluminuin base greases have an apparent of heretofore known greases.
neiting point by the Ubbelohde or builio (nethods it is a further and particular object of this
as high as 250 to 300 F., it will be found that they 30 invention to produce 3, grease which has a higia
Will soften Slaficiently to flow at temperatures of melting point, is Waterproof, 3rd is therasaaiy re
about 200 F. This may be demonstrated by plac versible and which is free for the Cectionable
ing & Small sample of the grease upon a 6-mesh features of heretofore known Sostitutes for ca
aretai screen and heating it for several hours. cium base greases.
Since many service conditions will impose a tem 35 Another object is to provide g, nethod of paroe
perature of over 200 F. for prolonged periods, ducing an anhydrous grease which will be ther
it is apparent that aluminum base greases are not maily reversible and will have improved regist
high neiting in the sense that soda, base greases ance against melting at high terrperatures.
are highnelting. These and other objects of this invention Will
By way of improvement, it has been heretofore 40 be further apparent from the following descrip
proposed to use barium base or mixed barium tion of a preferred eabodiment together with Seva
calcium base greases in lieu of straight calcium eral alternative compositions.
base greases. Such greases have certain advan This invention comprehends broadly the utili
tages, due chiefly to the barium base. Barium zation of a base comprising suitable soaps of
soaps, for example barium stearate, have the 45 barium, calcium and magnesium, said soaps in
property of imparting to a grease a higher melt cluding stearates, palmitates, a mixture of stear
ing point than calcium soaps. At the same time ates and palmitates, or other fatty acids either
the barium base grease retains the waterproof occurring naturally or produced synthetically,
qualities of the calcium base material. Examples 50
such as those derived from the oxidation of
of these are described in United States Patents petroleum wax. Strontium may be substituted in
2 2,889,523
part or in whole for the calcium in the base ma cordance with this invention possesses a re
terial. markable number of desirable properties. It is
In compounding greases according to the in waterproof, like the calcium and aluminum base
vention, the oil component will be selected and greases, but unlike both the latter it has a high
used from those petroleum oils which have melting point. Unlike aluminum base greases it
hitherto been used in grease making. In a typi does not gel to a rubbery state on heating. On
cal example, commercial Stearic acid (a mixture the contrary, as it is heated to above the melting
of stearic and palmitic acids), barium hydroxide point it changes from a sold to a viscous liquid,
octahydrate, hydrated line, magnesia and a min and on cooling it again assumes the same solid.
eral lubricating oil in quantity sufficient to render O form. Even repeated melting and solidification
the mixture and the reaction produce freely fluld do not cause the oil and soap to separate, so that
at an elevated temperature are stirred and heated it is truly thermally reversible Neither water nor
in an autoclave at about 300 to 330 F. until any other Substance besides the soaps and the
saponification and intermixture are complete. oils is essential to its manufacture. Preferably,
After releasing the pressure, thereby flashing of 15 it is employed in an anhydrous form although
a portion of the water, the autoclave is opened a very small percentage of water may be pres
and the mixture heated further until substan ent as is the case of substantially any form of
tially all of the water is driven off, after which grease.
sufficient mineral oil is added and stirred in to Following are specific compositions of greases
produce a grease of the desired consistency or 20 which have been found to be very desirable in
hardness. After the mineral oil is added the their properties:
grease is stirred and cooled to about 150 F.
before drawing from the autoclave. It will be
understood, however, that other procedures of Composition Example Fxample, 2
compounding may be employed so long as the 25
base comprises soaps of barium, calcium and Stearic acid, percent by weight, ...
Percent
17.8
prent
, ()
magnesium and the saponified mixture is ycliratic bariuri hydroxidy. . . . . . 7.2 8.
heated until substantially all the Water is driven Hydrated litro..................... . . . (), 47 0.44
Magnesia -----------....... . . . . . (). 2.) (). 18
off to form an anhydrous product, Acid treated naphthonic buse mineral
oil of viscosity 460 S. 8. F. at 100° F ... .
The term stearic acid is used in this descrip 30 solvent 7.93
tion to designate both the comparatively pure . . eral oiltreated naphthetic base min
of viscosity 350 S. S. U. at
acid and also the commercial product which 100° F . . . . . . .. . . . . . 73.
may contain a substantial fraction, in Some cases 100.00 100.00
up to 40%, of palmitic acid.
The barium soap is preferably employed in 85 A. S.Unworked.-------------------...--
T. M. ponctration, 77 F.:
125 58
greater amount than either of the other soaps Worked........................... f 242
and it is most advantageously used in an amount Melting point, F.----------------- 25 250
by weight exceeding the combined magnesium
and calcium Soaps. The preferred proportions of
the various soaps are set forth in the table be 40 In conclusion, it will be appreciated that the
OW: - - essential features of this invention appear to re
Per cent by weight of total soap side in the manufacture of an anhydrous grease.
Barium soap -----------'------------- 60 to 80 which is waterproof, thermally reversible and of a
Calcium and/or strontium Soap.--------- 10 to 30 high melting point, made from a mixture of bar
Magnesium soap --------------------- 10 to 20 45 ium, magnesium and calcium or strontium soaps
with a mineral oil. Although specific examples
As stated above, strontium may replace a part Of compositions, methods of compounding and the
or all of the calcium soap, and the stearic acid like have been given, it will be appreciated that
radical may be replaced in part or entirely by modifications may be made which will not depart
the palmitic acid radical. Furthermore, other 50 from this invention so that all such modifications
fatty acids may be used, such as the material and changes as fall within the scope of the ap
sold under the trade-mark "Hydrex' derived pended claims will be embraced thereby.
from hydrogenated fish oil or similar oils and claim: -
which consists of a mixture of saturated fatty 1. A mixed base, anhydrous grease consisting
acids in which the number of carbon atoms varies 55 of mineral oil and soaps of barium, magnesium
from about 14 to 22 or more. A typical average and at least one metal of the group consisting of
distribution would be as follows: calcium and strontium, said magnesium soap
Per cent being present in proportions ranging from 10 to
C-14 ------------------------------------ 7 20% of the soaps present so as to produce a ther
C-16 ------------------------------------ 32 60 mally reversible grease.
C-18 ------------------------------------ 23 2. A mixed-base, anhydrous grease consisting
C20 ------------------------------------ 23 of mineral oil and stearates and palmitates of
C22- ---------------------------------- 15 barium, calcium and magnesium, said magnesium
stearates and palmitates being present in such
100 65 proportions as to produce a thermally reversible
grease. to
The oil used in compounding the greases of 3. A mixed-base, thermally reversible grease
this invention may be any conventional lubricat consisting of mineral oil and a soap mixture,
ing oil used in grease manufacture, including the Said Soap mixture comprising about 10 to 20%
medicinal white oils and low viscosity oils suit 70 by weight of magnesium stearate, the other soaps
able for low temperature greases, but is prefer comprising calcium and barium stearates, the
ably derived from Western type naphthenic oils barium stearate exceeding the combined calciumi
having desirable solvent action and viscosity in and magnesium stearate content.
dices up to about 50. 4. A mixed base, anhydrous, thermally revers
It will be found that grease produced in ac 75 ible grease comprising mineral oil and a soap mix
 2,889,523
ture, said soap mixture composed of 60 to 80% 7. A mixed base, anhydrous, thermally revers
barium soap, 10 to 30% calcium soap and 10 to percentage composition by weight:
20% magnesium Soap. -
5. A mixed base, anhydrous, thermally revers Barium soap------------------------------
ible grease comprising mineral oil and a soap mix
ture, said Soap mixture composed of 60 to 80% Strontium Soap--------------------- - ers up uen-ow - 4.
barium SOap, 10 to 30% strontium soap and 10 Magnesium soap--------------------------- 3
to 20% magnesium soap. Oil --------------------------------------- 75
6. A mixed base, anhydrous, thermally revers 10 8. A mixed-base, anhydrous thermally revers
ble grease having approximately the following ible grease comprising mineral oil and a soap mix
percentage COmposition by weight: ture, said soap mixture composed of 60 to 80%
Percent barium soap, 10 to 20% magnesium soap, and
Barium soap------------------------------ 18 about 10 to 30% of soap chosen from the group
Calcium soap------------------------------ 4. consisting of calcium and strontium soaps.
Magnesium soap--------------------------- 3 FRANK. A. Y.O.A.
Oil --------------------------------------- 75