CA1063590A

CA1063590A - Antiwear hydraulic oil

Info

Publication number: CA1063590A
Application number: CA235,238A
Authority: CA
Inventors: Thomas D. Newingham; Alexander D. Recchuite
Original assignee: Sun Oil Company of Pennsylvania
Current assignee: Sunoco Inc R&M
Priority date: 1974-10-31
Filing date: 1975-09-11
Publication date: 1979-10-02
Also published as: JPS5165104A; DE2547793A1; US3923669A; NL7512138A; FR2289600A1; IT1044091B; BE835042A

Abstract

ABSTRACT OF THE DISCLOSURE

An improved antiwear hydraulic oil comprises major amounts of a mineral lubricating oil (preferably a hydrocracked oil which has been solvent extracted to improve ultra-violet light stability) and minor amounts of a "secondary" zinc dialkyl dithiophosphate antiwear agent, chelating type and film forming type metal deactivators, a neutral barium salt of a petroleum sulfonate and a succinic acid based rust in-hibitor. The hydraulic oil is especially useful in lubrication of high output (e.g., 100 gallons per minute) bronze-on-steel axial piston pumps.

Description

BACKGROUND OF THE INVENTION
-Zinc dithiophosphates are widely used in lubricants as anti-wear agents. Although ashless anti-wear materials have been gaining prominence because of the absence of heavy metals, the zinc dithiophosphates still continue to provide one of the most economical sources of anti-wear protection. There are three general types of zinc dithiophosphates from which to select, depending on the specific application. The zincs are classified as either primary, secondary, or aryl, depending . . ,j . . .
on the alcohols from which they are made, although the primary and secondary zincs are commonly re~erred to as alkyl. If the ; R-O- group in the structure for zinc dithiophosphate (shown below) is derived ~rom a primary alcohol, then the zinc is referred to as primary, likewise, if it is derived from a secondary alcohol, it is referred to as secondary and, i~
derived from an alkylated phenol, it is referred to as aryl.
~:~
R - O\
. / P = Sl Zn '.:',~ . LR--O
;~ 20 2 ., . ,.
~,~i .Zinc Dithiophosphate I R-O- Derived From: Classified as:
. .~, , .
' CH3- (CH2)n CH2 OH Primary ., i; .
CH3 (CH2)n fH Secondary , CH3 - (CH2)m CH2 - CH3 - (CH2)n C 2 ~ OH Aryl `~ Each o~ these zincs:usually displays a different combination o~ per~ormance properties as summarized below:
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1(~63~90 Per~ormance Type of Zinc Dithiophosphate CharacteristicPrimary Secondary Ary Wear ProtectionAverage Best Poorest Oxidation Inhibition Average Best Poorest Thermal StabilityAverage Poorest Best Demulsibility Best ~verage Poorest Cost Lowest Average Highest Based on their relative performance levels, zincs are selected for a particular application. For example, aryl zincs are used almost exclusively in diesel engine oils because of their excellent thermal stability. Primary zincs find a large application in both engine oils and hydraulic oils.
Secondary zincs are used mostly in hydraulic oils, transmission and gear oils. Primary and secondary zincs have been selected for these applications because of their relatively good anti-wear performance, good anti-oxidant qualities and low cost.
Where hydraulic oils are concerned, primary zincs have usually been preferred because they offered the best overall perfor-mance for the lowest cost.
.
However, problems have been encountered when pri.mary zincs are used in certain axial in-line piston pumps. In these pumps, the bronze piston pads slide o~ a steel swash ; plate. With certain zinc-containing anti-wear hydraulic oils, a reaction occurred at the interface of the bronze piston pads and the steel swash plate. The reaction products raised the friction level between the sliding surfaces and eventually generated enough heat to crack the swash plate.
... , , ~ . .

The present invention provides an anti-wear ; hydraulic oil-containing a secondary zinc and which provides superior performance in vein pumps and piston pumps and .~ . .

., . . . . .

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~ especially with such "bronze-on-steel" pumps.
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SUM~RY OF THE INVENllON :

An improved antiwear hydraulic oil comprises major amounts of a mineral lubricating oil, (preferably a hydro-cracked oil which has been solvent extracted to improve ! ultra-violet light stability) and minor amounts of a secondary" zinc dialkyl dithiophosphate antiwear agent, chelating type and film forming type metal deactivators, ~
,: ., ,;
;, a neutral barium salt of a petroleum sulfonate and a ~
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succinic acid based rust inhibitor. The hydraulic oil is especially useful in librication of high output (e.g., 100 gallons per minute) bronze-on-steel axial piston pumpg.
The preferred mineral oils consist mainly of oils termed "paraffinic" or "relatively paraffinic" by the viscosity gravity constant classification. Especially useful are the stabilized, hydrocracked oils described in U.S. 3,915,871 of Bryer et al. Blends of such hydro-cracked oils with a naphthenic acid-free naphthenic distillate can also be used on the present invention. The ;
~'polymer" and "soap" type antileak hydraulic oils shown in Canadian Patent 990,270 of Griffith et al can also be made containing the secondary zinc dialkyl dithiophosphates, for antiwear, if the two types of metal deactivator, a neutral :. ~1 : . . , barium sulfonate and a succinic acid type rust inhibitor ~ are included therewith.

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The relative proportions of the essential ingredients : . .:

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1063~90 , are important. The weight ratio of the secondary zinc dialkyl dithiophosphate to the total weight of the deactivator ; compounds is generally no greater than about 15 to 1 (typically about lO to 1).

The relative weight proportions of the succinic acid inhibitor and the neutral barium petroleum sulfonate are generally in the range of 3 to 1 to 1 to 1 (typically about

2 to 1). The relative proportion of the neutral barium petroleum sulfonate to the total metal deactivators is also important (and is best determined by experiment) since if the relative amount of the barlum compound is too great, the h~drolytic stability of the lubricant will be poor and high metal losses will be encountered in use in the pump.

I FURTHER DESCRIPTION

To predict which kinds of zinc dithiophosphates would cause swash plate cracking two test procedures are useful.
~ . .
One the beverage bottle hydrolytic stability test, measures the corrosive nature of the zinc-containing hydraulic oil in terms of metal loSs and total acidity. This test, as described ~- 20 in the ASTM handbook, also calls for the amount of insolubles ., ... , - .~
produced, the viscosity change of the oil, and the acid number of the oil. For this particular hydraulic oil problem, however, these data are not pertinent.
, The other, the sludge and metal corrosion test, also measures corrosiveness in terms o~ metal loss, bub measures sludge produced as well. The sludge and metal corrosion test is a combination oxidation and corrosion test. This test is run using the same conditions as the ASTM D 943 test. After a thousand hours, however, the test is terminated and the oil .
, , .. . . :, .

is analyzed for the total amount of sludge present ? as well as the amounts of copper and iron present in the combined oil, water and sludge fractions.

Before the beverage bottle hydrolytic stability test - and the sludge and metal corrosion tests were adopted to separate "good" and "bad" zinc-containing hydraulic oils, preliminary wor~ was done using the low velocity friction appa-ratus to compare a secondary zinc formulation which performed satisfactorily in piston pump service with a primary zinc formulation which did not. This comparison gave the first indication that there might be a signi~icant di~ference .,~,; .
between ~rimary and secondary zinc hydraulic oil formulations in lubrication of B bronze-steel piston pump.

The low velocity friction apparatus is an instrument which measures friction characteristics as a function of I sliding speed and applied load. For most testlng, a steel ~, !~ anulus is used which rotates on a steel plate. Both the anulus and plate are immersed in the test oil. To simulate the sliding conditions of the bronze-on-steel piston pump, ,:: .
however, a bronze anulus and a steel plate was used. In this ; case, testing was aimed at generating reaction products, rather than friction curves. At the end of the test the used oil was analyzed for copper content and also visually inspected.
As shown by the results below, the primary zinc formulation showed a aignificant increase ~n copper content, indicating a substantial amount of reaction products. The secondary zinc formulation, however, showed little change. Even more dramatlc was the dif~erence in appearance of the two formula-tions at the end of the test. The primary zinc showed very severe accumulat~on of black reaction products; the secondary formulation remained clear.

Low Velocity Friction Apparatus Test Oil Data Copper Content, ppm Primary Zinc Secondary Zinc Formulation ~A~ Formulation (D) ; New Oil 35 60 Used Oil 760 82 Appearance Heavy black Clear debris . 10 Conditions: Bronze-on-steel specimens, 200F, 80 lbs. load, 8 ft/minutes sliding speed, 17 hours. .-~

(a) .
These were fully formulated anti-wear hydraulic oils con- :

taining, in addition to zinc dithiophosphate, antioxidant, :
.
rust inhibitor and defoamer.

The beverage bottle hydrolytic stability test and the sludge and metal corrosion test have been adopted as :~
part of ~he an~i-~ear hydraulic oil specification ~or the :
bronze-on-stee' axial piston pumps by certain.pump manufacturers and the Military under the MIL speci~icati.on 24459. The hy~ro-lytic stabilit~ test is an ASTM-established test and is found in the current ASTM handbook under ASTM D 2619-67. In the test, ~. :
j5 grams of the anti-wear hydraulic oil are added to 25 grams of distilled water in a beverage bottle containing a copper strip. m e bottle is capped and placed in an oven where it ~:
rotates end over end at 5 rpm for 48 hours at 200F. At the : end of the test, the weight loss of the copper strip and the total acidity of the water layer are determined. They are :.
considered a measure of the corrosiveness of the oil. Those anti-wear hydraulic oils which produce no more than 0.5 mg/cm o~ copper loss and no more than 6.o mgKO~I total acidity - in the water portion are consi.dered satisfactory for bronze- :
. .
on-steel piston pump use, provided, o~ course, that they also : ~7~

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1063~90 satisfy the other requirement--the sludge and metal corrosion test. This test is a combination oxidation and corrosion test.
It is run using the same conditions as the more familiar ASTM
D 943 Turbine Oil Oxidation Test. At the end of a thousand hours, however, the oxidation test is terminated and the oil is analyzed for total sludge produced, as well as the copper and iron content of the combined oil, water, and sludge portions.
Maximum acceptable limits for the tes~ are:
Total insoluble sludge, mg 400 10Total Copper, mg 200 Total iron, mg 100 ;
Complete description of the test is found under Federal Test Method 3020.1.

~I With the results of the LVFA preliminary testing in mind, we evaluated the same primary zinc and secondary zinc formulations in the hydrolytic stability and sludge and metal corrosion tests. The results are shown in Table I. Note the cor.rerse relationship between the two zincs in the two tests. The primary zinc-containing formulations shows rela-tively poor hydrolytic stability primarily because of high metal loss which we believe is the more crucial part of this test. It does, however, perform well in the sludge and metal corrosion test. The secondary zinc-containing formulation, on the other hand, performed in the opposite fashion. It did relatively well in hydrolytic stability, but poorly in sludge and metal corrosion test.
., .
-; The poor hydrolytic stability of this particular general-purpose primary zinc was not unique. The hydrolytic !
stability of two other similar general-purpose primar~ zincs was examined and relatively high metal 105s was found. These ., .

ij. .

~ are identified as B and C in Table II. Also shown in Table II
.. .
is a secondary zinc, E, which shows the same degree of metal ~ -loss as the general-purpose primaries, indicating that the ~
relatively low metal loss of the secondary reference zinc ~ -was not characteristic of all secondary zincs.

One feature which these two tests do have in common is that they both measure metal loss. Both the primary and secondary zinc were showing metal loss, although in different forms. However, we discovered that the combined use of two types of metal deactivators can minimize metal loss.

There are two common types of metal deactivators.
One, the film-forming type, minimizes metal corrosion by plating out on the metal surface. In effect, this puts a protective barrier between the metal surface and the corrosive materials.
T~e second type of deactivator reduces metal loss by chelating . ~ . .
~ or tieing up the corrosive materials before they can catalyze .! .. .
further attack on the surfaces.

When the same primary and secondary zinc formulations as above are formulated using various types of metal deactiva-tors, the results are shown in Table III. Table III shows that 1. None of the deactivators improved the performanceof the general-purpose primary zinc dithiophos-phates sufficiently to pass the hydrolytic stability test.
~1 2. Both the chelating and combination type of metal deactivators were effective enough on the second-ary zinc formulation for it to pass the hydro-lytic stability test. The improvement in -minimizing metal loss was substantial. Although .... . .
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1063~90 ~ ~
the chelating metal deactivator was more effective than the combination type in lmproving h~drolytic stability, 1t had been linked to compatibility problems in earlier work. There-fore, the combination type was preferred because of its better compatibility. As shown in Table IV, this deactivator was also effective in dramatically reducing the sludge and metal -corrosion of the secondary zinc formulation.
,, .
These results show that the "pximary zinc" should not be used in formulations where hydrolytic stability was required. The secondary zinc formulation was clearly superior.
However, this lubricant is still defective and requires for ~ -satisfactory performance the surface active component, namely, two specific types of rust inhibitors.

Although the use of the two combined metal deactlva-tors represents a ma~or means of improving the hydrolytlc stability of the secondary zinc formulation, a far more . I :
successful lubricant is obtained by the proper selection of rust inhibitors. The effect of various types of rust inhibi-tors on the secondary zinc in the presence and absence o* the 1~ 20 combination type metal deactivator is shown in TableVI. Unlike ; the formulations shown in TablëVI, these blends were not fully formulated, but contained only the components shown. Note I that both the acidic and neutral type rust inhibitors~which 1 are surface active enough to provide adequate protection as ','1 measured by the ASTM D 665B test, also reacted with the zlnc to promote severe metal attack in the hydrolytic stability -i test. The dibasic rust inhibitor which did not provide adequate rust protection, however, did not promote metal I attack. The presence of the combination type metal deactivator did not substantlally change these results. Where the .

1063~90 deactivator did produce a significant change, however, was in the case of the mixed rust inhibitors which consisted of both acidic and neutral components used separately before.
Without deactivator, metal attack occurred, but in the presence of deactivator, metal attack was reduced within the acceptable ; limits with no loss of rust protection. Obviously, the combination of the acidic and neutral components provides a balanced rust inhibitor which is surface active enough to protect against rust, but not active enough to overpower the metal deactivator.

: With some commercially available secondary zinc dialkyl dithiophosphates, a precipitate or haze will form when an effective amount of the combination of the two types of metal deactivators is incorporated therein. For example, ~uch a precipitate formed with "E". This precipitate formation should be used as a screening test to determine the better "secondary zincs" for use in the present invention.

Based on the results discussed above, it can be seen -~
` that the reactivity of zinc dithiophosphates, particularly in combination with other components, has a significant effect on the bronze/steel metallurgy found in some piston pumps.
Specifically, these results indicate that:
1. The secondary zinc reference formulation performed satisfactorily in the axial piston pump because it is less reactive than the general purpose primary zinc tested. These, being more reactive, are unsuited for use in bronze-on-steel axial piston pumps.
2. The film-forming, chelating, and combination types of deactivators were not effect-lve in reducing metal loss in hydrolytic stability testing of the primary zinc examined.

.

: ':
However, the chelating and combination type deactivators were effective in reducing metal loss of the secondary zinc formulation.

3. That rust inhibitors which are surface active - enough to provide good ru~t protection can react with the 6econdary zinc to promote severe metal attack in the hydrolytic stability.test. The presence of a combination type deactivator is not effective in these cases.

4. That the use of a mixed acidic-neutral type rust inhibitor with the combination type metal deactivator provides l adequate rust protection wlthout promoting metal attack.

;l Commercially available "primary" zinc dialkyl dithiophosphates are well-known and include "Amoco 5959",*
"Elco 103"* and "Oronite 269N.* Simllarly, there are many ¦ commercially avallable "secondary" zinc dialkyl dithiophosphates, i e.g., "Lubrlzol 677A*(the "reference" or "D" of the present j ca6e), Lubrlzol 1097~, and Edwln Cooper "Hitec E653"* (identified as "E" herein).

The commercially available "chelating type" metal deactlvators include "Amoco 150"*(an alkyl derivative of 2,5-di-mercapto-1,3,4-thiadiazole) and the relatsd "compounds ln U. S. 2,719,125; 2,719,126 and 2,983,716.

The commercially available film-forming type metal deactivators include the benzotriazoles (e.g., Vanderbilt "BT Z"* and U. S. Rubber Company "Cobrate 99"*), and the Vander-bilt products "Cuvan 80"* (N,N'-disalicylidene-1,2-propane-diamine, 80% in organic solvent, "Cuvan 7676"* and "Cuvan XL"*.

The commercially available neutral barium petroleum sulfonates include NaSul BSN* of R. T. Vanderbilt Co.
:
~ - ~ *Trademark - 12 -!

1063S90 ~ ~
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- The commercially available acidic type rust inhibitors are primarily substituted-succinic anhydrides (e.g., "TPSA" or tetraphenyl succinic anhydride).

Accordingly, the following example is illustrative of lubricants which can be produced ln accordance with the present ` invention.

ILLUSTRATIVE EXAMPLE

An additive mixture, for use in formulation of antiwear hydraulic oils containing a æecondary dialkyl dithio-phosphate5 was made by blending the following ingredients:
Weight %
i ditertiary butyl paracresol 20.0 naphthyl amine 20.0 zinc diamyldithiocarbonate 3.0 : tetraphenyl succinlc anhydride 2.2 neutral barlum petroleum sulfonate 1.5 ' "Amoco 150"* chelate-type deactivator3.3 Cuvan 80* film-forming deactivator 6~7 diluent, paraffinic oil 43.3 loo. o The additive mixture was blended as indicated below to make an antiwear hydraulic oil:
COMPOSITION ? VOLUME %

UV stable hydrocracked oil99.23 Secondary ZDP ("D"~ 0.40 Additive mixture 0.35 Silicone antifoam 0.02 The hydrocracked oil had an SUS viscosity at 100F of 200, an ASTM VI of about 100 and was paraffinlc by VGC class. The properties (and typical control limits) of the blend (in metric units) follow:

' *Trademark A~ 13 -' '. ' ~ ' ' ' " ' ' ' ' TYPICAL
RANGE
TESTS METHOD MIN. MAX. EXAMPLE
Viscosity, cSt/37.8C D445 ~2.9 46 2 44.6 Vlscosity, cSt/40C D341 40.2 Viscos~ty, cSt/98.9C D445 6.50 Viscosity, cSt~lOOC D341 6 33 Viscosity Index D2270 100 106 Flash, COC, C D92 204 235 # Pour, C D97 -18 -18 Color D1500 2.0 0.5 - Densit~/15c, kg/m3 D1298 873 861 Total Acid No., mgKOH/g D664 1.0 Copper Strip, 3 hrs/lOOC D130 Sul~ur, % D2622 0.14 Conradson Carbon, % D189 0.25 l An line Point, C D611 112 l # Demulsibility/54.4C D1401 Separation, minutes 3 25 ~j 20 ~ Foam, Tendency/Stability D892 Sequence I, cm3 50/0 25/0 Sequence II, cm3 50/0 25/0 ; Sequence III, cm3 50/0 25/0 Rust, Syn. Sea WatexD665B Pass Pass Oxidation Stability, hr. D943 2000 >2000 Continental Oxid.,hr. 100 >100 ;j 4-Ball Wear Scar, mm :' 20 kg, 1800 rpm, 54.4C, lhr 0 35 # Appearance Visual Bright Bright 1 30 ~ Zinc, wt.~ .044 .054 .0~8 ~hosphorous, wt.% D1091 .039 .051 .044 l # ~BPC, wt.% .070 .087 .077 .~, . . .
l When non-hydrocracked solvent refined paraffinic oils 41 are substituted for the hydrocracked oil, 0.50~ of the mixture ~ is required for equivalent performance.
.
Similarly, blends of hydrocracked and non-hydrocracked lubes can be used in the present example, as can unstabilized hydrocracked oils; however, in general the U.V. stabilized (by solvent extraction or hydrorefining) hydrocracked lube provides the best performance at lower additive levels.
. , .
Similarly, blends (as of 100 and 500 SUS, at 100F) of oils can be substituted for the 200 SUS base oil and higher or lower viscosity base oils (e.g., 80-2000 SUS) can be used, as in this example, to make hydraulic oils of varied viscosities.

.~ .

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106359~ ~

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In commercial addltives, the type and amount of ZDP can vary from brand to brand of additlve; however, in a given lubricant formulation, the amount of a glven ZDP can be determined by calculation from the zinc content. As a rule of thumb, such substitutions are done by the zinc equivalent method.
In the above example, the amount of additive should incorporated in the range of 0.044 to 0.054 Zn (typically o.o48 wt.%).
In the work reported in the Tables, the ZDP additives were ; ~ used at about the same Zn levels. The representative secondary ZDP, Lubrizol 677A* (sometimes identified as "D") analyzes 9.25 wt.~ Zn and 8.5 wt.~ P.
: .
Compositions according to the present invention can be made wherein the viscosity Or the base petroleum oll is in the range of 60-3000 SUS at 100F. In general, for use as a . ~
hydraulic oil the typical base oil viscoslty will be below 1000 SUS at 100F; however, lubricants consisting e~sentially of a 1000-3000 SUS at lOO~F base oil are useful as gear lubri-cants ~
", ~ :

The terms "compatible amount" and "mutually compatibleamounts" as used herein mean that no precipitate ls observed in the final lubricant when it is stored for 24 hours at about 65F.

*Trademark _ 15 --1~6359V

Table I
COMPARISON OF PRIMARY AND SECONDARY ZDP*
PERFORMANCE
-Maximum Acceptable Primary Secondary Te~t Limits ZDP ZDP
ASTM D 2619 Results Beverage Bottle ~ydrolytic Stability Test -Copper Wt. Loss, mg/cm2 0.5 3.5 0.5 -Total Acidity of Water Layer, mgKOH 6.0 6.2 8.9 Federal 3020.1 Results Sludge & Metal Corrosion - Insoluble Sludge, mg 400 198 921 - Metals in Combined Oil Water & Sludge Copper, mg 20Q 76 306 Iron, mg 100 13 341 * Zinc dlalkyldithiophosphate The base oil, in all tables herein, was 200 SUS, at 100F, "U.V" ætabilized (by solvent extraction) hydrocracked oll (ASTM VI about 100), available commercially as "Sunpar LW120"* or "Sunpar HPO 200"*, from the Sun Oil Company. The lubricant contained 0.5 Vol. ~ of the ZDP, 0.07 wt.% of diter-tiary butyl paracre~ol, 0.07 wt ~ naphthalamine, o. oo6 vol. ~
NaSul BSN*, .oo88 vol. ~ TPSA, 0.012% zinc diamyldithiocarbonate (Vanlube AZ*), and 2 ppm "active" silicon antifoam.

*Trademark .
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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition useful as an antiwear hydraulic oil or as a gear lubricant, comprising major amounts of a mineral lubricating oil and minor, effective and mutually compatible amounts of a secondary zinc dialkyl dithiophosphate antiwear agent, chelating type and film forming type metal deactivators, and, as rust inhibitors, a neutral barium salt of a petroleum sulfonate and an alkyl or aryl substituted succinic acid or acid anhydride, the weight ratio of the secondary zinc dialkyl dithiophosphate to the total weight of the deactivator compounds being generally no greater than about 15 to 1, and the weight proportions of the succinic acid, inhibitor and the neutral barium petroleum sulfonate being generally in the range of 3 to 1 to 1 to 1.

2. The composition of Claim 1, wherein said mineral lubricating oil consists enssentially of oil having an SUS
viscosity at 100°F in the range of 60-3000 SUS and a viscosity-gravity constant in the range of 0.780-0.819.

3. The composition of Claim 1, wherein said chelating type metal deactivator is an alkyl-substituted derivative of 2,5-di-mercapto-1,3,4-thiodiazole.

4. The composition of Claim 1 wherein said film-forming type metal deactivator is N,N'-disalicylidene-1,2-propane-diamine.

5. The composition of Claim 3 wherein said film-forming type metal deactivator is N,N'disalicylidene-1,2-propane-diamine.

6. The composition of Claim 1 wherein one said rust inhibitor is tetraphenyl succinic anhydride.

7. The composition of Claim 5, and containing tetra phenyl succinic anhydride.

8. The composition of Claim 7 wherein said lubricant is useful as a hydraulic oil and contains effective and com-patible minor amounts of a naphthyl amine, zinc dlalkyldithio-carbonate and ditertiary butyl paracresol.

9. The composition of Claim 8 wherein said base oil consists essentially of one or more hydrocracked oils having a viscosity gravity constant below about 0.80 and which have been stabilized against degradation by ultra violet light by extraction with an aromatic selective solvent.

10. The composition of Claim 9 and containing an effective amount of an antifoaming agent.