Evaluation and Performance of Turbine Oils G . H. VON FUCHS, N. B. WILSON, AND K. R. EDLUND Shell Oil Company, Inc., Wood River, Ill.
sponsible for the antirusting quality were, however, removed by these methods and the stable oils produced became inferior to less heavily refined or partly deteriorated oils with respect to rust-preventing characteristics. I n the presence of oils which provide no protective coating, steel surfaces are attacked by water with the formation of ferric oxide and black magnetic oxide. As rusting proceeds, these substances scale off and may be carried in suspension ia the oil. The oxide particles sometimes score bearings, plug oil lines, and lead to faulty operation or even sticking of delicate governor parts. Difficulties due to rusting in the governor mechanism of new turbogenerators have in the past few years become prevalent, often causing severe economic loss (1). It is the purpose of the present paper to advance methods for evaluating turbine oils, particularly in reference to stability and rust-prevention. This work has involved the develop ment of laboratory tests for predicting these important characteristics, as well as a critical review of the older tests for properties. The usefulness of these performance tests in discriminating between turbine oils meeting ordinary specifications is demonstrated by application to a wide variety of such products. Finally, the chemical factors studied in the development of an accelerated test for the stability of turbine oils are considered in relation to their effect upon performance in service.
Progress in the design and construction of steam turbines has introduced new problems in lubrication and aggravated old ones. The importance of predicting the behavior in service of turbine oils has led to the development of suitable accelerated laboratory tests. Two essential requisites of a good turbine lubricant are the ability to protect steel surfaces against rusting and high stability toward oxidation. These tests are capable of revealing wide differences among turbine oils which meet conventional specifications. A discussion is presented of the chemical factors which influence the performance of oils in relation to the various methods employed by turbine operators to maintain an oil in serviceable condition.
I
T IS becoming increasingly recognized that the perform-
ance of lubricating oils in modern steam turbines is but slightly if at all predictable from the conventional tests upon which specifications are commonly based. I n general, these tests are able to exclude carelessly refined oils but make no distinctions as to the ultimate suitability of various wellrefined products. Furthermore, progress in the design and construction of steam turbines has raised new problems in lubrication and aggravated old ones. Since oils were employed in early steam turbines merely to provide lubrication, no special processing was necessary. With the advent of larger turbine installations, oil-circulating systems were introduced and several other functions were assigned to the oil. I n addition to conventional hydrodynamic lubrication of the turbine shaft and thrust bearings and, in large units, also of couplings, the oil was required t o act as a coolant. More recently, the same oil has been employed as a transfer medium to actuate the governor, and in geared units it lubricates high-speed gears. Development of larger and more efficient turbines operating a t higher steam pressures and temperatures has further increased the demands on the lubricant. Early turbine oils lacked stability toward oxidation and the products formed caused emulsification with water, foaming, and deposition of sludge (6). At first the improvement of turbine oils was chiefly directed toward reduction of their sludging tendency. It soon became apparent, however, that oil-soluble deterioration products (organic acids, etc.) were also harmful. Attention therefore began to be directed toward oxidation characteristics, to the neglect of other considerations such as ability to wet metal surfaces and thus to prevent rusting of turbine parts in the presence of water. The earlier-type turbine oils either contained certain components which promoted the formation of an adherent film of oil or soon produced similar compounds through oxidation. Improvement in sludging and emulsification characteristics necessitated by the more exacting requirements of the newer turbines was brought about largely by the application of modern refining methods. The desirable wetting agents re-
Testing of Turbine Oils
It is clear that two types of test are indispensable in both the production and application of modern turbine oils: (1) methods must be available for determining the actual properties of a lubricant in service so that progressive deterioration may be followed; (2) accelerated laboratory tests are required for predicting performance characteristics in a reasonable time (86). Standard testing procedures have been adopted where significant and certain new testing methods
.O
sm
COO
gm no0 iwo isto TIME OF AGING ( W S )
tics
zuu
FIGURE1. OXIDATION CHARACTERISTICS OF NEW-TYPE HIGHLY REFINED TURBINE OILS (TURBINE OIL STABILITY
TEST)
306
May 15, 1941
ANALYTICAL EDITION
307
have been devised in cooperation with turbine manufacturers and operators. TESTSFOR INSTANTANEOUS PROPERTIES. Interfacial Tension against Water. This property is a function of certain polar molecular groups present in an oil and bears a relation to its emulsifying tendencies. It may conveniently be mea& ured by the pull-ring method employing the du Nouy interfacial tensiometer. Cloudy oil samples should be filtered (or centrifuged) before testing to avoid Contamination of the water phase in the measurement. Scale readings are converted to absolute values by means of a correction factor (37) which depends on the difference in density of the phases and on the dimensions of the ring. New highly refined oils usually have high interfacial tensions (above 40 dynes per cm.) but formation of oxidation products (or contamination with used oil) sharply reduces the value. It is well known that polar molecules (soaps, acids, etc.) concentrate at the oil-water interface and orient themselves with the carboxyl groups toward the water phase; they can thus produce marked effects even when present in minute concentrations. This fact is used t o great advantage because, in early stages of oxidation while mere traces of impurities are formed (values down to 30 dynes per om.), interfacial tension is the most practical means for detectina them (Figure 1). Interfacial tension m e ~ * u ~ p n i mht ix w b w eniployd ~ 3.- a cuutrol in 1I.c refining of lubricating 011 ($11). They wcw illso rerorlullended to 1l.e firat turbine 011 cornmutec of the A. 5. 'T. hl. about 20 years ago ( I S ) for following the deterioration of turbine
FIGURE 2. RUSTINQ TESTSON Srx NEW-TYPEHIGHLYREFINED 015s AFTER 48 HOURS
oils. Determinations were carried out by a drop-volume method using a modilied Donnan pipet and aqueous phases of pure water and 0.01 N sodium hydroxide (7).
Above. Assembly
NEUTRALIZATION NUMBER.This is determined by a standard procedure (A. S. T. M. Designation D188-27T, Method A) and measures the acid content expressed in milligrams of equivalent potassium hydroxide per gram of oil. Since wellrelined turbine oils have no measurable neutralization number (less than 0.05), free acids are a sign of oil deterioration or contamination. These substances are emulsifying agents and seriously affect the interfacial tension of the oil. When the interfacial tension drops below 30 dynes per em., measurable quantities of acids are usually present. Some organic acids attack copper and iron and form oil-soluble soaps which, in addition to being promoters of emulsification, act as powerful oxidation catalysts. Since various types of acids are formed on oxidation, depending on operating conditions and oil composition, a strict l i t on neutralization number cannot be set. Highly refined oils should generally not exceed a neutralization number of 1.0 in service. At this point the interfacial tension of the oil bas become extremely low (15 or less) and permanent emulsions often tend to form. While interfacial tension and neutralization number are normally sufficient to characterize the condition of a highly refined turbine oil in service, the following tests can provide additional information:
Sludge. This determination has lost much of its significance with the advent of modern nonsludging turbine oils. The oxldation products in such oils remain in solution long after the oil has become unfit for service. However, permanent water-oil emulsions, which usually contain some metal soaps as stabilizers, often clog filters and appear as sludge. Sludge deposits in neglected turbine installations present a serious problem because they not only interfere with lubrication but also drastically reduce the life of subsequent charges of oil. The ash content of sludge consists mainly of iron oxide, often with a trace of copper (S 67). Appearance. Badly deteriorated oils are usuahy ,very dark colored. Occasionally, however, an ail shows a persistent haze
Saponification Number (A. S. T. M. Designation D9436). This value is expressed in the same units as the neutralisation number but includes esters, soaps, and some potential acids (peroxides) in addition to free acids. The saponification number is thus always larger than the neutralization number (often as much as five to ten times as high) and embraces a large part of the oxidation products present iu the oil. A sharp increase in saponification number is an indication of approaching oil breakdown and sludge formation. The saponification number of sludge is very high. Viscosity Increase. An inorease of the oil viscosity in service is due to an accumulation of oil-soluble oxidation products and is a forerunner of sludge formation.
tions of theb;.der df one dart per million can be detected. This reagent was first applied by Fischer (11, f%) and the procedure was later adapted to the determination directly in oil solution by waring (3%). Steam Emulsian Number (A, S. T. M. Designation D157-36). This is generally rscognieed as the best method uow available for
Specimens
Below.
oxide from rust and dudw deposiis in the oil system. Such cou-
~ . ~ = . ~ ~~~~~~
~~~~
~
~~
lome organic acids forked f on deterioration of i n 09 attack ecp~er.forming oil-soluble soaps which are powerful
(dithiaone) in carbon tetrachloride (5 mg. per 100 ml.) is added
more. &e relationbetween steam ehulsion number and state of
308
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 13, No. 5
I n modifying the test in these laboratories to comply more nearly with conditions met in operation, the testing temperature is raised to 75" C., 10 per cent of water is added instead of 1 per cent, and stirring is carried on continuously for 48 hours. Under these more severe conditions rusting naturally proceeds rapidly in any oil which allows rust formation a t room temperature. However, the converse is not true, for an oil which is effective at room temperature does not necessarily protect steel surfaces at 75" C. The more discriminating test has given results in better agreement with service data.
COPPEnCOlL
FIGURE 3. OXIDATION CELLFOR TURBINE OIL STABILITY TEST
ACCELERATED TESTS FOR PREDICTING PERFORhlANCE CHARACTERISTICS. Turbine Oil Rusting Test. A clear distinction should be made between several kinds of corrosion which may occur in turbines. One type, which has been experienced for many years in the upper parts of oil reservoirs, etc., is caused by the action of water vapor and volatile acids from oxidized oil. Since the metal surfaces involved are not normally covered by oil, this is not essentially a problem in lubrication but can probably best be solved by application of a protective coating. A second type of corrosion is the attack of metal surfaces, which come in contact with the oil, by organic acids formed through oxidation. This problem can be eliminated by using an oil of high stability. In the present paper primary consideration is given to a type of attack which often occurs after only a short period of operation with new oils free of acid. This is purely a rusting phenomenon caused by droplets of liquid water coming in contact with steel surfaces which have presumably been covered by the lubricant and displacing it. An oil will protect against this more serious action only if it wets steel surfaces preferentially as compared with water. The importance of the antirusting quality in turbine oil has become recognized. A test devised three years ago by Kuebler (21) in the laboratories of one of the major turbine builders employs a highly polished steel specimen suspended in the oil t o be tested which is then stirred for a time to ensure wetting of the specimen. One per cent by volume of distilled water is added and stirring continued 8 hours a day for 5 days at room temperature.
The general arrangement of the test apparatus is shown in Figure 2. The oil samples are contained in 600-ml. heavy-walled Pyrex beakers which are mounted on thermostatically controlled hot plates. Vigorous stirring is provided by all-glass stirrers. The test specimens are lom-carbon cold-rolled steel with a hole a t one end to allow suspension by means of an enameled or lacquered wire. They are ground, polished, and cleaned before use and must not be touched with the fingers; great care must be exercised in preparing the strips t o ensure reproducible results. The specimen should not touch the sides of the beaker because a dead space will form in which water remains stationary, causing erratic results. Water is added during the test to replace that lost by evaporation. At the conclusion of the test the specimens are washed with naphtha and acetone and examined visually. Extent of rusting is expressed in per cent of surface rusted. Photographs of specimens from tests (Figure 2) show the wide variation in antirusting characteristics of several modern-type turbine oils.
Turbine Oil Stability Test. Turbine oils are expected to withstand continuous operation at moderately elevated temperatures in the presence of air, water, and metals without forming sludge or emulsions. Their service conditions are essentially different from those of automotive lubricants and, hence, efforts to evaluate turbine oils by commonly accepted oil-testing methods carried out a t excessive temperatures were singularly unsuccessful. One of the first tests adapted specifically for turbine oils was that of Funk (14, 15). This test was later modified and other tests were devised (6, 10, 23). The turbine oil stability test, developed in these laboratories for predicting the useful life expectancy of turbine oils, combines several features of earlier tests (10, 20,83,26, 29). Samples of oil are aged under accelerated conditions which do not deviate qualitatively from those met in practice and with the provision that all factors influencing rate of deterioration are maintained constant. A 300-ml. sample of the oil under investigation is placed in a large test tube, 60 ml. (20 per cent by volume) of distilled water are added, and metal catalysts are introduced (a coil of iron and a coil of copper wire joined together). Pure iron wire (analytical grade) is employed, whereas co per wire ordinarily manufactured for electrical purposes is satisgctory. Both metal surfaces are carefully cleaned before usin . Enough wire is taken to give 0.5 sq. cm. of copper surface an8 0.5 sq. cm. of iron surface exposed per ml. of oil. Pure oxygen is supplied to the oil a t a rate of 3 liters per hour through a glass tube terminating in a fritted-glass plate which disperses the gas into fine bubbles, ensuring intimate contact with the liquid and vigorous agitation. The oxygen escapes through a reflux condenser which retains water and volatile oxidation products to a considerable extent. The oxidation cell (Fiogure 3) is immersed in a thermostated bath maintained at 100 * 1" C. and the temperature of the sample comes to equilibrium at some value a few degrees lower because heat is continually lost through evaporation of water. I n the tests carried out in these laboratories, the temperature was 9 5 O * 1' C.; it may deviate somewhat from this figure in other apparatus if the rate of heat transfer is different. The water which is lost slowly throughout the test is replaced occasionally, so as to maintain its level at least 3 cm. above the sintered plate. Test tubes, thermostat, and oxygen-flowmeters are, for convenience, similar to those employed in the Indiana oxidation test ( 8 ) . Small portions of the oil are withdrawn for interfacial tension and neutralization number measurements a t intervals, as determined by appearance or the emanation of acidic odors, and the results are plotted as a function of time (Figures 1 and 4). Parts of the copper and iron coils are also removed, to maintain a constant ratio of metal surface to oil volume; the frequency of s m -
May 15, 1941
ANALYTICAL EDITION
TIME OF A G I N G (
[email protected])
FIGURE 4. OXIDATIONCHARACTERISTICS OF EARLY-TYPE LIGHTLYREFINEDTURBINEOILS (TURBINEOIL ST.4BILITY TEST)
309
The two metals together are less active than copper alone (Figure 5, C1) probably because iron, which stands higher in the electromotive series, hinders the solution of copper, which is the more active catalytically. Different results were obtained when copper and iron coils were connected together and when they were separated (Figure 5, C3). The former arrangement was adopted for the test so as to parallel turbine construction; good electrical contact must be maintained at all times in order to avoid variable galvanic effects which may lead to erratic results. Since the use of tin-plated copper tubes has been proposed for turbine oil coolers, a single experiment was performed with
pling then has no appreciable effect on the results. It can be seen that interfacial tension is more significant during early stages of oxidation, whereas neutralization number is more indicative when appreciable deterioration has occurred. Appearance and other tests previously described may yield significant information. With careful manipulation the life of an oil, taken as the time to reach a neutralization number of 1.0, is reproducible within a = t 5 per cent range. The test correlates well with practice, inasmuch as oils are rated in the same relative order as by their known service records. Because of the wide variation in operating conditions to which oils are subjected, a hard and fast prediction of their life expectancy in a given turbine cannot be made on the basis of any laboratory test. For example, it has been found that the ratio of the useful life of a certain oil in service to its life in the turbine oil stability test has ranged from 200:l to 5 : l .
Factors Influencing Oil Deterioration in Laboratory Tests Several important variables have been investigated in the laboratory in establishing the above conditions for accelerated aging. OXYQEN FLOW RATE. It is obviously desirable to maintain the flow rate a t so high a value that the oil is kept saturated with oxygen a t all times; the reaction velocity will then be insensitive to variations in flow above t h a t rate. Data obtained a t several rates (all other variables being held constant) are given in Figure 5 , A . It was found that 3 liters per hour are sufficient for saturation but 1 liter per hour seemed to be somewhat inadequate. Excessively high flow rates should not be employed, so as to avoid the rapid elimination of volatile oxidation products (see Volatile Oxidation Products, below). TEMPERATURE. Although no study of temperature coefficients has been made, reaction velocity is doubtless strongly dependent on this variable and precise control is therefore essential. The lower the temperature, the more time is required for testing. The temperature adopted is as high as is compatible with the presence of liquid water a t atmospheric pressure. METALCATALYSIS.The general catalytic effect of metals on oil oxidation has been known for some time (SS), but there has been confusion as to the difference in action of the various metals (8, 9, 20, 28, 33, 34, 55). Recently copper and iron have received special attention (10, 23, 29). Since both these metals are present in turbine lubricating systems, they were included in the laboratory stability test. The rate curves given in Figure 5, C1, demonstrate clearly the accelerating action of both metals, singly and in combination, in the presence of water. Although the activity of iron is less than that of copper per unit area, catalysis by iron may be the more important because of its greater extent of surface in a turbine. Since the reaction velocity varies with surface area exposed per unit quantity of oil (Figure 5 , C2), the importance of keeping this ratio constant is evident.
FIQURE5. FACTORS INFLUEKCING OIL DETERIORATION IN TURBINE OIL STABILITY TEST A.
C.
D.
Oxygen flow rate Metal catalysis: (1) kind of metal ( 2 ) ratio of metal aurfaces to oil volume, (3) galvanlio effects Effect of water
INDUSTRIAL AND ENGINEERING CHEMISTRY
310
TABLEI. PROPERTIES OF EARLY-TYPE LIGHTLYREFINED TURBINE OILS Oil designation
seconds seconds Davis water a t 77’ F., dynes
per cm. Steam emulsion numbei Specific dispersion (81)
1 2 3 26.6 28.6 24.9 3+ 5+ 6f +15 +25 +30 415 390 395 475 450 455 177 281 480 40 52 59.5 62 104 82 0.05 0.05
