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Antifoaming additives to turbine oils

Article  in  Chemistry and Technology of Fuels and Oils · July 1989

DOI: 10.1007/BF00719336

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CHEMMOTOLOGY

ANTIFOAMING ~ D I T I V E S TO TURBINE OILS

P. A. Kalinin, V. N. Bakunin, UDC 621.892.098

A. I. Echin, A. T. Podkhalyuzin,
and G. T. Novosartov

In modern steam turbines with high unit capacities and small size the lubricating oils
work under severe conditions: at high temperatures and loads, and at rapid recirculation
of the oil. As a result of the last, the air, which has been picked up by the oil during
operation, cannot be removed completely while the oil is in the oil reservoir. A stable
air-oil emulsion is formed, i.e., the oil becomes aerated.
Aeration can lead to undesirable changes in the exploitation properties of the oil:
the modulus of elasticity by volume decreases, the transfer of the hydraulic pulses in the
regulation system slows down~ the stability of the oil film decreases, the delivery and pressure
head of the oil pumps decreases, and oxidation of the oil intensifies [I]. S u r f a c e foam
is also formed in the contact of the oil with a large amount of air. However, foaming of
turbine oils is not a parameter which can be used to assess the reliability of operation
of the engine [2].
In the current design of oil reservoirs the presence of foam affects only the oil level
and increases its consumption due to losses through the ventilation openings. Aeration of
the oil represents a more serious hazard. The deaerating properties of turbine oils deterior-
ate in the presence of siloxane additives, which are added to prevent excessive foaming [3].
These additives effectively destroy surface foam, however, they enhance the formation of
a highly dispersed air-oil emulsion and reduce significantly its sedimentation rate. The
search for new additives which would inhibit foaming and at the same time would not affect
negatively the deaerating properties therefore represents an acute task.
From thermodynamic concepts it follows that single-component liquids are not capable
of forming a stable foam; it breaks down rapidly, regardless of the surface tension. A stable
foam can occur 0nly in a multicomponent system, where even one of the components possesses
surface-active properties and is capable of adsorbing at the interface. Lubricating oils
.represent complicated multicomponentsystems which contain different surfactants in the base
oil as well as in the additives. Consequently, many oils are inclined to foaming in the
exploitation process which leads to the need of adding antifoam agents. Turbine oils manu-
factured according to GOST 9972-74 contain the antifoam PMS-200A organosilicon additive.
Organosilicon compounds are being widely used as antifoaming agents. They are chemically
inert, stable and effective at high temperatures~ available~ and inexpensive. Their viscosity
and surface tension vary within wide limits [4]. The antifoaming properties of siloxane poly-
mers are due to the unusually low surfice strength of their films and to the ability of dis-
placing the not strongly enough adsorbed molecules of the foam stabilizer.
The mechanical strength of the mixed adsorbed film is lost due to deep changes related
to the occurrence of weakened sections. These sections are the first to break down under

TABLE 1
I Foamingtendency JDeaeration
Oil (~s~ no58-75), = l ~ n e,
at ~ 5 . c lat ~o.c I~t 95,c
I
Without additive 130 70 25 1,75
With VTES 20 20 15 6,5
With VTES and FO
copolymer
2:1 15 10 7 7,25
I:I 45 15 15 3~
1:2 110
0
65
0
25
0
2~
12,0
With PMS-2OOA

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 7, pp. 16-17, June, 1989.

348 0009-3092/89/0708-0348512.50 9 Plenum Publishing Corporation

 12D
f
/

eo
I
/ 8 Fig. i. Foaming tendency H at 60~
(solid curve) and deaeration time
(broken curve) of a turbine oil as
4~ function of the concentration c of
the antifoaming additive~

o,ooz 0,002 0,005

c,%

the action of different factors: gravitation forces of surface tension, vibrations, etc. Among
the siloxane fluids with different molecular mass studied the PMS 200A fluid is best suited
as an antifoaming additive for turbine oils [5]~
Nevertheless, it noticeably affects the deaerating properties of the oil. This is due
to several causes. Primarily, this is due to the formation of smaller air bubbles as the
surface tension decreases. Their rising speed therefore also decreases according to Stokes'
law
~=2r2(Qs
where v is the speed of rising of the air bubble, m/sac; r is the radius of the bubblej m;
Ps Pa is the density of the liquid and air, kg/m 3, q is the viscosity of the liquid, Pa'seco
The diameter of the air bubbles decreases in the presence of PMS-200A approximately by
a factor of 2, the rising speed by a factor of 4 [6]~ Secondly, an adsorption layer of the
surfactant additive is formed at the air-oil interface, which prevents the coalescence of
the air bubbles, thus increasing the deaeration time~
The optimum PMS-200A concentration, at which the turbine oils have satisfactory deaerat-
ing properties and do not form foam, is taken to be 0~ [7]. However, according
to [8] an optimum concentration cannot be found for silicone antifoaming additives: a concen-
tration of at least 10-4% is required to achieve satisfactory antifoaming properties, while
the concentrationmust not exceed 5.10-6%, so that the additive has no effect on the deaerat-
ing properties of the turbine oils.
Our results confirm that a PMS-200A concentration of 0~ is not the optimum concentra ~
tion; reducing it to 5~ does also not give the desired affect~ Evidently, the PMS-200A
antifoaming additive cannot satisfy the more severe requirements to turbine oils. The effi-
ciency of the organosilicon compounds depends on their structure and can be improved by the
introduction of COOH, (CH2)2CN groups and others, and also by using additional technological
approaches, and by changing the manufacturing regimes (it is known that sulfur and boron
atoms can be introduced into the polymethylsiloxane molecules [4])~
New antifoaming additives have been developed on the basis of modified polysiloxanes
[9]. With respect to their working characteristics they are all close to PMS-200Ao The proper-
ties of the latter are due to a large number of Si-O bonds; the surface activity of the sub-
stance and consequently its antifoaming effect depends on these bonds. They are also responsi-
ble for the deterioration of the deaerating properties of the oil; it was therefore decided
to reduce their number in the molecule. This is difficult to achieve directly in the poly-
methylsiloxane; another antifoaming additive, vinyltriethoxysilane oligomer (VTES) [I0],
containing Si-O bonds in the side chain instead of in the main chain of the oligomer, was
therefore taken as the modified product. This makes it easy to change its composition by
copolymerization with other monomers, for instance, fluorinated olefins (FO).
We have synthesized such additives containing different amounts of VTES and FO in the
polymer chain and investigated a turbine oil with different concentrations of these additives~
Based on the foaming and deaeration parameters the best results are obtained with a polymer
with the component ratio i:i, added in the concentration of 0.0003-0.0005%. The results
obtained in investigating the influence of additives with different VTES and FO ratios at a
concentration of 0.0005% on the foaming and deaerating properties of a turbine oil are pre-
sented in Table i. It can be seen that the pure oil possesses good deaerating properties
but forms abundant foam.

349
 PMS-200A completely inhibits foam formation, but the deaerating properties of the oil
becomes unsatisfactory. Based on the minimum deaeration time and a satisfactory antifoaming
effect, a VTES:FO ratio of i:i was used for the further investigations. The optimum concen-
tration of the antifoaming additive was derived from the data presented in Fig. I.
The additive used was a copolymer with the VTES:FO ratio of i:i. It was found that,
when varying its concentration in the range 0.0003-0.0005%, the additive gives a satisfactory
foam extinction (height of foam column 25-30 mm), while the deaerationtime of the oil is
insignificant. Thus, the oligomers of vinyltriethoxysilane and fluorinated olefins represent
effective antifoaming additives which have practically no adverse effect on the deaerating
properties of the oil. Such additives can be used to develop turbine oils which satisfy the
most severe exploitation requirements.

LITERATURE CITED
i. V. N. Kazanskii, Lubrication Systems of Steam Turbines [in Russian], Energiya, Moscow
(1974).
2. O. P. Kulyaev, V. K. Gusev, L. A. Gavrilov, et al.', Khim. Tekhnol. Topl. Masel, No. 3,
38-40 (1987).
3. P. A. Kalinin, G. T. Novosartov, and B. F. Kirdakov, Khim. Tekhnol. Topl. Masel, No. 8,
41-43 (1986).
4. V. K. Tikhomirov, Foams. Theory and Practice of Their Preparation and Extinction, 2nd
ed. [in Russian], Khimiya, Moscow (1983).
5. V~ N. Grishakin and A. G. Drobyshev, Tekhnol. Organiz. Proizvod., N~. 4, 40 (1966).
6. L. Dollinger, Erdol Kohle, 36, No. 3, 282 (1980)o
7. E. I. Gulin, D. P. Yakubo, V. A. Somov, et al., Handbook of Fuels and Lubricating Mate-
rials in Naval Technology, 2nd ed. [in Russian], Sudostroenie, Leningrad (1987).
8. P. D. Claxon, Tribology, February 8-13 (1972).
9. K. Weber, U. Riemann, and H.-U. Reichardt, Schmierungstechnik, 16, No. 2, 51-55 (1985)o
i0. Patent (USA) No. 2862885.

INFLUENCE OF THE HYDROCARBON GROUP COMPOSITION OF BASE OILS ON

THEIR SCALE-FORMING PROPERTIES

A. A. Chesnokov, N. Z. Chesnokova, UDC 665.765-404.033

and G. V. Polyaev

One of the most important characteristics of hydraulic oils is their thermalstability.

It is assessed on the basis of their scale-forming properties which depend on the many factors,
before all on the chemical composition of the base oil and consequently on the quality of
the crude. The literature* contains d a t a o n the antiscale-forming properties of base oils,
prepared from the same crude, but differing in their viscosity and depth of refining. The
objective of the present study was, to investigate the antiscale-forming properties of base
oils, prepared from different crudes, but with the same viscosity levels and depths of re-
fining.
The investigations were carried out with 1-20A base oils (GOST 20799-75) from the follow-
ing crudes: West Siberian; mixtures of Volga-Ural crudes with West Siberian crudes in the
ratios 80:20 and 30:70; mixtures of crude from the "Druzhba" pipeline with Surgutsk crude in
the ratio 50:50; and also with hydrocarbon groups, isolated from these oils by chromatography.
The scale-forming tendency of the oils was assessed in the standard lacquer deposition
unit for the determination of the volatility of oils in beakers according to GOST 20354-74.
The aluminum cup with the oil sample (0.2 g) was placed in the lacquer deposition unit on
the disc, heated to 320~ When evaporation of the oil stopped, the cup was covered with a

*Ao A. Chesnokov and N~ Z. Chesnokova, in: Oils and Fluids for Industrial Equipment [in Rus-
sian], TsNllTEneftekhim, Moscow (1983), p. 152.
Kuibyshev Branch, All-Union Scientific-Research Institute of the Petroleum Industry.
Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 7, pp. 17-19, July, 1989.

350 0009-3092/89/0708-0350512.50 9 Plenum Publishing Corporation

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