Volume 6 Preprint 48
Ecological Characteristics of New Fewcomponent Anticorrosion Conservation Materials Based on Oil
L.E. Tsygankova, V.I. Vigdorovitch and N.V. Shell
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Volume 6 Paper C116
ECOLOGICAL CHARACTERISTICS OF NEW FEWCOMPONENT ANTICORROSION CONSERVATION
MATERIALS BASED ON OIL
L.E. Tsygankova, V.I. Vigdorovitch, N.V. Shell
Department of Physical Chemistry, Derzhavin State University,
33, Internatsyonalnaya st., Tambov, 392622, Russia
The toxicological characteristics of the components of the anticorrosive conservation
materials based on oil, including a series of the mineral oils, polyaminoamide TVK-1,
amides of the carboxylic acids, a mixture of synthetic fat acids of C10-C16 fraction, the
synthetic fat acid bottoms, some individual amines, normal fractions of primary
amines C7-C9, C16-C20 and C10-C16, have been studied. Conservation materials
dispersion from the place of their application in the square with 600 m side has been
The oil conservation materials (CMs) are used for the metal protection against
atmospheric corrosion . The conception of the creation of the few-component CMs
has been suggested . These CMs are characterized by high technological efficiency
of their preparation and the practical use, a low cost price, a wide raw material base.
Simultaneously they must not have more low efficiency than the traditional
multifunctional compositions. It is more easy to prepare the few-component CMs as
ecological safe. The last demand determines a necessity of the integral estimation of
the toxicological properties of such compositions and their components.
Toxicological and physical-chemical meaning of the criterion quantities
LACwz - the limiting admitted concentration of a working zone – characterizes a
maximum admitted real concentration of the given individual substance or the
product at the working place ( on data of the State Standard of Russian Federation).
LACmd - the limiting admitted middle day (24 hours) concentration - characterizes a
maximum admitted real concentration of the given individual substance or the product
in the atmospheric air of the constant places where people live.
LACwz / LACmd ≥ 10
LACms - the maximum single once limiting admitted concentration - characterizes a
maximum admitted real concentration of the individual substance or the product in the
atmospheric air where the workers are present during 30 minutes (no more).
LACw - the limiting admitted concentration in water of the natural or the artificial
LACms >> LACwz
BCO5 - the biochemical consumption of oxygen in conditions of self-cleaning water in
a basin during 5 days – is expressed with mg O2 consumed from 1 ml of a solution. If
the substances are slightly soluble BCO5 is measured with mg O2 consumed from 1
ml of a saturated aqueous solution or from the diluted saturated solution.
CCO - the chemical consumption of oxygen in conditions of self-cleaning water in a
basin – is measured with the same units as BCO5. The LAC is famous for BCO5 and
CCO too. LAC (BCO5) is equal to 0,006 mgO2/ml and 0,002 mgO2/ml for the waste
water and the fish economic water basin respectively. LAC (CCO) is equal 0,003
mgO2/ml for first and is not set for last.
The estimation of CCO and BCO5 values has been made according to . A
calculation of the quantities of the middle year and the maximum single once
throwing away pollutants into the environment during the period of the anticorrosion
protection of equipment has been carried out according to [4-7]. Conservation
materials dispersion from the place of their application in the center of the square with
600 m side has been studied by the universal program «Ecologist» . The criterion
values have been received for number multifunctional additives to the oils: the amides
of the carboxylic acids , the synthetic fat acids (SFA) and the synthetic fat acid
bottoms (BSFA) , TVK-1 , mineral unused and waste oils  and others.
Sometimes the calculation of the LACmd has been made according to approximate
The values of LACwz have been determined for the simplest aliphatic amines (AA)
and the fractions of primary saturated AA (Table 1). LACms for the synthetic fat acids
of the C10-C16 fraction, TVK-1, mineral oil, saturated hydrocarbons of the C12-C19
fraction are equal to (mg/m3) 0,6; 100; 25 and 900 respectively. The active part of
some few-component anticorrosion CMs on oil base and themselves mineral oils and
waist ones are slightly soluble in water and neutral aqueous solutions. Therefore CCO
and BCO5 values have been estimated for their saturated solutions (SS) and the media
received by a dilution of last 2, 4 and 8 times.
LACi of some individual compounds and mixtures
Fractions of AA:
C7 – C9
C10 – C16
C16 – C20
C7 – C9
C10 – C16
C16 – C20
SFA C10 – C16
the limiting concentration with respect to the processes of a selfcleaning of the
the limiting concentration according to an influence on the organs of feelings;
a recalculation to CH3(CH2)3COOH; ****a calculation according to Eq.(1).
A. Mineral oils. The oils are widely used as a labricant and a solvent-support of the
anticorrosion conservation materials. They catch into the water of the basins together
with sewage. They are practically insoluble in water, but it is necessary to take
account 2 moments, at least:
1. The oils moisten water well spreading along its surface in the form of the thin
(monomolecular, in limit) film. A presence of such films above the water surface must
increase CCO and BCO because the oil components may be oxidized by dissolved
oxygen, other oxidizers and by the biochemical way. At any case the oils will
decrease a dissolved oxygen concentration.
2. The mineral oils contain always the factory additives being surface active
substances (SAS), the waste motor oils – in addition the products of the hydrocarbon
oxidation being SAS too. At such situation a presence of the oils in the water results a
formation of the emulsions of «oil in water» type. Such emulsions become stable in
the presence of above SAS as the effective emulsifying agents. This fact, in his turn,
causes a large increase of CCO and BCO and an aggravation of water quality.
In Fig.1 it is shown CCO and BCO5 values of the saturated aqueous solutions of some
mineral oils and media received by their dilution with distilled water 2, 4 and 8 times.
It is clear that CCO values of the oils SS exceed the corresponding LAC(CCO) many
times. The industrial oil I-20A is characterized by the largest CCO (Fig.1a, curve1).
The values of CCO and BCO5 for the transformer oil (TO) SS are less (Fig.1a, curve
2) that may be connected, in certain measure, with smaller number and smaller
concentration of the factory additives in it than in the I-20A. Dilution of the saturated
solutions decreases their CCO and BCO5 (Fig.1, curve 1 and 2), but slightly. The oil
M 10-G2 being used for lubrication of the motor and tractor engines in summer is
characterized by essentially smaller CCO and therefore it is more ecological. The
same picture is observed for TAD-17 I oil (being used for lubrication of the
transmissions) and waste motor oil (WMO) and its filtered fraction (Fig.1a, curves 3 –
Fig.1. The influence of the oil nature and its concentration in the aqueous
solutions on its values of CCO (a) and BCO5 (b). The oils: 1 – I-20 A; 2- TO; 3 – M
10-G2; 4- waste motor oil (WMO); 5 – filtered fraction of WMO ; 6 – TAD-17 I. C- a
concentration of the saturated solution here and further.
Fig. 2. The influence of the alkane nature and its concentration in the aqueous
solutions on its values of CCO (a) and BCO5 (b). The alkane: 1 – hexane; 2 – heptane;
3 –octane; 4 – nonane;
5 – decane; 6 – pentadecane.
The BCO5 values of the saturated solutions of the studied oils are less than their
CCO. The following row for the BCO5 values of the saturated solutions is observed:
TO > I-20 A > TAD-17 I ≈ M 10-G2 ≈ WMO > filtered WMO
The peculiarity of the oils is the frequent exceeding of the real values of BCO5 above
LAC(BCO5) including the diluted media.
B. Alkane hydrocarbons. It is interesting to estimate CCO and BCO5 values for
the saturated aqueous solutions of the C6 – C15 alkanes because they are components
of the mineral oils. The corresponding values are shown in Fig.2. Synonymous
dependence between a number of carbon atoms in the alkane molecule and the values
of CCO in the saturated solutions is absent. In the diluted solutions a character of this
dependence is more complicated. In whole the values of CCO in this media is less in
comparison with the oil solutions because the oils contain the factory additives and
the products of oxidation.
The attempt to estimate an influence of the carbon atoms number nC in the alkane
molecule on its CCO and BCO5 values is shown in Fig 3. Simultaneously the
influence of a dilution of the SS on these values is considered (nC = const). The
tendency of increase of the CCO values with increasing nC is observed. But one can
see a second periodical dependence. The alkanes with the odd number of carbon
atoms in the molecule are oxidized more lightly, by bichromate in particular, in
comparison with the molecules having the even number of carbon atoms. The same
dependence is repeated under the dilution of the saturated solutions two and 8 times
(Fig.3, curves 2 and 3). It allows to confirm that the observed dependence is reliable
sufficiently. The dilution of the studied solutions results decreasing CCO values. But,
of course, a character of CCO dependence from nC is different for the different
concentration solutions. However the differences have a quantitative character, but
not qualitative one.
Fig.3. The influence of a carbon atoms number in the alkane molecules and the
their aqueous solutions on CCO (a) and BCO5 (b) values. 1- a
saturated solution; a dilution of SS: 2- twice, 3 – 8 times.
The dependence BCO5 = f(nC) is the same qualitatively as the CCO = f(nC) (Fig.3b).
C. Amides of the carboxylic acids. The amides of the carboxylic acids are the
effective thickening agents of the mineral oils, the oil-soluble corrosion inhibitors and,
on whole, the perspective multifunctional additives into the oils. The ecological
toxicological characteristics have been studied for the amides of the saturated
monobasic carboxylic acids with nC equal to 5,
10 – 13 (mixture of the synthetic fat acids (SFA)), 11 and the unsaturated
C17H33CONH2 and C21H41CONH2. Amid of capric acid (C5H11CONH2) is soluble in
water and we have used its initial concentration equal to 0,5 g/l (0,0058 mole/l). The
corresponding experimental results are given in Table 2. For the saturated solutions
CCO values decrease in the following line:
C10-13H21-27CONH2 > C11H23CONH2 > C17H33CONH2 > C5H11CONH2 >
A dilution of the SS changes the above tendency and decreases the CCO values. The
BCO5 values of the SS of amides decrease in the following line:
C11H23CONH2 > C10-13H21-27CONH2 > C17H33CONH2 > C21H41CONH2 >
A dilution of the SS draws together the BCO5 values of the studied solutions of
D. Anticorrosion multifunctional additives.
1) BSFA. BSFA are a mixture of C19-C23 saturated carboxylic acids (about 86
SFA), higher paraffins, polymeric acids with nC = 34 and more. The CCO value of the
SS of BSFA is essentially less in comparison with the CCO values of the SS of I-20 A
and TO (Fig.1) and other oils. Moreover the CCO value decreases quickly with
increasing dilution of the SS but exceeds LAC (CCO) value even at 8 repeated
dilution. The same picture is characteristic for the BCO5 values of the BSFA
solutions. Thus BSFA are ecological more pure than the mineral oils. Therefore an
introduction of BSFA into the oils increases the ecological purity of the compositions
consisting of components of the 4th hazard category.
The CCO and BCO5 values of the aqueous solutions of the multifunctional additives
into the oils.
Concentration of the CCO, mg O2/ml
BCO5, mg O2//ml
C – a concentration of the saturation, **C=0,0058 mole/l
2) G-89. This multifunctional additive is a narrow fraction of homologues with
where n = 8 – 9. This substance shows very large thickening and anticorrosion action.
It is a product of the interaction of heptyl and SFA narrow fraction.. The CCO value
of G-89 saturated solution is less then for BSFA (Table 2) and decreases quickly with
increasing dilution of SS mounting to 0,055 mg O2/ml at 8 repeated dilution
(LAC(CCO) = 0,03 mg O2/ml). Thus the saturated solutions of G-89 are capable to a
self-cleaning at 8 repeated dilution. Unfortunately we could not estimate the BCO5
values of the G-89 solutions. Perhaps this product is not exposed to biochemical
oxidation or it proceeds very slowly.
3) TVK-1. It is very effective component for preparation of the few-component
conservation materials on the oil base. TVK-1 is a product of the interaction of
polyethylenepolyamine and SFA of the C21-25 fraction. It is polyaminoamide having
following molecule formula
where R is CmH2m+1 hydrocarbon radical, m = 20 – 25, n = 2 – 5. It is a substance of
the 4th hazard category. The CCO value of the TVK-1 SS is close to that of BSFA.
The BCO5 values of the TVK-1 solutions is even less than that of BSFA and only at 8
repeated dilution of the SS these values become identical.
Pollutant dispersion in atmosphere. Duration of the preparation of the
anticorrosion conservation materials on oil base in the place of their use with 300 kg
mass is taken equal to 16 hours (chronometer). Duration of the conservation process
at the heating of the composition up to 70-800 C for pneumatic pulverization is equal
to 15 hours. The sum mass of the dispersing material is equal to 30 kg (10%). The
dispersion source has no the extract ventilation and other apparatus to take out the
pollutants into atmosphere. The throwing out diameter is 0,5 m, a height is equal to 2
m, the throwing out rate is equal to 1,0 m/s. The middle temperature of a flow is equal
to 300 C. For example the results of the calculation of a dispersion of C16-20 aliphatic
amines and TVK-1 are shown in Fig.4 and Fig.5. They are pictured as isosters in
portions of LACms. The value of the background concentration has been taken equal
to 0,3 LACms. The maximum concentrations of substances are observed in the square
with 50 m side in the center of which the throwing out source is situated. Their values:
- a mineral oil
- the aliphatic amines of C10-15 fraction
- the aliphatic amines of C16-20 fraction
Fig. 4. The concentration of air pollution of the machine yard by C16-20 aliphatic
amines expressed in portions of LACms .
Fig.5. The same for TVK-1.
The tendency of increase of the CCO and BCO5 values with increasing nC is observed.
The alkanes with the odd number of carbon atoms in the molecule are oxidized more
lightly, in comparison with the molecules having the even number of carbon atoms.
On given criterions BSFA are ecological more pure than the mineral oils because the
CCO and BCO values of its SS are essentially less than for the SS of the mineral oils.
The saturated solutions of G-89 are capable to a self-cleaning at 8 repeated dilution.
The CCO value of the TVK-1 SS is close to that of BSFA. The BCO5 values of the
TVK-1 solutions are even less than that of BSFA.
The conducting operations on the preparation of the few-component conservation
materials and the anticorrosion processing of the agricultural machines don’t cause
above standardized pollution of the environment.
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Corrosion”, Corrosion and corrosion Protection, Proceedings volume 2001-22,
Pennington, USA, 2001.
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