AZƏRBAYCAN ALİ TEXNİKİ MƏKTƏBLƏRİNİN

XƏBƏRLƏRİ

PROCEEDINGS
OF AZERBAIJAN HIGHER TECHNICAL
EDUCATIONAL INSTITUTIONS

Cild 24. № 4
Vol. 24. № 4
 Azərbaycan Ali Texniki Məktəblərinin
XƏBƏRLƏRİ
BAŞ REDAKTOR: PROFESSOR MUSTAFA BABANLI
Baş redaktor müavini – Lətafət Qardaşova
İdarəedici menecer – İsmayılova Mehriban

REDAKSİYA HEYƏTİ:
V.M. Əhmədov, İ.A. Qaraqaş, H.B. Quliyev, R.S. Qurbanov,
K.Y. Deqtaryov, N.Ə. İmamverdiyev, N.Ş. İsmayılov, A.D. İsmayılzadə,
J. Kaspşik, A.T. Məmmədov, V. Pedriç, Ç,Q. Rəsulov, N.M. Səfərov,
V.M. Seyidov, E.F. Sultanov, A.İ. Timurziyev, Ə.A. Feyzullayev,
V.M Valyayev, A.V. Yazenin, Ə.Z. Zalov, N.P. Zapivalov

Jurnal Azərbaycan Respublikası Prezidenti yanında

Ali Attestasiya Komissiyasının qərarı ilə dissertasiya işlərinin
dərc olunduğu nəşrlər siyahısına daxil olunub

NEWS
of Azerbaijan Higher Technical Educational Institutions

EDITOR-IN-CHIEF: PROFESSOR MUSTAFA BABANLI

Deputy editor-in-chief – Latafat Gardashova
Managing editor – Mehriban Ismayilova

EDITORIAL BOARD:
V.M. Ahmadov, I.A. Garagash, H.B. Guliyev, R.S. Gurbanov,
K.Y. Degtarev, N.A. Imamverdiyev, N.Sh. Ismayilov, А.D. Ismailzadeh,
J. Kacprzyk, A.T. Mammadov, W. Pedrycz, Ch.G. Rasulov, N.M. Safarov,
V.M. Seidov, E.F. Sultanov, A.I. Timurziev, A.A. Feyzullayev,
V.M. Valyaev, A.V. Yazenin, A.Z. Zalov, N.P. Zapivalov

The journal by decision of Higher Attestation Commission under

the President of Azerbaijan Republic is included in the list of scientific
editions, in which the results of thesis works publish
 CONTENTS

Geology
E.Kh. Iskandarov, A.N. Baghirov,
Sh.A. Baghirov, Z.I. Farzalizade
Technology of cleanıng the bottomhole zone of oıl
wells from arp deposıts…………..................................................................................6

J.M. Eyvazov
Comparative study of cumulative oil production in different water
influx models as a result of increased drainage area…...…………………………...…10

ChemIstry and chemIcal technology

V.H. Babayeva, N.V. Salamova

Study of the oil collecting and dispersion properties of the amide
octyl bromide complex based on bicyclo[2.2.1]-hept-5-ene-2-carboxylic
acid and triethylenetetraamine…………………………………………………………….19

F.S. Gurbanova
The mechanism of the reaction of cyclopentadiene
alkylation with cyclohexyl alcohol…………………………………………………………24

R.A. Asadova
Plant growth stimulants based on organic acids………………………………………..29

A.A. Aliyeva
Application of the dynamic light scattering
method in nanotechnology…………………………………………………………..…….39

Mechanics and machine engineering

N.A. Gurbanov
Investigation of impact strength of hybrid fml composites
reinforced with different nanoparticles……………………………………………………47

M.A. Mammadova
Long durability of the damaged hollow shaft at torsion…………………………………52

Energy and power engineering

T.D. Veliyeva
Excitation regulators for synchronous machines
under variable load………………...............................................................................57

Economy and management

M.O. Nagiyev
Applıcatıon of economıc modelıng to evaluate the effıcıency of bankıng..................63

3
 MÜNDƏRİCAT

Neft və qaz

E.X. İskəndərov, Ə.N. Bağırov, Ş.Ə. Bağırov, Z.İ. Fərzəlizadə

Neft quyularının dibi zonasının AQPÇ-dən təmizlənməsi texnologiyası.......................6

C.M. Eyvazov
Drenaj sahəsinin artması nəticəsində müxtəlif su axını modellərində
cəm neft hasilatının müqayisəli tədqiqi..................………………………………...…...10

Kimya və kimya texnologiyası

V.H. Babayeva, N.V. Salamova

Bitsiklo[2.2.1]-hept-5-en-2-karbon turşusu və trietilentetraamin
əsaslı amidin oktil bromid kompleksinin neftyığma və dispersləmə
xassələrinin tədqiqi.....................................................................................................19

F.S. Qurbanova
Tsiklopentadienin tsikloheksil spirti ilə alkilləşmə
reaksiyasının mexanizmi……….................................................................................24

R.A. Əsədova
Üzvi turşular əsasında bitkilərin böyüməsinin stimulantları…………………………….30

A.A. Əliyeva
Nanotexnologiyada işığın dinamik səpilməsi üsulunun tətbiqi…………………………39

Mexanika və maşınqayırma

N.A.Qurbanov
Müxtəlif nanohissəciklərlə gücləndirilmiş hibrid FML
kompozitlərin zərbə gücünün tədqiqi……………………………………………………..47

M.Ə. Məmmədova
Zədələnmiş valın burulmada uzunmüddətli
möhkəmliyi məsələsinin həlli………………………………………………………………52

E n e r g e t i k a v ə e n e r j i m a ş ı n q a yı r m a s ı

T.D. Vəliyeva
Dəyişən yükdə işləyən sinxron maşınlarının
təsirlənmə tənzimləyiciləri………………………………………………………………….57
Iqtisadiyyat və idarəetmə

M.O. Nağıyev
Bank fəaliyyətinin səmərəliliyinin qiymətləndirilməsi üçün
iqtisadi modelləşdirmənin tətbiqi………………………………………………………….63

4
 СОДЕРЖАНИЕ

Нефть и газ

Э.Х. Искендеров, А.Н. Багиров, Ш.А. Багиров, З.И. Фарзализаде

Технология очистки призабойной зоны нефтяных
скважин от отложений АСП……………………………………………………………….6

Дж.М. Эйвазов
Сравнительное исследование накопленной добычи нефти
в различных моделях притока воды в пласт в результате
увеличения площади дренирования…………………………………………………..10

Химия и химическая технология

В.Г. Бабаева, Н.В. Саламова

Изучение нефтесобирающих и дисперсионных свойств октил бромидного
комплекса амида на основе бицикло(2.2.1)-гепт-5-ен-2-карбоновой
кислоты и триэтилентетраамина………………………………………………............19

Ф.С. Гурбанова
Механизм реакции алкилирования циклопентадиена
циклогексиловым спиртом……………………………………………………………….24

Р.А. Асадова
Стимуляторы роста растений на основе органических кислот……………………30

А.А. Алиева
Применение метода динамического рассеяния света в нанотехнологии………39

Mеханика и машиностроение

Н.А. Гурбанов
Исследование ударной вязкости гибридных МВЛ композитов,
армированных различными наночастицами………………………………………….47

М.А. Маммадова
Долговечность поврежденного полого
вала при кручении………………………....................................................................52

Энергетика и энергетическое машиностроение

Т.Д. Велиева
Регуляторы возбуждения синхронных машин при переменной нагрузке……….57

Экономика и менеджмент

М.О. Нагиев
Применение экономического моделирования для оценки
эффективности банковской деятельности……………………………………………63

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OİL AND GAS UDC 622.276

Pp. 6-9

TECHNOLOGY OF CLEANING THE BOTTOMHOLE ZONE OF OIL

WELLS FROM ARP DEPOSITS
E.Kh. Iskandarov, A.N. Baghirov, Sh.A. Baghirov, Z.I. Farzalizade
Azerbaijan State Oil and Industry University
Email: [email protected]

ABSTRACT

The development of a new and effective technology for the elimination of complications
caused by ARPD in the bottomhole zone of oil wells is considered. The main attention is
paid to the more sparingly soluble part of ARPD – asphaltenes, which are prone to re-
deposition. The effectiveness of the impact on the bottomhole zone with a light pyrolysis
resin, which is a good solvent for asphaltenes, is shown.
A technology has been proposed for deeper cleaning of the channels of liquid movement in
the bottomhole zone by using naphthenic acids, which are solvents for resins. A greater
cleaning effect was obtained due to a deeper splitting of tar-asphaltene compounds by the
action of naphthenic acid, followed by the dissolution of additionally released asphaltenes.
Based on the results of field tests, generalizing conclusions were made and appropriate
recommendations were given.
Keywords: oil well, near-wellbore zone, ARPD, asphaltenes, light pyrolysis resin, naph-
thenic acid.

Introduction: Due to the accumulation of asphalt, resin, and paraffin deposits (ARPD)
in the bottomhole zone, complications arise during oil production, which reduces the flow
rate and significantly reduces the workover period of wells. The main components of the
deposits are asphalt-resinous substances (ARS) (20-40% wt.) and paraffins (20-70%
wt.), as well as silica gel resin, bound oil, and mechanical impurities in the form of sand,
clay, salts, and water [1].
Also, the composition may contain metal oxides in small quantities (vanadium, iron). The
intensity of deposition of ARP particles depends on several factors: lowering the pressure
at the bottom of the well and disturbing the hydrodynamic balance of the system; lowering
the bed temperature; hydrocarbon composition of the fluid, etc [2].
Methods against the deposition of ARP are divided into measures to prevent formation of it
and methods of removing deposits. The impact is carried out at all stages of field
development to restore and improve the filtration characteristics of the bottomhole zone in
order to increase the flow rate of producing wells and the injectivity of injection wells.
Despite a significant amount of research and the availability of many technologies to fight
against ARPD, the development of new and more effective methods for eliminating the
complications caused by them is in high demand.

Objective: Depending on the geological and technical conditions and the causes of
contamination of the filter and near-wellbore zones, various technological operations are
carried out to clean them up [3].
Carbonate reservoirs that do not contain sediment-forming inclusions (sulfates, iron
compounds, etc.) are treated with a 10-16% aqueous solution of hydrochloric acid. Acetic
(10%) or sulfamic (10%) acids are also used. When exposed to collectors containing iron

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compounds, 2-3% acetic or citric acid is added to the hydrochloric acid solution to prevent
precipitation. In terrigenous reservoirs with a carbonate content of less than 10%,
hydrochloric (10-12%) and fluoric (3-5%) acids are used.
In order to restore the well flow rate and increase the oil recovery factor for the development
of new methods of influencing the bottomhole zone, the results of the analysis of samples
of ARPD of various compositions of a number of fields were studied. Thus, the oils of the
Mud Sopka field of the Neft Dashlary Oil and Gas Production Department (Oil Rocks) contain
11% resins, 1% asphaltenes and 0.64% paraffins. In two samples taken from the wells of
OGPU named after N. Narimanov, the composition of ASPO was as follows: mechanical
impurities 1.32 and 2.0%, asphaltenes 8.02 and 12.0%, resins 16.97 and 7.0%, paraffins
71.97 and 78.0%.
At various fields, diesel fuel, kerosene, gas condensate, and various solvents were used to
clean ARPD [4,5].
In recent years, a wide use of light pyrolysis resin has begun at a number of fields for
cleaning of paraffin deposits accumulated in the near-wellbore zone. As a result of the
impact of light pyrolysis resin on the bottomhole zone, operated for a long time (more than
10 years) at the fields of OGPU "Neft Dashlary", named after. A. Amirov and "Absheronneft",
an increase in oil production by more than 50% was recorded. After the impact on the
bottomhole zone in 21 wells, the period of stability of increased production averaged 1 year
or more. For greater effect, a demulsifier (1%) is added to the solvent.

Methods: Based on the complexity of the ARPD structure model (including asphaltenes,
resins, paraffins, water phase and mechanical impurities), the main attention should be paid
to the more sparingly soluble part of the ARPD – asphaltenes prone to re-deposition.
The question of the mechanism of dissolution of substances is one of the most difficult. The
process of ARPD dissolution upon contact of deposit ingredients with solvent molecules
occurs at the molecular level. As key factors, the composition and physicochemical
properties of solid hydrocarbons of various oil fields should be studied.
Asphaltenes and resins have the highest resistance to dissolution, and paraffins have the
least. Along with the resinousness and high viscosity of the production of most wells,
mechanical particles accumulate in the near-wellbore zone – a mixture of sand and clay,
and heavy oil components accumulate on the surface of these particles and in the pores of
the reservoir rocks. For a deeper cleaning of the channels of liquid movement in the near-
wellbore zone, in addition to the above solvents, the possibility of using naphthenic acids,
which are resin solvents, was studied. Naphthenic acids are the main part of the oxygen-
containing components of oils (0.5-3%) and are extracted from oil with an aqueous solution
of alkali in the form of salts (naphthenates). Naphthenic acids are a thick colorless (turns
yellow during storage) liquid with a boiling point of 130-280°C, a freezing point below 80°C,
practically insoluble in water, soluble in petroleum products and other organic solvents. They
are used as a solvent for resins [6].
Back in 1883, the Russian chemist V.V. Markovnikov acknowledged the presence of acids
in crude oil from Azerbaijan containing carboxyl groups associated with carboxylic acids.
Petroleum acids obtained from naphthenic-based Baku oil are also called natural naphthenic
acids due to their composition and physicochemical properties. The properties of acids
change depending on the boiling point.
For laboratory studies, oil samples were taken from wells 103, 2127, 308 and 1862, operated
by OGPU named after. A. Amirov, which has already achieved an increase in production
because of the use of a composition of light pyrolysis resin + demulsifier. As a result of tests
with the addition of 5-20% naphthenic acid, a decrease in the viscosity of the mixture by 7-
26% at 20-50°C was recorded. The rate of increase in the density of solutions turned out to

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be lower than the rate of increase in the density of naphthenic acid, which indicates the
occurrence of side physicochemical processes. Depending on the production of the well, at
a certain concentration and in a certain temperature range, naphthenic acid provides a
decrease in viscosity.
An analysis of the technologies used to clean the near-wellbore zone from ARPD allows
us to draw the following conclusions: the light pyrolysis resin currently used, containing
50-70% aromatic hydrocarbons (benzene compounds), mainly ensures the dissolution of
asphaltenes on the contact surface; better cleaning of the channels of fluid movement
can be achieved by deeper splitting of asphaltene-resin compounds by the action of
naphthenic acid, followed by the dissolution of additionally released asphaltenes.
For a deeper cleaning of the fluid flow channels, a technology has been developed for
sequential placement of components in the near-wellbore zone.
The consumption of naphthenic acid is determined based on statistical data depending on
the composition of the produced oil, reservoir characteristics, perforation interval, well life
and is set within 100-300 liters for initial implementation with subsequent correction.

Field tests were carried out at well No. 1862 in the following sequence: 2 tons of light
pyrolysis resin were mixed with 20 liters of alkan demulsifier and pumped into the well;
further, after 100 liters of water, 200 liters of naphthenic acid were pumped into the well; 4
tons of light pyrolysis resin were squeezed into the reservoir, a decrease in pressure on the
injection line was noted; fresh water in a volume of 2 m3, the light pyrolysis resin remaining
in the lines was pumped into the reservoir, the valve was closed. An hour later, the well was
put into production. The well was monitored before and after the test. With a flow rate of 0.3
tons of oil and 2.0 tons of water before the test, a flow rate of 0.5 tons of oil (66% increase)
and 4.0 tons of water after the test remained stable for a long time. Along with the increase
in flow rate, as the main result of any implementation, it should be noted its stability, which
is an important factor.
To assess the overall industrial efficiency of the technology that has passed field tests, it
would be useful to test the proposed composition in other fields with different geological
conditions and physicochemical properties of the produced oils.

Conclusion:
1. A new solvent-based technology for deeper cleaning of fluid flow channels in near-well-
bore zone has been developed.
2. The higher efficiency of the proposed technology in comparison with the analogue (only
light pyrolysis resin + demulsifier) is associated with the splitting of tar-asphaltene compo-
unds by the action of naphthenic acid, followed by dissolution of additionally released as-
phaltenes, removal of a larger amount of resins and asphaltenes from the near-wellbore
zone.

REFERENCES

1. Persiansev M.N. Oil production in difficult conditions. – “NedraBusinesscenter” LLC. –

2000. – 653 p.
2. Kayumov M.S., Tronov V.P., Guskov I.A., Lipaev A.A. Accounting for the formation of
asphaltene-resin-paraffin deposits at the late stage of oil field development. // Oil industry.
– 2006, №3. – Pp.48-49.
3. Wild J. Chemical treatment to control paraffin deposits. / Translated from English. Klepinin
V. // Oil and gas technologies. – 2009, №9. – Pp.25-29.

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4. Ramazanova E.E. The use of chemical reagents of complex action for the inhibition of
asphalt, resin and paraffin deposits / E.E. Ramazanova, A.N. Zeynalov // Azerbaijan Oil
Industry. – 2018, №3. – Pp.29-31.
5. Sharifullin A.V. Composite compositions for the processes of removal and inhibition of
asphaltene-resin-paraffin deposits. / Monograph. Publishing house of KSTU. – Kazan, 2010.
– 304 p.
6. Nametkin N.S. Naphthenic acids and products of their chemical processing. / N.S.
Nametkin., G.M. Egorova, V.K. Khamaev. – M.: Chemistry, 1982. – 184 p.

XÜLASƏ
E.X. İskəndərov, Ə.N. Bağırov, Ş.Ə. Bağırov, Z.İ. Fərzəlizadə
Neft quyularının dibi zonasının AQPÇ-dən təmizlənməsi texnologiyası

Neft quyularının quyudibi zonasında (QDZ) AQPÇ-nin yaratdığı fəsadların aradan qaldırıl-
ması üçün yeni və effektiv texnologiyanın işlənib hazırlanmasından bəhs edilmişdir. Əsas
diqqət AQPÇ-nin daha az həll olunan hissəsinə - təkrar çökməyə meylli olan asfaltenlərə
verilir. Asfaltenlər üçün yaxşı həlledici olan yüngül piroliz qatranı ilə QDZ-yə təsirin effektivliyi
göstərilir. Qatranlar üçün həlledici olan naften turşularından istifadə etməklə QDZ-da maye-
nin hərəkət kanallarının daha dərindən təmizlənməsi texnologiyası təklif edilmişdir. Naften
turşusunun təsiri ilə qatran-asfalten birləşmələrinin daha dərindən parçalanması, ardınca
əlavə olaraq ayrılan asfaltenlərin həll edilməsi hesabına daha böyük təmizləmə effekti əldə
edilmişdir. Sahə sınaqlarının nəticələrinə əsasən ümumiləşdirici nəticələr çıxarılıb və müva-
fiq tövsiyələr verilib.
Açar sözlər: neft quyusu, quyudibi zona, AQPÇ, asfaltenlər, yüngül piroliz qatranı, naften
turşusu.

РЕЗЮМЕ
Э.Х. Искендеров, А.Н. Багиров, Ш.А. Багиров, З.И. Фарзализаде
Технология очистки призабойной зоны нефтяных скважин от отложений АСП

Представлена разработка новой эффективной технологии ликвидации осложнений,

вызванных АСПО в призабойной зоне нефтяных скважин. Основное внимание уделе-
но наиболее труднорастворимой части АСПО – асфальтенам, склонным к повторному
отложению. Показана эффективность воздействия на призабойную зону легкой пиро-
лизной смолой, которая является хорошим растворителем асфальтенов. Предложена
технология более глубокой очистки каналов движения жидкости в призабойной зоне с
использованием нафтеновых кислот, являющихся растворителями смол. Больший
очищающий эффект получен за счет более глубокого расщепления смолисто-асфаль-
теновых соединений действием нафтеновой кислоты с последующим растворением
дополнительно выделившихся асфальтенов. По результатам полевых испытаний
сделаны обобщающие выводы и даны соответствующие рекомендации.
Ключевые слова: нефтяная скважина, призабойная зона, АСПО, асфальтены, лег-
кая пиролизная смола, нафтеновая кислота.

Publishing history
Article received: 30.08.2022
Article accepted: 04.05.2022

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OİL AND GAS UDC 622.276.43

Pp.10-18

COMPARATIVE STUDY OF CUMULATIVE OIL PRODUCTION

IN DIFFERENT WATER INFLUX MODELS AS A RESULT
OF INCREASED DRAINAGE AREA
J.M. Eyvazov
Oil and Gas Scientific Research and Design Institute
Email: [email protected]

ABSTRACT

A natural influx of water in oil reservoir surrounded by water aquifers play a very important
role in increasing oil recovery. Such reservoir caused by the production of hydrocarbon pro-
motes the influx of water from the surrounding aquifer to offset it. This can drive more hy-
drocarbons towards the surface thus enhancing the oil recovery. The calculation of water
influx is very difficult as it involves much uncertainty such as aquifer size, shape, structure
and aquifer rock properties. The present study was performed to show the quantitative po-
tential importance of water influx. The objective is that water influx models are utilized for
stimulating the aquifer performance. They take an important role in estimating the water
influx for operations like material balance calculations. Reservoir simulation makes better
optimization of hydrocarbon recovery by focusing on production and scheduling. The simu-
lation can be used for estimating the amount of oil in place or the production of oil at the
time interval with a specific water influx rate that depends on the permeability of the aquifers.
Keywords: water influx, history matching, oil recovery, sensitivity, drive mechanism.

Introduction: Petroleum reservoir drive mechanisms are often associated in some form or
another with formation waters as nearly all hydrocarbon reservoirs are bounded by water-
bearing rocks called aquifers which is a major source of water influx (water encroachment).
Although there are other sources of water movement into the reservoir, which includes re-
charge of the reservoir by surface water from outcrops and water injection from the surface
to supplement a weak aquifer. This aquifer may be larger than the hydrocarbon reservoir
that adjoin as to appear infinite in size, or they may be so small in size. Reservoir drive
mechanisms may be from the expansion of connate water within the gas or oil reservoir or
from an external aquifer at the edge of the reservoir, or from an underlying aquifer. High-
permeability reservoirs are often in contact with an aquifer that provides pressure support
through water influx.

Objective: A drop in the reservoir pressure due to fluid production causes the aquifer water
to expand and flow into the reservoir. That is to say as reservoir fluids are produced and
reservoir pressure declines, a pressure differential develops from the surrounding aquifer
into the reservoir (Figure 1).

Figure 1. Conceptual influx of water into the petroleum reservoir

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Hence, it is needful to characterize the reservoir-aquifer systems 3, which are classified

based on: degree of pressure maintenance, flow regimes, outer boundary conditions and
flow geometrics. But for the purpose of this study an aquifer will be classified based on flow
geometries edge water-drive and bottom-water drive (Figure 2).

Figure 2. Flow geometries describing water influx into the reservoir

Aquifers are water saturated permeable rocks surrounding a hydrocarbon reservoir, often of
much greater volume than the hydrocarbon part of the reservoir [2]. For a significant amount
of hydrocarbon reservoirs this aquifer provides a drive mechanism. Smith et al. (1992) list
different mechanism, which result in the driving force:
• water expansion;
• contraction of the pore volume due to the pressure decline from production and the com-
pressible nature of the rock;
• expansion of another hydrocarbon accumulation that shares the same aquifer with the
reservoir in production;
• artesian flow, where surface water recharges the aquifer.
Although early on it is difficult to determine if a natural water influx is taking place into the
reservoir, there can be some hints. A low and decreasing reservoir pressure decline rate
during increasing cumulative withdrawal of the reservoir can be a hint to an aquifer, although
the reason for this phenomenon could also be influx of another fluid from a yet undeveloped
region of the reservoir. Ahmed and McKinney (2005) warned that early water production,
although a possible hint towards an active aquifer, can be easily misinterpreted. This is es-
pecially true in the case of a fractured reservoir or a reservoir with high-permeability streaks.
Methods: Analytical Determination of Aquifer Parameters. Van Everdingen et al. (1953)
published a statistical method for deriving aquifer parameters for the Van Everdingen and
Hurst aquifer model based on a material balance approach. The cumulative water influx is
represented as an proportionality factor times the water pressure drop period and the di-
mensionless inflow function. For each available data point the proportionality factor can be
calculated. When the correct aquifer parameters have been chosen the proportionality factor
should remain constant for each material balance calculation step. An improvement for this
method was published by Mueller (1962), who expanded the applicability of the method to
aquifers with linearly varying aquifer properties. McEwen (1962) developed a technique for
assessing water influx parameters where initially only the oil in place is calculated and the
water influx constant is taken as proportional to the oil in place. This leads to better results
than the method by Van Everdingen et al. when the reservoir pressure data is erratic. The
ratio between the proportionality factor and the oil in place is calculated as a function of initial

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formation volume factor, effective aquifer fluid compressibility and the water saturation of
the reservoir before water influx. Havlena and Odeh (1963) proposed straight-line material
balance relationships. By plotting the ratio of net production in reservoir barrels F and the
expansion of oil EO, against the ratio of aquifer influx function S and expansion of oil (i.e.
F/EO vs. S/EO), the correctness of the assumed aquifer parameters can be tested. In case
of a correct water influx this plot shows a straight line. The intercept of the straight line with
the ordinate gives a value for the original oil in place and the slope of the line gives the
aquifer influx constant. Tehrani (1985) published an improved method for calculating the
water influx constant from a different but algebraically equivalent form to the one proposed
by Havlena and Odeh.
Sills (1996) then combined the Havlena Odeh straight line approach with the Tehrani ap-
proach. Also this method was developed for the Van Everdingen and Hurst unsteady-state
radial aquifer model. A combined aquifer/reservoir expansion term is introduced. When the
water influx parameters in the aquifer model are correct, a plot of the net production in res-
ervoir barrels against this combined aquifer/reservoir expansion term should give a straight
line. The best fit values for the original oil in place are determined with the technique devel-
oped by Tehrani.
Numerical Determination of Aquifer Parameters. Numerical determination of analytical
aquifer properties can be done via the history matching procedure. History matching is a
process where reservoir model properties are varied until measured field data reasonably
matches the output of the dynamic reservoir model calculated with a reservoir simulator.
Adjustable parameters include permeabilities, porosities, fault transmissibilities and throws,
compressibilities, initial fluid contact depths and also aquifer properties. History matching
mainly deals with aquifer properties, since this part of the hydrodynamic system is of great
importance for the pressure match and typically only sparse information about this domain
is available.
Generally two approaches can be taken. One method is to manually adjust the reservoir
model parameters and the second one is to automatically determine the parameters within
a given range.
Williams et al. (1998) described a manual, traditional history matching approach, where the
aquifer model parameters are one of the first adjusted parameters within the process of the
pressure matching. It should be noted that this history matching approach is not specifically
designed for the determination of parameters for analytical aquifer models, but a general
approach that can be applied also for gridded or other aquifer models.
Anterion et al. (1989) developed a method that assists history matching, which can be
viewed as a first step towards automated history matching, but this method itself cannot be
understood as an automated history matching technique. In this approach gradients of the
components of the objective function as a function of the history matching parameters are
calculated. However, it is still the decision of the reservoir engineer which parameters have
to be changed and by what amount.
In recent years many different approaches to automated history matching have been devel-
oped. Gradient methods, based on the approach presented by Anterion et al. (1989), are
one of the main methods. Bissel et al. (1994) applied this approach for automated history
matching on a full field case, by finding a local minimum of the objective function using non-
linear regression algorithms. Another type of automated history matching is the use of sto-
chastic samplers or optimizers. Within this category fall ant colony optimization (e.g. Hajiza-
deh et al. 2009), genetic algorithms (e.g. Castellini et al. 2005), evolutionary algorithms (e.g.
Schulze-Riegert et al. 2002) and other similar strategies. The advantage of these ap-
proaches is that they are more able to find a global minimum, but difficulties with the quan-
tification of uncertainties are a shortcoming of this method (Christie et al. 2013).
The third category of automated history matching methods is the use of filtering techniques.

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An example is the Ensemble Kalman Filter. A comprehensive literature review on this filter
can be found in Aanonsen et al. (2009). When faced with realistic field cases, problems
originating from ensemble collapse have been observed (Myrseth and Omre 2010). Also no
specific case of aquifer parameter determination using this technique could be found in the
literature.
Another approach specifically designed for the determination of aquifer parameters has
been presented by Mittermeir et al. (2004) and Pichelbauer (2003). They published the Tar-
get Pressure Method (TPM), which is a numerical method for the determination of aquifer
parameters, well suited for reservoir simulation and can be easily introduced in any simula-
tion package. This method presents a tool for the automated matching of the pressure his-
tory. It is an explicit method that determines the required water influx at every step of the
history run to match measured pressure data. At the end of the history simulation the best
fitting aquifer parameters for the Fetkovich, Carter-Tracy and Vogt-Wang aquifer models are
calculated, which can be viewed as the minimization of an objective function.
Experimental Determination of Aquifer Parameters. Experimental methods for determin-
ing aquifer parameters are very uncommon in the oil industry. Direct measurement of the
model parameters for a Van Everdingen and Hurst radial aquifer would require the determi-
nation of the following aquifer properties: reservoir drainage radius, effective reservoir ra-
dius, aquifer permeability, reservoir thickness, aquifer porosity, total aquifer compressibility
and the aquifer water viscosity.
Water influx volume as well as the flow geometrics has a significant role to play in the re-
covery factor. Estimation of water influx volumes into the reservoir is significant in number
of applications such as material balance for estimation of reserves, reservoir simulation stud-
ies for model calibration, production scheduling and setting up development strategies to
optimize hydrocarbon recovery. An accurate estimation of water influx into the reservoir is
required with the aid of an efficiency aquifer model that can capture the real dynamics of
petroleum subsurface system.
Further, it is important to characterize the aquifer behaviour before start aquifer modelling
or inclusion of aquifer into the reservoir simulation model. This is because during aquifer
characterization, the understanding of aquifer properties and strength is increased.
Aquifer characterization is a challenging task in aquifer modelling. This is because most of
aquifer properties such as aquifer size, aquifer permeability, aquifer porosity and water en-
croachment angle are uncertain. One of the main reasons is the cost of drilling wells into the
aquifer to gain necessary information is often not justified.
The aquifer can be classified as finite or infinite (bounded). Geologically all formations are
finite, but may act as infinite if the changes in the pressure at the oil-water contact are not
felt at the aquifer boundary. Some aquifer outcrops are infinite acting because of surface
replenishment. In general, the outer boundary governs the behaviour of the aquifer and,
therefore:
1. Infinite system indicates that the effect of the pressure changes at the oil/aquifer boundary
can never be felt at the outer boundary. This boundary is for all intents and purpose at a
constant pressure equal to initial reservoir pressure.
2. Finite system indicates that the aquifer outer limit is affected by the influx into the oil zone
and that the pressure at this outer limit changes with time.
Three flow regimes are basically considered in describing fluid flow in the reservoir. These
are steady state, semi-steady state (pseudo-steady state), and unsteady state. Steady state
flow regime occurs when the rate of change of pressure at every location in the reservoir is
zero. This is when the reservoir is supported by pressure maintenance operations or when
there is a recharge from strong aquifer. Semi-steady state occurs when the rate of change
of pressure is constant and unsteady state flow regime occurs when the rate of change of
pressure is not zero or constant. The driving mechanism most commonly encountered is

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one in which both water and free gas are available in some degree to displace the oil toward
the producing wells. Two combinations of driving forces can be present in combination drive
reservoirs. For instance, depletion drive and a weak water drive, depletion drive with a small
gas cap and weak water drive.
Water Influx Models. Water influx models are mathematical models that simulate and pre-
dict cumulative water influx into the reservoir. Various researchers have proposed models
that estimate cumulative water influx into the reservoir. Out of them three models are con-
sidered more realistic to date: the van Everdingen-Hurst model, Carter-Tracy model and
Fetkovich model. The following are some of models applied in estimating water influx into
the reservoir listed based on author:
1. Pot aquifer model.
2. Schilthius steady-state model.
3. Hurst’s modified steady-state model.
4. Van Everdingen and hurst unsteady-state model.
5. Coats model or Allard and Chen model.
6. Carter Tracy water influx model.
7. Fetkovich water influx model.
The methodology adopted in this research is to calculate water influx for edge and bottom
water drive from pressure history data obtained from a field in the Niger Delta using Fetko-
vich steady state model. The calculated water influx is used to determine the recovery fac-
tors using the material balance equation algorithm (MBAL) software.
The workflow for MBAL reservoir modelling for this study was generated by first defining the
studied reservoir. Next step was to input the necessary PVT data, followed by the reservoir
pressure and production data. After inputting these data, it was necessary to conduct a his-
tory matching process and to run simulations, which would yield prediction needed for the
study. At this point desired results are achieved.
The key input data for building the MBAL model of the reservoirs include PVT, production
and pressure, average reservoir/petrophysical parameters, and depth versus pore volume
from the geological static model.
Historic production data was imputed in to the MBAL Tank model. The production data was
matched with the model simulation by regressing on rock and fluid parameters with high
uncertainty. The match parameters were recorded as the base parameter and other sensi-
tivity on aquifer parameters using the Fetkovich model for a bottom and edge water drive
was performed to compare the relative increase in cumulative oil production. Some of the
parameters used for sensitivity are:
- aquifer volume;
- aquifer permeability;
- dimensionless reservoir size.
Modelling Assumptions. The following assumptions were adopted:
1. The reservoirs are assumed to be a tank.
2. The reservoirs are assumed to be homogenous (thus, they have uniform reservoir prop-
erties).
3. The reservoir pressure and temperature are uniformly distributed.
4. Uniform thickness.
5. Uniform porosity.
6. Constant rock compressibility.
7. Constant water compressibility.
This study was conducted on tank reservoir modeling in MBAL software. Tank reservoir
model was created in MBAL software and this model was for X horizon of Gunashli field.
Originally oil in place was 57892900 m3. The following figure shows tank parameters for the
model (Figure 3).

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Figure 3. Tank parameters

There are 5 wells in the system. It has been included 5 historical wells into the model
(Figure 4).

Figure 4. Well scheme in model

The study was based on how aquifer permeability and encroachment angle influence to the
cumulative oil production in Fetkovich water influx model and the effect of aquifer permea-
bility to the cumulative oil production in Carter Tracy water influx model (Figure 5).

Figure 5. The effect of aquifer permeability to the cumulative

oil production in Fetkovich water influx model

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In case of 350 mD for aquifer permeability, cumulative oil production will be 7113750 m3.

Figure 6. The effect of encroachment angle to the cumulative

oil production in Fetkovich water influx model

In case of 210 degrees for encroachment angle, cumulative oil production will be 7638750 m3
(Figure 6).

Figure 7. The effect of aquifer permeability to the cumulative

oil production in Carter Tracy water influx model

In case of 350 mD for aquifer permeability, cumulative oil production will be 7163250 m3
(Figure 7). This shows that, after 300 mD of aquifer permeability, cumulative oil production
will stay same.
Conclusion: The power of the water aquifers plays a very important in reservoir modeling.
Aquifer permeability and encroachment angle influence cumulative oil production very
strongly. In Fetkovich and Carter Tracy's water influx models, the cumulative oil production
will increase as a result of increased aquifer permeability. In the Fetkovich water influx
model, an increase in encroachment angle affects the cumulative oil production from the
reservoir.

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REFERENCES

1. Sospeter Maganga. Aquifer Characterization and Modelling a case study of Norne Field.
– 2017, 10(1). – Pp.1-18.
2. Ahmed T. Reservoir engineering handbook. // Water influx (3rd ed.). – Burlington: Gulf
Professional Publishing, 2006.
3. Knut. Petroleum Geoscience from Sedimentary Environments to rock physics. – 2015.
DOI 10.1007/978-3-642-34132-8_8.
4. Al-ghanim J.A., Nashawi I.S., Malallah A. Prediction of Water Influx of EdgeWater Drive
Reservoirs Using Nonparametric Optimal Transformations. – Cairo: Society of Petroleum
Engineers. DOI: http://dx.doi.org/10.2118/150662-MS.
5. Craft B.C., Hawkins M., Terry R.E. // Aplied Petroleum Reservoir Engineering (2nd ed.).
Englewood cliffs. – New Jersy: Printice Hall, PTR Dake L.P., 1978. Fundamentals of Res-
ervoir Engineering (1st ed.). – Amsterdam: Elsevier Science B.V.
6. Shepherd M. Factors Influencing Recovery from Oil and Gas Fields. // AAPG Memoir 91.
– 2009. – Pp.37-46.
7. Jahn Wiley, Cook M., Graham M. Hydrocarbon Exploration and Production. // ISBN:
0444828834. – 1998.
8. Schlumberger, Aquifer Characterization Techniques (Methods in Water Resources Eval-
uation). – 2007. ISBN 978-3-319-32137-0.
9. Petrowiki. Water influx models. Retrieved April 27, 2019. http://petrowiki.org/Water_in-
flux_models.
10. Leung W.F. Numerical Laplace Inversion Methods. // Application to the Calculation of
the Water Influx from Aquifer Connected to petroleum Reservoirs. – 1986, 30(1). – Pp.74-
88. DOI: 10.1080/10916461003752611.
11. Dake L.P. Fundamentals of Reservoir Engineering. – 1978.
12. Allard D.R., Chen S.M. Calculation of Water Influx for Bottomwater Drive Reservoirs.
Society of Petroleum Engineers. – 1988, 03(02). – Pp.369-379. DOI: https://doi.org/10.2118/
13170-PA.

XÜLASƏ
C.M. Eyvazov
Drenaj sahəsinin artması nəticəsində müxtəlif su axını modellərində
cəm neft hasilatının müqayisəli tədqiqi

Təbii su axını su layları ilə əhatə olunmuş neft laylarında neftvermənin artırılmasında çox
mühüm rol oynayır. Karbohidrogen hasilatı nəticəsində yaranan belə su axını onu kompen-
sasiya etmək üçün ətraf su laylarından suyun axınına kömək edir. Bu, daha çox karbohid-
rogenləri səthə çıxara bilər, beləliklə də neftverməni artırır. Su axınının hesablanması çox
çətindir, çünki sulu təbəqənin ölçüsü, forması, strukturu və sulu təbəqənin süxur xüsusiyyət-
ləri kimi bir çox qeyri-müəyyənliyi ehtiva edir. Bu tədqiqat su axınının potensial əhəmiyyətini
göstərmək üçün aparılmışdır. Məqsəd ondan ibarətdir ki, su axını modellərindən sulu təbə-
qənin fəaliyyətini stimullaşdırmaq üçün istifadə edilir. Material balansının hesablanması kimi
əməliyyatlar su axının təxminində mühüm rol oynayır. Kollektor simulyasiyası hasilat və
planlaşdırma üzərində fokuslanaraq karbohidrogenlərin çıxarılmasını daha yaxşı optimal-
laşdırır. Simulyasiya sulu təbəqələrin keçiriciliyindən asılı olan xüsusi su axını sürəti ilə vaxt
intervalında neft ehtiyatını və ya neft hasilatını qiymətləndirmək üçün istifadə edilə bilər.
Açar sözlər: su sahəsinin təsiri, hasilat tarixinin bərpası, neftvermə əmsalı, həssaslıq, basqı
rejimi.

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РЕЗЮМЕ
Дж.М. Эйвазов
Сравнительное исследование накопленной добычи нефти
в различных моделях притока воды в пласт в результате
увеличения площади дренирования

Естественный приток воды в нефтяной пласт, окруженный водоносными горизонтами,

играет очень важную роль в повышении нефтеотдачи. Такой горизонт, вызванный до-
бычей углеводородов, способствует притоку воды из окружающего водоносного гори-
зонта для его компенсации. Это может вытолкнуть больше углеводородов на поверх-
ность, тем самым повысив нефтеотдачу. Расчет притока воды очень сложен, посколь-
ку он связан с большой неопределенностью, такой как размер, форма, структура и
свойства горных пород водоносного горизонта. Данное исследование было прове-
дено, чтобы показать количественное потенциальное значение притока воды. Цель
состоит в том, чтобы модели притока воды использовались для стимуляции произво-
дительности водоносного горизонта. Они играют важную роль в оценке притока воды
(обводненности) для таких операций, как расчет материального баланса. Симуляция
горизонта (моделирование пласта) улучшает оптимизацию извлечения углеводоро-
дов за счет сосредоточения внимания на добыче и планировании добычи. Моделиро-
вание может быть использовано для оценки запасов нефти в пласте или добычи неф-
ти на временном интервале с определенным расходом воды, зависящим от проница-
емости водоносных горизонтов.
Ключевые слова: обводнение (приток воды в пласт), историческое восстановление
добычи, нефтеотдача, чувствительность, механизм вытеснения

Publishing history
Article received: 30.08.2022
Article accepted: 04.05.2022

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CHEMİSTRY AND CHEMİCAL TECHNOLOGY UDC 632.953.541.2

Pp.19-23

STUDY OF THE OIL COLLECTING AND DISPERSION PROPERTIES OF

THE AMIDE OCTYL BROMIDE COMPLEX BASED ON BICYCLO[2.2.1]-
HEPT-5-ENE-2-CARBOXYLIC ACID AND TRIETHYLENETETRAAMINE
V.H. Babayeva, N.V. Salamova
Institute of Petrochemical Processes of the National Academy of Sciences of Azerbaijan
Email: [email protected]

ABSTRACT

The synthesis of a new surfactant and the study of its oil-collecting and dispersing
properties has been presented. The article shows the synthesis of an amide based on
bicyclo[2.2.1]-hept-5-ene-2-carboxylic acid and triethylenetetraamine and the octyl
bromide complex of the resulting amide. Bicyclo[2.2.1]-hept-5-ene-2-carboxylic acid was
first synthesized on the basis of cyclopentadiene and acrylic acid. The amide was then
obtained by reacting bicyclo[2.2.1]-hept-5-ene-2-carboxylic acid with triethylenetetraamine.
The synthesis of the complex of the resulting amide with octyl bromide (C8H17Br) in a ratio
of 1:2 was carried out. The density and refractive index of the resulting complex were
determined. This compound has been found to have a high surface activity. The oil-
collecting and dispersion properties of the obtained complex were tested. It has been
experimentally established that the maximum value of the oil collection coefficient in
distilled water for ~27.0-31.0 hours is K=30.40, for ~51.0-99.0 hours K=60.71, in drinking
water at ~0 it is K=30.40, at ~1.0-6.0 hours K=60.71 The dispersant exhibits dispersion
properties in drinking water for ~51.0-88.0 hours KD=96.7%, at ~99.0 hours KD=95.6%,
and in sea water at ~ 27.0-88.0 hours KD=93.4%, at ~99.0 hours KD=95.6%.
Keywords: bicyclo[2.2.1]-hept-5-ene-2carboxylic acid, triethylenetetraamine, amide, oil
recovery and dispersion.

Introductıon: In recent years, along with the rapid development of the oil industry, there
has been a sharp environmental pollution [1,2]. As a result of substandard transportation
and storage, improper processing of oil, serious damage is caused to flora and fauna.
Pollution of water basins with oil as a result of various accidents is becoming one of the
key problems facing humanity. One type of such pollution is the formation of a thin oil layer
on the surface of the water. Currently, intensive work is underway to collect spilled oil on
the surface of the water and clean this contaminated surface from traces of oil. In this
direction, an indispensable role is played by the use of physicochemical methods and
means.

Objective: The most effective method for cleaning a thin oil layer (thickness < 1 mm) on
the water surface is the colloid-chemical method [3,4]. As a result, the search for new and
effective reagents that have oil-collecting and dispersant properties, capable of dispersing
thin oil layers, allowing biochemical decomposition, removing oil from the water surface
and at the same time obtained on the basis of relatively less environmentally harmful raw
materials does not lose its relevance to this day [ 5-7]. The presented work is very relevant
for solving the above environmental problem.

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Methods: First, to obtain bicyclo[2.2.1]-hept-5-ene-2-carboxylic acid, dicyclopentadiene

was monomerized. To do this, dicyclopentadiene is poured into a three-necked flask and
heated to 140-150°C. To prevent reverse dimerization of the resulting monomer, the
receiver is intensively cooled. Then, the calculated amount of a solution of acrylic acid in
benzene is added to the flask. A solution of acrylic acid in benzene is added to the
monomerized cyclopentadiene and stirred. The reaction is exothermic and therefore the
experiment is carried out at room temperature with cooling.
In the course of the amide synthesis, bicyclo[2.2.1]-hept-5-en-2-carboxylic acid is placed in
a round bottom flask, and triethylenetetraamine (TETA) in a separating funnel. When the
temperature in the flask reaches 70-80oC, TETA is added dropwise to it. The reaction
proceeds for 2 hours at a temperature of 130–140oC with the release of 1 mole of water.
The resulting amide is a viscous liquid, soluble in water and isopropyl alcohol. The amide
yield was 83%.
C8H17Br was used to obtain a complex from alkyl halides. For synthesis, 1 mole of amide
is dissolved in isopropyl alcohol and added to the flask, 2 mole of octyl bromide is added to
it. The reaction is usually carried out at a temperature of 50-60oC for 3 hours. The solvent
used is 25 ml of isopropyl alcohol. As a result of the reaction, an amide complex with
C8H17Br is formed in 98% yield [8]. The physicochemical parameters of the synthesized
complex were determined and presented in Table 1.

Table 1. Physicochemical properties of the synthesized complexes

Density, Refraction,
Name of complex Molar ratio 20 20
d 4 , кg/m3 nD
NTA+C8H17Br 11: 2 1.3731 1.4130

Results and ıts dıscussıon: Bicyclo[2.2.1]-hept-5-ene-2-carboxylic acid was obtained by

the reaction of interaction of dicyclopentadiene with acrylic acid. The reaction proceeds
according to the following equation:

O
+

OH
O OH

Scheme 1.

Based on the obtained bicyclo[2.2.1]-hept-5-ene-2-carboxylic acid and triethylenetetra-

amine, an amide was synthesized by follow reaction:

140 0C
H NH2
H2NCH2 CH2 NHCH2CH2 NH CH2 CH2 NH2 + N
-H2O N
NH
C C H

O O
OH
Scheme 2.
Then the complex was synthesized by the reaction of the resulting amide with C8H17Br
octyl bromide. The formation of the complex proceeds according to the following reaction:

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Scheme 3.

where RX= C8H17Br

The possibility of using the synthesized complex for purification of water basins
contaminated with a thin oil layer, i.e. oil-collecting and dispersed properties of the
complex.
The oil-collecting and dispersing capacity of the resulting reagent was studied under
laboratory conditions according to the procedure [9]. According to this method, after
adding a reagent (usually 0.02 g of the active substance) to the oil layer (0.165 mm thick)
on the water surface (40-50 ml), the area of the collected oil layer is measured, the oil-
collecting coefficient is determined and denoted by K. The oil-dispersing ability of the
reagent is determined by retention time () of the state of dispersed oil after adding a
surfactant (0.02 g of active substance) to an oil layer (0.165 mm thick) on the water
surface (40-50 ml). Laboratory tests were carried out using samples of oil from the
Balakhani field, forming a thin layer on the surface of water with various degrees of
mineralization (distilled, drinking and sea) and the results of these studies are presented in
Table. 2. The reagent was applied to the surface of oil-contaminated water in the form of a
5% aqueous solution.

Table 2. Results of studying the oil-collecting and dispersed

properties of the NTA + C8H17Br complex

Distilled water Drinking water Sea water

Reagent , h. K KD , h. К KD , h. К KD
NTA+C8H17Br (1:1)
55 % water 00-6.0 224.32 11.0-6.0 330.40 00-6.0 ДDisp.95.6%
solution 227.0-31.0 330.40 551.0-88.0 224.32 227.0-88.0 ДDisp.93.4%
551.0-99.0 660.71 99.0 ДDisp.96.7% 999.0 ДDisp.95.6%
ДDisp.95.6%

Conclusion:
1. Synthesis of bicyclo[2.2.1]-hept-5-ene-2-carboxylic acid was carried out based on the
reaction of interaction of cyclopentadiene and acrylic acid
2. An amide was obtained based on the reaction of bicyclo[2.2.1]-hept-5-ene-2-carboxylic
acid and triethylenetetraamine. The synthesis of the complex of the obtained amide with
octyl bromide was carried out, its physicochemical parameters were determined
3. The possibility of using the synthesized complex for purification of water basins
contaminated with a thin oil layer, i.e. oil-collecting and dispersed properties of the
complex. It has been established that the resulting complex is surface-active and has a
high oil-collecting capacity. The dispersant exhibits a dispersion effect in drinking water for
~99.0 hours KD=95.6%, and in sea water for ~99.0 hours KD=95.6%

REFERENCES
1. Mariano A.J., Kourafalou V.H., Srinivasan A. et al. On the modeling of the 2010 Gulf of
Mexico Oil Spill. // Dynamics of Atmospheres and Oceans. – 2011. – Vol.52. – Pp.322-
340.
2. Asadov Z.H., Huseynova Kh.A., Rahimov R.A., Ahmadova G.A., Zubkov F.I. Alkyl chain
and head-group effect of mono- and diisopropylolalkylamine-polymethacrylic acid comple-

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xes in aqueous solution. // Journal of Molecular Liquids. – 2017. – Vol.244. – Pp.533-539.

3. Asadov Z.H., Huseynova S.M., Ahmadova G.A., Rahimov R.A., Sharbatov S.U., Zub-
kov F.I., Jafarova R.A. Synthesis, Colloidal-Chemical and Petroleum Collecting Properties
of New Counterion Coupled Gemini Surfactants Based on Hexadecylbis(2-hydroxypropyl)
amine and Dicarboxylic Acids. // Journal of Dispersion Science and Technology. DOI:
10.1080/01932691.2019.1650755.
4. Vorobyov Yu.L., Akimov V.A., Sokolov Yu.I. Prevention and liquidation of emergency
spills of oil and oil products. – M.: Inoktavo, 2005.
5. Asadov Z.H., Salamova N.V., Akhmedova G.A., Zarbaliyeva I.A. Obtaining, physico-
chemical characteristics, oil-collecting and dispersing properties of hydroxypropyl ethers of
fish oil acid fraction and their phosphates. // Natural and technical sciences. – 2009, №3
(41). – Pp.64-68.
6. Asadov Z.H., Salamova N.V., Rahimov R.A., Akhmedbekova S.F. Obtaining and pro-
perties of aminoamides based on beef fat triglycerides and their phosphate modifications.
// Bulletin of the Voronezh State University, series: Chemistry, Biology, Pharmacy. – 2014,
№4. – Pp.12-17.
7. Babayeva V.H., Mammadbayli E.H., Agamaliyeva D.B. i dr. Synthesis of complexes of
norborn-5-ene-2-carboxylic acid amide with hexylbromide and study of their influence on
the biocorrosion process. // Neftepererabotka i neftekhimiya. – 2019, №3. – Pp.21-26.
8. Gumbatov G.G., Dashdiyev R.A. The use of surfactants for the elimination of emergen-
cy oil spills on the water surface. – Baku: Elm, 1998. – 210 p.

XÜLASƏ
V.H. Babayeva, N.V. Salamova
Bitsiklo[2.2.1]-hept-5-en-2-karbon turşusu və trietilentetraamin əsaslı amidin oktil
bromid kompleksinin neftyığma və dispersləmə xassələrinin tədqiqi

Yeni səthi aktiv maddənin sintezinə və neftyığma və dispersləmə xassəsinin tədqiqindən

bəhs edilir. Məqalədə bitsiklo[2.2.1]-hept-5-en-2-karbon turşusu və trietilentetraamin
əsasında amid və alınmış amidin oktil bromid kompleksinin sintezi öz əksini tapmışdır. İlk
olaraq tsiklopentadienin akril turşusu ilə qarşılıqlı təsirindən bitsiklo[2.2.1]-hept-5-en-2-
karbon turşusu sintez edilmişdir. Daha sonra bitsiklo[2.2.1]-hept-5-en-2-karbon turşusu
trietilentetraaminlə qarşılıqlı təsir reaksiyasından amid alınmışdır. Alınmış amidin
alkilhalogenidlərdən oktil bromidlə (C8H17Br) 1:2 nisbətdə kompleksi sintez edilmişdir.
Alınan kompleksin sıxlığı və şüasındırma əmsalı təyin edilmişdir. Müəyyən olunmuşdur ki,
bu birləşmə yüksək səthi aktivliyə malik birləşmədir. Alınmış kompleksin neftyığma və dis-
persləmə qabiliyyəti sınaqdan keçirilmişdir. Təcrübə zamanı müəyyən edilmişdir ki,
reagentin maksimal neftyığma əmsalı distillə suyunda 27.0-31.0 saatda K=30.40,
51.0-99.0 saatda K=60.71, içməli suda 0 saatda K=30.40, 1.0-6.0 saatda K=60.71
səviyyəsindədir. Dispergent içməli suda 51.0-88.0 saatda KD=96.7%, 99.0 saatda
KD=95.6%, dəniz suyunda isə 27.0-88.0 saatda KD= =93.4%, 99.0 saat müddətdə
KD=95.6% dispersləyici təsir göstərir.
Açar sözlər: bitsiklo[2.2.1]-hept-5-en-2-karbon turşusu, trietilentetraamin, amid, neftyığma
və dispersləmə.

РЕЗЮМЕ
В.Г. Бабаева, Н.В. Саламова
Изучение нефтесобирающих и дисперсионных свойств октил бромидного
комплекса амида на основе бицикло(2.2.1)-гепт-5-ен-2-карбоновой кислоты
и триэтилентетраамина

Проведен синтез нового поверхностно-активного вещества и изучены его нефтесо-

бирающие и диспергирующие свойства. В статье показан синтез амида на основе
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бицикло(2.2.1)-гепт-5-ен-2-карбоновой кислоты и триэтилентетраамина и октил бро-

мидного комплекса полученного амида. Сначала на основе циклопентадиена и акри-
ловой кислоты был осуществлен синтез бицикло(2.2.1)-гепт-5-ен-2-карбоновой кис-
лоты. Затем взаимодействием бицикло(2.2.1)-гепт-5-ен-2-карбоновой кислоты и три-
этилентетраамина получен амид. Осуществлен синтез комплекса полученного ами-
да с октил бромидом (C8H17Br) в соотношении 1:2, определены плотность и показа-
тель преломления полученного комплекса. Установлено, что это соединение обла-
дает высокой поверхностной активностью. Проведены испытания нефтесобирающих
и дисперсионных свойств полученного комплекса. Экспериментально установлено,
что максимальное значение коэффициента нефтесобирания в дистиллированной
воде в течение ~27.0-31.0 ч. составляет K=30.40, в течение ~51.0-99.0 ч. K=60.71,
в питьевой воде при ~0 составляет K=30.40, при ~1.0-6.0 ч. – K=60.71 Диспергент
проявляет дисперсионные свойства в питьевой воде в течение ~51.0-88.0 ч. –
KD=96.7%, при ~99.0 ч. – KD=95.6%, а в морской воде при ~27.0-88.0 ч. – KD=93.4%,
при ~99.0 ч. KD=95.6%.
Ключевые слова: бицикло[2.2.1]-гепт-5-ен-2карбоновая кислота, триэтилентетра-
амин, амид, нефтесобирание и диспергирование.

Publishing history
Article received: 30.08.2022
Article accepted: 28.03.2022

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CHEMİSTRY AND CHEMİCAL TECHNOLOGY UDC 632.953. 541.2.

Pp.24-29

THE MECHANISM OF THE REACTION OF CYCLOPENTADIENE

ALKYLATION WITH CYCLOHEXYL ALCOHOL
F.S. Gurbanova
Institute of Petrochemical Processes of the National Academy of Sciences of Azerbaijan
E-mail: [email protected]

ABSTRACT

The reaction of alkylation of cyclopentadiene with cyclohexyl alcohol in the presence of a

catalytic system consisting of an aqueous solution of potassium hydroxide and nanosized
magnesium oxide was carried out. The yield and physicochemical parameters of the syn-
thesized dicyclohexyl-cyclopentadiene were determined. The structure of the obtained
compound was confirmed by IR spectroscopy. An interpretation of the probable mecha-
nism of this reaction is given. It has been shown that the reaction under study proceeds
with the formation of an intermediate pseudoaromatic compound, cyclopentadienyl anion,
followed by the addition of an electrophilic particle (alkyl radical) and elimination of a water
molecule.
Keywords: cyclopentadiene, alkylation with cyclic alcohols, pseudoaromatic system, na-
nosized catalyst.

Introduction: Cyclic alcohols are often used as alkylating agents for various organic sub-
strates. In this direction, there are a number of reports showing the possibility of using
cyclanols as alkylating agents. Among cyclic alcohols, cyclohexanol is most often used for
this purpose. Thus, in [1], the effectiveness of clays treated with p-toluenesulfonic acid (p-
TSA) was studied in the alkylation of p-cresol with cyclohexanol under microwave irradia-
tion without a solvent. Various aspects of reaction studies include varying temperature,
contact time between reactants, molar ratio of cresol to cyclohexanol, and varying degrees
of p-TSA treated clay. Acid strength as well as reaction parameters such as temperature
and time have been found to be major factors controlling reactivity and selectivity. The re-
action was carried out in the temperature range 413–443 K. O-alkylation dominated at low
temperatures, while C-alkylated p-cresol was obtained at higher temperatures. The cata-
lyst retained catalytic activity even after three successive runs. The results obtained with
clays were compared with other solid acid catalysts such as aluminum replacement clay,
hydrochloric acid treated clay, and K-10.
Shape-selective catalysts for the alkylation of biphenyl with cyclohexanol were prepared by
modifying the MCM-22 zeolite using the process of chemical liquid deposition with tetrae-
thylorthosilicate [2]. The modified MCM-22 catalysts were characterized by X-ray diffrac-
tion, N2 physical adsorption-desorption, NH3 temperature-programmed desorption, and
pyridine-adsorbed infrared spectroscopy. Modification is not observed significant structural
changes. Precipitated SiO2 can reduce the number of external Bronsted acid sites of zeo-
lites without a noticeable decrease in the total number of acid sites. Form-selective alkyla-
tion of biphenyl with cyclohexanol was carried out on the synthesized catalysts. The selec-
tivity of 4-cyclohexylbiphenyl and 4,4'-cyclohexylbiphenyl peaked at 80.4% and 63.7%, re-
spectively, when the reaction was carried out for 200 minutes at 190℃ at atmospheric
pressure. Experimental data showed that isomerization reactions at external Bronsted acid

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sites were effectively reduced. In addition, the catalytic activity of the used zeolites was
almost restored by calcination.

Objective: A simple synthesis of hexagonal α-zirconium phosphate (ZP) nanoparticles as

an efficient, environmentally friendly and recyclable solid acid catalyst has been studied.
Polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA) were used as an organic matrix
that acted as dispersing agents and acted as a matrix for the nanoparticles. Apparently,
hydrogen bonds between ZP and PVA or PVP along the polymer chains lead to better dis-
persion of ZP formed in situ. Pure hexagonal ZP nanoparticles were obtained after calcina-
tion with PVA/ZP or PVP/ZP. The catalysts have been characterized by several physico-
chemical methods. The acid properties were studied by alkylating phenol with cyclohexa-
nol in the absence of a solvent, resulting in 2-cyclohexylphenol (2-CP), 4-cyclohexylphenol
(4-CP) and 2,4-dicyclohexylphenol (2,4-DCP). This alkylation reaction was also carried out
on P2O5/Al2O3, P2O5/SiO2, α-ZrP (produced in the absence of polymers) and various ionic
liquids using cyclohexanol and cyclohexene as alkylating agents. Using hexagonal ZP na-
noparticles as a catalyst under optimized reaction conditions, excellent phenol conversion
and selectivity to 4-CP were obtained. The catalyst was easily removed from the reaction
mixture, regenerated, and reused at least four times without significant loss of its catalytic
activity [3].

N-alkylation of morpholines with aliphatic and alicyclic alcohols in the gas and solid phas-
es was studied in a fixed bed reactor over a CuO-NiO-γ-Al2O3 catalyst obtained by the im-
pregnation method [4]. It was shown that N-methylmorpholines are formed with a conver-
sion of 95.3% and with a 93.8% selectivity. In this case, the corresponding apparent acti-
vation energy is 46.20 kJ/mol. The present catalyst system is also applicable to other low-
er primary alcohols. However, secondary alcohols have relatively low product selectivity,
since the resulting ketone is a poorer electrophile than the aldehyde. For cyclohexanol, low
conversion and selectivity are mainly due to steric effects. The catalyst exhibits high cata-
lytic activity without obvious fluctuations over a long period of 120 hours.
It was shown in [5] that during the alkylation of phenol on solid surfaces in the liquid phase,
the catalytic activity, the kinetic mechanism (Langmuir-Hinshelwood or Eli-Ridil) and the
preferred reaction route (for example, C- or O-alkylation) depend on the type and strength
of acid site, nanoenvironment size, alkylating agent (electrophile), temperature, and sol-
vent. In this paper, the authors report a detailed kinetic and mechanistic study of cyclohex-
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anol/cyclohexene alkylation of phenol catalyzed by a range of solid acids containing vari-

ous proportions of Bronsted and Lewis centers in aqueous and nonpolar solvents.
Alkylation of phenol with cyclohexanol, catalyzed by SO3H-functionalized ionic liquid, was
studied [6]. The influence of the reaction temperature, reaction time, molar ratios of rea-
gents, amount and recycling of the ionic liquid on the alkylation reaction has been studied.
The results showed that under optimal reaction conditions of phenol/cyclohexanol/ionic
liquid molar ratio =14:10:1, reaction temperature 200°C and reaction time 6 h, the conver-
sion of phenol and the selectivity of para-cyclohexylphenol were 75.7% and 61.5% respec-
tively. When the ionic liquid was reused more than three times, its catalytic activity practi-
cally did not change.
The alkylation of phenols is of great importance in synthetic chemistry, as well as the val-
orization of lignocellulosic raw materials obtained from biomass [7]. Using a detailed kinet-
ic and mechanistic study of phenol alkylation with cyclohexanol/cyclohexene, it is shown
that alkylation requires the formation of carbenium ions by protonation of the intermediate
formed alkene. In situ measurements of the reacting species using NMR spectroscopy
helped to identify the reaction steps.
In this regard, we carried out the alkylation of cyclopentadiene with cyclohexyl alcohol in
the presence of a catalytic system consisting of an aqueous solution of KOH and na-
nosized magnesium oxide.

Methods: For the study, the following initial reagents were used with the following physi-
cochemical parameters: dicyclopentadiene DCPD (boiling point 1700C, density 0.976
g/cm3, refractive index 1.5050), cyclohexyl alcohol (boiling point 160-1610C, density 0.962
g/cm3, refractive index 1.4610, melting point 23.90C).
Nanosized magnesium oxide is an odorless white powder substance with high strength,
purity and melting point. Its structure was studied using a C3MY-5 atomic force micro-
scope in the semi-contact and phase modes.
The experimental procedure was as follows. The calculated amount of cyclohexyl alcohol
and the corresponding calculated amount of the catalytic system were loaded into a four-
necked round-bottom reaction flask equipped with a mechanical stirrer, addition funnel,
Dean-Stark nozzle with a reflux condenser (to trap the resulting water) and a thermometer.
Before heating, a portion of DCPD (0.05 mol) was added to the reaction mixture. After the
water began to collect dropwise in the Dean-Stark nozzle, the remaining portion of DCPD
was added over 1.5 hours. After the addition of DCPD was completed, the reaction mixture
was heated for 4 hours. After cooling, the mixture was washed with water, hexane, dried
over MgSO4, and distilled under vacuum. Then the physicochemical properties of the ob-
tained di-n-cyclohexylcyclopentadiene were determined.
The resulting dicyclohexyl-cyclopentadiene had the following physical and chemical pa-
rameters: density - 0.9470 g/cm3; boiling point - 130-1320C (15 mm Hg); refractive index -
1.4720. The product yield was 56%. On Figure 1 shows the IR spectrum of the synthe-
sized dicyclohexyl-cyclopentadiene.
Results and discussions. The reaction of alkylation of cyclopentadiene with cyclohexyl
alcohol in the presence of an alkaline catalyst proceeds according to the scheme:

R
+ 2 ROH
2 H 2O
R,

where R = cyclohexyl.

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Figure. IR-spectrum of dicyclohexyl-cyclopentadiene

In all likelihood, the alkylation reaction of CPD with cyclohexyl alcohol in the presence of a
basic catalyst (KOH) proceeds according to a mechanism that includes successive stages:
Stage I: the dicyclopentadiene molecule undergoes decomposition with the formation of
two cyclopentadiene molecules:
С10Н12 → 2С5Н6
Stage II: the presence of delocalization in the CPD molecule activates the mobility of hy-
drogen atoms and the hydroxyl anion abstracts a proton from the catalyst molecule to form
a very stable cyclopentadienyl anion, which is a pseudo-aromatic system:
KOH → K+ + OH–
OH + H–C5H5 → HOH + C5H5–
–

Stage III: the alcohol molecule reacts with the resulting carbanion to form an intermediate
complex:
С5Н5– + R+OH– → (С5Н5–R)+OH–
Stage IV: finally, the resulting complex cleaves off the hydroxyl anion to form an alkylcy-
clopentadiene:
(С5Н5–R)+OH– → С5Н5–R + OH–
The resulting hydroxyl anion interacts with the potassium cation and forms a molecule of
the initial KOH catalyst. The substitution of the second hydrogen atom in the CPD mole-
cule occurs according to a similar scheme with the formation of di-n-cycloalkyl-cyclopen-
tadiene. This process, depending on the molar ratio of cyclopentadiene: alcohol, can pro-
ceed sequentially up to the formation of polyalkylcyclopentadienes; therefore, the deter-
mining factor, obviously, is the molar ratio of the initial reagents. Thus, potassium hydrox-
ide in this reaction performs not only the function of a medium, but also a catalytic function,
providing proton abstraction and the formation of a carbanion.

Conclusion: Thus, it can be concluded that the alkylation of cyclopentadiene with alicyclic
alcohols occurs by the mechanism of electrophilic substitution, as in the case of aromatic
hydrocarbons. The main step of this reaction is the formation of a pseudoaromatic system,
the cyclopentadienyl anion. Such systems, along with aromatic systems of the benzoid

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type, have a number of special properties:

- tendency to reactions of substitution, but not addition
- gain in energy, in comparison with the system of non-conjugated double bonds. (reso-
nance energy) the gain is so great that the molecule undergoes significant transformations
to achieve an aromatic state;
- the presence of a ring magnetic current, which ensures the shift of the chemical shifts of
protons associated with the aromatic ring into a weak field (7–8 ppm for the benzene ring),
and protons located above / below the plane of the aromatic system – Into a strong field;
- the presence of the plane itself (minimally distorted), in which all the atoms that form the
aromatic system lie;
- the Huckel rule is almost always observed: only a system containing (in the ring) 4n + 2
electrons (where n = 0, 1, 2, ...) can be aromatic. A system containing 4n electrons is anti-
aromatic (in a simplified sense, this means an excess of energy in a molecule, inequality of
bond lengths, low stability – a tendency to addition reactions).
It is the formation of the pseudoaromatic cyclopentadienyl anion that is responsible for the
further course of the reaction, in which the electrophilic particle (R+) to any of the equiva-
lent carbon atoms of the cyclopentadienyl anion molecule, and the subsequent elimination
of the hydroxyl ainone occurs with the formation of a water molecule.

REFERENCES

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XÜLASƏ
F.S. Qurbanova
Tsiklopentadienin tsikloheksil spirti ilə alkilləşmə reaksiyasının mexanizmi

Kalium hidroksid sulu məhlulundan və nanoölçülü maqnezium oksidindən ibarət olan kata-
litik sistemin iştirakı ilə tsiklopentadienin tsikloheksil spirti ilə alkilləşməsi reaksiyası aparıl-
mışdır. Sintez edilmiş ditsikloheksiltsiklopentadienin çıxımı və fiziki-kimyəvi parametrləri
müəyyən edilmişdir. Alınmış birləşmənin quruluşu İQ-spektroskopiyası ilə təsdiq edilmişdir.
Bu reaksiyanın ehtimal mexanizminin şərhi verilmişdir. Göstərilmişdir ki, tədqiq olunan
reaksiya aralıq psevdoaromatik birləşmənin, tsiklopentadienil anionunun əmələ gəlməsi,
ardınca elektrofilik hissəciyin (alkil radikalının) əlavə edilməsi və su molekulunun aradan
qaldırılması ilə gedir.
Açar sözlər: tsiklopentadien, tsiklik spirtlərlə alkilləşməsi, psevdoaromatik sistem, nanoöl-
çülü katalizator.

РЕЗЮМЕ
Ф.С. Гурбанова
Механизм реакции алкилирования циклопентадиена
циклогексиловым спиртом

Проведена реакция алкилирования циклопентадиена циклогексиловым спиртом в

присутствии каталитической системы, состоящей из водного раствора гидроксида
калия и наноразмерного оксида магния. Определены выход и физико-химические па-
раметры синтезированного дициклогексилциклопентадиена. Строение полученного
соединения подтверждено данными ИК-спектроскопии. Дается интерпретация веро-
ятного механизма этой реакции. Показано, что исследуемая реакция протекает с об-
разованием промежуточного псевдоароматического соединения – циклопентадие-
нильного аниона с последующим присоединением электрофильной частицы (алкиль-
ного радикала) и отщеплением молекулы воды.
Ключевые слова: циклопентадиен, алкилирование циклическими спиртами, псев-
доароматическая система, наноразмерный катализатор.

Publishing history
Article received: 05.04.2022
Article accepted: 25.08.2022

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CHEMİSTRY AND CHEMİCAL TECHNOLOGY UDC 615.634

Pp.30-38

PLANT GROWTH STIMULANTS BASED ON ORGANIC ACIDS

R.A. Asadova
Institute of Petrochemical Processes of the National Academy of Sciences of Azerbaijan
e-mail: [email protected]

ABSTRACT

The prospects for the use of plant growth stimulants and fertilizers for agricultural products
has been presented. The stimulating effect of complex compounds and salts of organic
acids on the growth of tomato seeds has been established. The synthesis of the com-
pounds was carried out at the Institute of Petrochemical Processes of NASA, and the ex-
periments were carried out at the Scientific Research Institute of Vegetable Growing. The
Institute of Petrochemical Processes of NASA used a fraction of natural petroleum acid
(NPA), boiling in the range of 80-1800C (3.99 MPa) and acids formed during the hydrolysis
of sunflower oil. Complexes of petroleum acid with triethanolamine and isobutylamine, as
well as sodium salts of PNA and sunflower oil acids were synthesized. The physicochemi-
cal properties of the synthesized salts and complex compounds have been studied. Thus,
seeds moistened in a solution of a triethanolamine complex with PNA give 100% germina-
tion. It is shown that 0.0001% solutions of triethanolamine complex with PNA, taken as a
control variant (ordinary irrigation water), compared to other solutions, have a greater ef-
fect on the growth of green biomass of tomato seedlings, as well as on yield.
Keywords: natural petroleum acids, triethanolamine, isobutylamine, sunflower oil, growth
substance, stimulants, yield

Introduction. Due to population growth and climate change, the yield of vegetable plants
is decreasing, which requires more and more attention to this area [1-4]. One of the prom-
ising methods for increasing plant resistance to environmental influences is the use of
plant growth substances - stimulants. Plant growth regulators are organic compounds
added in small amounts that affect the growth and development of plants [5,6]. In many
countries, 50-80% of agricultural plants are cultivated with the help of growth regulators
[7,8]. Stimulants, affecting the root and stem systems of plants, strengthen their resistance
to various climate changes and increase productivity [9–11]. Stimulants at low concentra-
tions regulate a number of metabolic processes, increase plant resistance to various nega-
tive environmental effects (drought, high or low humidity, radiation, herbicides and fungi-
cides). Stimulants, penetrating the endospermines of plant seeds, stimulate the synthesis
of hydrolytic enzymes. They also increase the rapid growth of plant sprouts, development,
ripening of fruits, and also cause increased yields.
One of the most important tasks is to create a base of growth substances in the republic.
In this regard, at the Institute of Petrochemical Processes of ANAS named after academi-
cian Yu.H. Mammadaliyev, systematic studies were carried out in a number of areas and
certain results were obtained.
For the first time, the synthesis of water-soluble salts of PNA has been carried out, and
these substances have been tested as stimulants for the partial growth of plant seeds.
Thus, it is known about the positive effect of oil on plant growth, and this property also ap-
plies to petroleum acids [12]. The richness of Azerbaijani oils in the content of these acids
makes it possible to synthesize stimulants based on local raw materials.

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Laboratory and field tests of sodium, potassium and ammonium salts obtained on the ba-
sis of the first fraction of PNA revealed their stimulating ability for plants and the first re-
sults obtained show broad prospects for their use in agriculture [9-14].
With the aim of an easy approach to raw materials in the direction of obtaining stimulants
of petroleum origin, a synthesis of a number of water-soluble compounds based on PNA
was carried out and tested as plant stimulants. It has been established that when plant
seeds are soaked in 0.001-0.0001% solutions of these substances for a certain time, the
germination of the planted control preparation occurs faster and the percentage of germi-
nation is much higher. The root system of plants increases by 70-80%, which leads to the
growth of plants planted on the site and an increase in yield. Studies conducted with the
addition of organic salt solutions to tomato, corn, and pea seeds have shown that synthe-
sized compounds are effective growth substances [15].
It should be noted that during planting, wetting seeds and seedlings with these compounds
has a positive effect, but during the growing season, the repeated addition of these sub-
stances has a negative effect on plant growth. Therefore, during the period of plant devel-
opment, the repeated addition of these substances is impractical.
In continuation of the research, the effect of water-soluble salts and complex compounds
of PNA, as well as salts synthesized on the basis of vegetable oil acids on tomato seeds,
included in the gene pool of the Research Institute of Vegetable Growing, was studied.

Objective: The main purpose of the study is the creation of growth stimulants. For this
purpose, the effect of synthesized substances on the number of germinated tomato seeds,
their growth and yield was studied.

Methods: The Institute of Petrochemical Processes of NASA carried out the synthesis of
water-soluble salts and complex compounds of petroleum acid obtained on the basis of
petroleum acid completely purified from phenol and free hydrocarbons, as well as salts
synthesized on the basis of a mixture of acids isolated as a result of hydrolysis of acids
vegetable oils and studied their effect on tomato seeds. To this end, the following work
was carried out:
1. Obtaining a fraction of PNA, boiling up in the range of 80-1800C (3.99 10-4MPa) and
sunflower oil hydrolysis acids.
2. Study of the physicochemical parameters of the obtained acids.
3. Synthesis of the sodium salt of PNA with an acid value of 270 mg KOH/g.
4. Synthesis of PNA complexes with an acid number of 270 mg KOH/g with triethanola-
mine (TEA) and isobutylamine (İBA).
5. Synthesis of sodium salt of a mixture of acids obtained by hydrolysis of vegetable oil.
6. Study of physical and chemical parameters of synthesized salts and complex com-
pounds.
7. Preparation of 0.001-0.0001% solutions of synthesized salts and complex compounds.
8. Research of the obtained solutions as plant growth stimulators.
For the synthesis of salt and complex compounds of PNA, a calculated amount of petrole-
um acid is added to a three-necked flask equipped with a stirrer and a heater, and at a
temperature of 40-50, an appropriate amount of a 20% solution is added to the acid, TEA
or İBA is added, stirred for 20-30 minutes. Synthesis of sodium salts of a mixture of acids
obtained by the hydrolysis of vegetable oils (GYT) are obtained by a similar method.
The reaction proceeds according to the following scheme:
O O
R-C + NaOH 40-50oC
R-C + H 2O
OH
ONa

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R= C17H35; C17H33; C17H31; C17H29; C17H27; C15H31; C13H27

-
O +
+
R-C + N(CH 2-CH2-OH)3 R-COO - HN-(CH2-CH 2OH)3
OH
+
O
R-C + -
R-COO H 3N-CH2-CH-CH3
H 2N-CH2-CH-CH3
OH
CH 3
CH3
R – the first fraction of PNA (boiling range 80-180[C /3.99 MPa)
The physicochemical parameters of the synthesized salts and complex compounds of or-
ganic acids have been studied, and their structure has been confirmed by spectral meth-
ods.
Physicochemical parameters of PNA with an acid number of 270 mg KOH/g are presented
in Table. 1

Table 1. Physical and chemical parameters of PNA with a.n. 270 mg KOH/g

Density at 20 ̊C,
Compound Boiling interval, 0С Refractive index, n20D
кg/m3

PNA with a. n. 270 80-180/3,99 10-4MPa 951.5 1,4672

Physicochemical parameters of 0.001-0.0001% solutions of salts and PNA complexes are

shown in Table 2.

Table 2. Physicochemical parameters of solutions of PNA compounds

Examples Concentration, Density, Refractive pH Pour point,

% g/sm3, 20oC index, ηD20 o
C
Complex PNA with TEA 0,0001 0.9983 1.0031 7.5 -6
Complex PNA with İBA 0,0001 0.9981 1.3331 7.1 -8
Na salt of PNA 0,0001 0.9990 1.3335 7.3 -4
Complex PNA with TEA 0,001 0.9981 1.0031 7.5 -8
Complex PNA with İBA 0,001 0.9991 1.3330 7.1 -10
Na salt of PNA 0,001 0.9969 1.3333 7.3 -4

Physicochemical parameters of GYT are presented in Table 3.

Table 3. Physical and chemical parameters of GYT

Density,
Iodine number,
Plant oils Acid number, Average d420, Refractive
100 g J/g
mg КOH/g molecular weight кg/m3 index, ηD20
of compound

Sunflower oil 138 269 107 9010 1.4673

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Physicochemical indicators of 0.001 and 0.0001% solutions of GYT sodium salts are
shown in Table 4.

Table 4. Physical and chemical parameters of 0.001 and 0.0001% solutions of GYT sodium salts

Plant oils Concentration, Density, Refractive pH Pour point,

% g/sm3 20oC index , ηD20 o
C

0,0001 0.9987 1.3330 7.0 -6

Sunflower oil
0,001 0.9983 1.3331 7.0 -6

The electrical conductivity properties of the used 0.001 and 0.0001% solutions were stud-
ied and the results obtained are presented in Table 5.

Table 5. Electrical conductivity properties of the used 0.001 and 0.0001% solutions
Concentration,
Compounds R, Om ρ, Om·m χ, S/sm
%
Complex of PNA with a.n.
0,0001 3.3·103 6.6·102 1.51·10-5
270 with TEA
Complex of PNA with a.n.
0,0001 3.0·103 6.0102 1.66·10-3
270 with IBA
Na salt of PNA with a.n. 270 0,0001 1.56·104 7.8·104 1.28·10-5
Na salt of GYT 0,0001 3.3·103 6.6·102 1.51·10-5
Complex of PNA with a.n.
0,001 4.0·103 8.0·102 1.25·10-5
270 with TEA
Complex of PNA with a.n.
0,001 3.6·103 7.2·102 1.38·10-3
270 with IBA
Na salt of PNA with a.n. 270
0,001 1.4·105 2.8·104 3.6·10-7
Na salt of GYT 0,001 3.9·103 7.8·102 1.28·10-5
Distillate water - 5.8·103 1.2·103 8.3·10-6

The structure of the synthesized complexes and salts was confirmed by IR spectroscopy;
the spectra were taken on an ALPHA IR - Furye apparatus of the German company
BRUKER.

Figure 1. IR spectrum of GYT sodium salt Figure 2. IR spectrum of the sodium salt of PNA

In the IR spectrum of the sodium salt of GYT, the following absorption bands are found
(Figure 1): mathematical vibrations of the C-H bond of the CH2 group (718 cm-1); bending

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vibrations of the С-Н bond of the HC=CH group (921 cm-1); C-O bond (1095 cm-1); bend-
ing vibrations of the С-Н bond in the CH3, CH2 and CH groups (1312, 1405, 1440, 1458
cm-1); stretching vibrations of the С-Н bond of the CH3, CH2 and CH groups (2852, 2922,
2954 cm-1); stretching vibrations of the С-О bond of the COO- group (1641, 1546 cm-1);
stretching vibrations of the С-Н bond in the -HC=CH- group (3010 cm-1); stretching vibra-
tions of the OH group (3363cm-1).
Analysis of the IR spectra of GYT and sodium salts obtained on its basis that the ab-
sorption bands of stretching and deformation vibrations characteristic of acidic functional
groups (COOH, C=O 938.1708 cm-1) practically disappear in the region corresponding to
the C-O bond of the salt COO- (1641.1546 cm-1) new absorption bands are formed, which
is explained by the replacement of the hydrogen atom of the carboxyl group by the sodium
atom as a result of the formation of the salt.
The IR spectra of PNA, its sodium salt, the complex of PNA with İBA, and the complex
of PNA with TEA were also taken and their structure was studied (Figure 2).
In the IR spectrum of PNA, absorption bands are observed: stretching vibrations of the
carbonyl group C=O (1702 cm-1); stretching vibrations of the carboxyl group COOH (2668
cm-1), bending vibrations of the acid hydroxyl group OH (935 cm-1).
In the IR spectrum of the sodium salt of the first fraction of PNA, the following absorption
bands are observed: 932 cm-1 – C-H bond of the naphthenic ring; 1110 cm-1 C-O bond;
1317, 1406, 1454 cm-1 – bending vibrations of the С-Н bond of CH2, CH3 groups;
1550.1669 cm-1 – bond C-O group; 2856, 2922, 1951 cm-1 stretching vibrations of the
CH3,CH2 and CH groups С-Н bond. It is clearly seen from the spectra, that the absorption
bands of stretching and bending vibrations characteristic of acid functional groups almost
completely disappear and an absorption band of the sodium salt of the acid is formed. This
is due to the complete replacement of the hydrogen atom of the carboxyl group by the so-
dium atom as a result of the formation of the salt.
The following absorption bands are observed in the IR spectrum of the PNA complex
with İBA (Figure 3): 657, 700, 803, 875, 925 cm-1 – C-H bond; 1023, 1091,1167,1192,1218
cm-1 - C-O bond; 1311,1394,1461, 2869, 2922, 2952 cm-1 - bending and stretching vibra-
tions of the С-Н bond of CH3, CH2 and CH groups; 1535.1627 cm-1 - stretching vibrations
of the С-О bond of the COO group; 2597, 2687 cm-1 - ammonium band; 1535, 1627 cm-1 -
COO- group, and the absence of ammonium bands in the region of 2597, 2687 cm-1 indi-
cates the formation of an ammonium salt. Analysis of the spectra of PNA and the synthe-
sized complex of PNA with İBA shows that in the spectrum of PNA, the absorption bands
characteristic of acid in the region of 1702, 935 cm-1 disappear, and new absorption bands
appear in the regions of 2597, 2687, 1535, 1627 cm-1. This shows the formation of an
ammonium complex.

Figure 3. IR spectrum of PNA with İBA Figure 4. IR spectrum of the PNA complex with -TEA

The following absorption bands are observed in the IR spectrum of the PNA complex with
TEA (Figure 4): 729 cm-1 – pendulum vibrations of the C–H bond of the CH2 group; 909
cm-1 acid group - COOH; 1035, 1069, 1097 cm-1 - stretching vibrations of the С-О bond of
the COH group; 1710 cm-1 C=O bond from acid; 1559 cm-1 band characteristic of the car-
boxylate ion (-COO-); 1211, 1280 cm-1 stretching vibrations of the tertiary amine C-N bond;
1398, 1450, 2867, 2923, 2950 cm-1 – bending and stretching vibrations of the С-Н bond of

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CH3, CH2 and CH groups.

The absorption bands characteristic of acidic groups disappear, and bands characteristic
of the complex salt are formed.
Experiment. In order to study the biological activity of prepared 0.001 and 0.0001% solu-
tions, tomato seeds were kept at room temperature (20-220C) for 24 hours. Tests were
carried out on tomato seeds in Petri dishes and 50 seeds were placed in each dish . In the
first Petri dish with 10 ml of prepared solutions and another Petri dish taken as a control
experiment, 10 ml of irrigation water was added to the seeds. After the seeds were kept in
the solution for 24 hours, they were released from the solution. To observe subsequent
growth, the seeds were transferred to a new Petri dish. In the following days, only irrigation
water was added to the seeds.

Table 6. Germination percentage of seeds soaked in 0.001% solution and irrigation water

Compound Number Number of germinated tomato seeds

of seeds 2-nd 3-d 4 -th 5-th 6-th % germi-
day day day day day nation
Complex of PNA with ТЕА 50 7 3 36 42 43
Complex of PNA with ТЕА 50 10 33 38 40 40 83
Complex of PNA with IBA 50 12 27 35 39 42
Complex of PNA with IBA 50 6 35 39 40 42 84
Na salt of PNA 50 5 20 39 40 42 83
Na salt of PNA 50 6 31 39 41 41
Na salt of GYT 50 13 32 39 40 37 78
Na salt of GYT 50 16 37 41 41 41
NEZ 50 23 33 37 37 37
NEZ 50 13 36 37 37 39 76

From the results of Table 6 it can be seen that at a concentration of 0.001% in the complex
of PNA with TEA, 83% of seeds germinate, in the complex of PNA with İBA 84%, in the
sodium salt of PNA 83%, in the sodium salt of GYT 78%, and in irrigation water 76%. The
percentage of seed germination when wetting with solutions with a concentration of
0.001% is higher compared to the control experiment.
From the results of Table 7 shows that at a concentration of 0.0001%, 89% of seeds ger-
minate in the PNA complex with TEA, 86% in the PNA complex with İBA, 86% in the PNA
sodium salt, 88% in the GYT sodium salt, and 76% in the irrigation water.

Table 7. Germination percentage of seeds soaked in 0.0001% solution and irrigation water

Compound Number Number of germinated tomato seeds

of seeds 2-nd 3-d 4 -th 5-th 6-th % germi-
day day day day day nation
Complex of PNA with ТЕА 50 19 41 43 44 44 89
Complex of PNA with ТЕА 50 15 36 37 39 45
Complex of PNA with IBA 50 12 22 35 42 42 86
Complex of PNA with IBA 50 9 36 41 41 44
Na salt of PNA 50 16 37 38 43 44 86
Na salt of PNA 50 9 32 40 40 42
Na salt of GYT 50 13 32 39 40 37 78
Na salt of GYT 50 16 37 41 41 41
NEZ 50 23 33 37 37 37 76
NEZ 50 13 36 37 37 39
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As can be seen, when seeds are wetted in a solution with a concentration of 0.0001%, the
percentage of germination is higher than in the control variant.
germination, %-
90

85

80

75

70

65
PNA - TEA GYT - Na PNA - IBA PNA - Na Control

Figure 5. Germination percentage of seeds soaked in 0.0001% solution and in irrigation water

germination, %
86

84

82

80

78

76

74

72
PNA - TEA GYT - Na PNA - IBA PNA - Na Control

Figure 6. Germination percentage of seeds soaked in 0.001% solution and in irrigation water

It follows from the diagrams that the best results are observed in a 0.0001% solution.

Conclusion: 0.001 and 0.0001% solutions of salts and complex compounds synthesized
at the Institute of Petrochemical Processes of NASA were studied on tomato seeds at the
Research Institute of Vegetable Growing. From the studies carried out, it was found:
1. Seeds soaked in 0.0001% PNA-TEA complex showed 100% germination.
2. Under the influence of a 0.0001% solution of the PNA complex with TEA, faster growth
and development of seedlings was observed, resistance to diseases, stress factors
(drought, etc.) increased.
3. A 0.0001% solution of the PNA complex with TEA, compared with other solutions and
the control variant (ordinary irrigation water), had a greater effect on the growth of green
biomass of tomato seedlings.

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lı Z.İ. Təbii neft turşularının bəzi duzlarının noxud bitkisinin inkişafına stimullaşdırıcı kimi
təsirinin tədqiqi. / Ümummilli lider Heydər Əliyevin anadan olmasının 92-ci ildönümünə
həsr olunmuş“ Müasir biologiya və kimyanın aktual problemləri elmi-praktik konfrans” ın
materialları, 05-06 may. – 2015. – S.347-351.
15. Asadova R.A., Abbasov V.M., Allahverdiyev E.I., Gurbanova G.G. Study of the effect
of synthesized compounds on the bases of organic acids on plant seeds. // PPOR. – 2020.
– Vol. 21, № 1. – Pp.155-167.

XÜLASƏ
R.A. Əsədova
Üzvi turşular əsasında bitkilərin böyüməsinin stimulantları

Kənd təsərrüfatı məhsulları üçün bitki böyüməsi stimulyatorlarının və gübrələrin istifadəsi

perspektivləri təqdim olunur. Üzvi turşuların kompleks birləşmələri və duzlarının pomidor

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toxumlarının böyüməsinə stimullaşdırıcı təsiri müəyyən edilmişdir. Birləşmələrin sintezi

AMEA-nın Neft-Kimya Prosesləri İnstitutunda, təcrübələr isə Tərəvəzçilik Elmi Tədqiqat İn-
stitutunda aparılıb. AMEA-nın Neft-Kimya Prosesləri İnstitutu 80-1800C (3,99 MPa) aralı-
ğında qaynayan təbii neft turşusunun (TNT) bir hissəsindən və günəbaxan yağının hidrolizi
zamanı əmələ gələn turşulardan istifadə etmişdir. Neft turşusunun trietanolamin və izobuti-
lamin ilə kompleksləri, həmçinin TNT-nın natrium duzları və günəbaxan yağı turşuları sin-
tez edilmişdir. Sintez edilmiş duzların və kompleks birləşmələrin fiziki-kimyəvi xassələri -
tədqiq edilmişdir. Beləliklə, trietanolamin kompleksinin TNT ilə məhlulunda nəmləndirilmiş
toxumlar 100% cücərmə verir. Göstərilmişdir ki, nəzarət variantı (adi suvarma suyu) kimi
qəbul edilən TNT ilə trietanolamin kompleksinin 0,0001% məhlulları digər məhlullarla mü-
qayisədə pomidor şitilinin yaşıl biokütləsinin böyüməsinə, həmçinin məhsuldarlığa daha
çox təsir göstərir.
Açar sözlər: təbii neft turşuları, trietanolamin, izobutilamin, günəbaxan yağı, böyümə mad-
dəsi, stimulantlar, məhsuldarlıq

РЕЗЮМЕ
Р.А. Асадова
Стимуляторы роста растений на основе органических кислот

Представлены перспективы использования стимуляторов роста растений и удобре-

ний для сельскохозяйственной продукции. Установлено стимулирующее действие
комплексных соединений и солей органических кислот на рост семян томата. Синтез
соединений проводился в Институте нефтехимических процессов НАНА, а экспери-
менты проводились в НИИ овощеводства. В Институте нефтехимических процессов
НАНА использовали фракцию природной нефтяной кислоты (НПК), кипящую в ин-
тервале 80-180°С (3,99 МПа), и кислоты, образующиеся при гидролизе подсолнечно-
го масла. Синтезированы комплексы нефтяной кислоты с триэтаноламином и изобу-
тиламином, а также натриевые соли ПНК и кислот подсолнечного масла. Изучены
физико-химические свойства синтезированных солей и комплексных соединений.
Так, семена, увлажненные в растворе комплекса триэтаноламина с ПНК, дают 100%
всхожесть. Показано, что 0,0001% растворы триэтаноламинового комплекса с ПНК,
взятые в качестве контрольного варианта (обычная поливная вода), по сравнению с
другими растворами оказывают большее влияние на рост зеленой биомассы про-
ростков томата, а также на урожайность.
Ключевые слова: природные нефтяные кислоты, триэтаноламин, изобутиламин,
подсолнечное масло, ростовые вещества, стимуляторы, урожайность.

Publishing history
Article received: 30.03.2022
Article accepted: 25.08.2022

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CHEMİSTRY AND CHEMİCAL TECHNOLOGY UDC 54061 + 543.4

Pp.39-46

APPLICATION OF THE DYNAMIC LIGHT SCATTERING

METHOD IN NANOTECHNOLOGY
A.A. Aliyeva
Institute of Petrochemical Processes of the National Academy of Sciences of Azerbaijan
E-mail: [email protected]

ABSTRACT

Nanoparticles provide important functionality across a wide range of materials, applica-

tions and sectors. Dynamic light scattering (DLS) analysis makes it possible to reliably
measure particle size distribution profiles in the submicron range. This method is especial-
ly useful for studying the behavior of nanoparticles in suspensions. Combined with zeta
potential information, the DLS data over time provide insight into the tendency of nanopar-
ticles to agglomerate. Like solid particles, DLS is invaluable for registration how surfactant
molecules combine into micellar structures. This arrangement varies depending on the
concentration of the surfactant and the concentration of simple electrolyte ions. The size of
biological nanoparticles can help elucidate the mechanisms of major molecular pathways
in complex diseases. The use of the DLS method, which measures the hydrodynamic size
of nanoparticles in suspension, is noted to characterize specific examples of engineered
and natural nanoparticles. In the presented work, the analysis of the results of scientific
research in the field of application of the method of dynamic light scattering in nanotech-
nology, in particular, to determine the size of nanoparticles, is carried out.
Keywords: dynamic light scattering method, nanotechnology, nanoparticles, zeta poten-
tial, particle distribution, polydispersity and particle size

Introduction: Nanoparticles are playing an increasingly important role in a number of in-

dustrial and commercial products, as well as in the study of molecular and particle aggre-
gation phenomena. Advanced nanotechnology could enable the precise location of can-
cerous tumors and prevent unwanted microbial growth and contamination of medical de-
vices and consumer products such as textiles. But the analysis of nanoparticles can still be
a very challenging task. While the physical properties of bulk materials remain constant
regardless of their size, the size of nanoparticles often determines their physical and che-
mical properties. Therefore, it is critical to be able to characterize nanoparticles in order to
successfully commercialize and understand their potential environmental, health and safe-
ty risks. One of the major problems faced in the development of nanoparticles is their sen-
sitivity to small differences between superficially similar particles. Minor changes in the en-
vironment can cause particles to aggregate, change in size, and react with the environ-
ment to oxidize or absorb contaminants. Understanding the time dependence of the prop-
erties of nanoparticles is vital for storage, environmental and health impacts, as well as
production and product stability. In addition, the rules governing the use of engineered na-
noparticles have not yet fully defined.
Methods for the analysis of nanoparticles have been available since the 1980s. Dynamic
Light Scattering offers one of the most versatile characterization toolkits. The three most
common types of analytical light scattering include: multi-angle (MALS), dynamic (DLS)
and electrophoretic (ELS), which can be used to characterize various properties of nano-

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particles contained in liquids. This work shows the application of dynamic light scattering
(DLS) methods in nanotechnology, in particular, to determine the size of nanoparticles.

Objective: It was shown in [1] that in recent years nanoparticles have been increasingly
used in biomedicine as vehicles for the delivery of drug components and also as biosen-
sors. A wide range of nanoparticle sizes from 10 nm to 1 μm, as well as their optical prop-
erties, make it possible to use the latter in spectroscopic methods of analysis. For their
more efficient use, it is necessary to take into account the particle size, charge distribution
on the surface of the particles, as well as derivatization characteristics. These properties
must be optimized taking into account the expected biodistribution of nanoparticles and
their target. In this review, the authors consider methods which are based on the phenom-
enon of light scattering - dynamic light scattering and zeta-potential, which are used to
characterize nanoparticles. DLS is using for determination of nanoparticle size, as well as
to evaluate the influence of time, temperature, pH and other factors on their stability. The
zeta potential allows to determine the surface charge of nanoparticles and gives an idea of
their stability and surface interaction with other molecules. Also in this work, attention was
focused on the characterization of nanoparticles and their application in infectious, onco-
logical and cardiovascular diseases.
The authors of [2] provided a complete overview of the use of the DLS method to determi-
nation of the type of distribution of nanoparticles by their size and stability of magnetic col-
loidal nanoparticles. A calculated analysis is presented related to receiving of data about
the dimensions from the correlation function and measuring the average data of Z-
potential. It has been shown that the process of self-assembly of magnetic nanoparticles
with an anisotropic structure can also be efficiently controlled using DLS.

Methods: The DLS method is applied to the dusty component of a complex (dusty) plas-
ma, revealing the autocorrelation function of the Gaussian intensity for scattering angles
from 4° to 175° [3]. The Gaussian decay form represents the free (ballistic) motion of a
particle and allows one to determine the one-dimensional square of the particle's velocity.
It is shown that at scattering angles less than 1°, the intensity autocorrelation function is a
combination of Gaussian and exponential functions. This makes it possible to simultane-
ously determine the particle velocity and diffusion constants. The dust system is complete-
ly described by two components of movement in the horizontal and vertical directions.
These two components are measured simultaneously on two scattering paths using only
one incident laser beam. Unlike standard imaging methods, the DLS method can be ap-
plied even to a disordered phase state, when dust particles have very high kinetic ener-
gies. In an ordered phase state, the assumptions of the DLS approach were tested using
the method of independent charge-coupled devices at the fundamental kinetic level.
An important criterion is the toxicity of nanoparticles, since this indicator is a priority. It is
important to have an idea about the sizes of nanoparticles, their size distribution, morpho-
logical composition of particles, surface area and its chemical composition, as well as the
reactivity of particles in [4], a wide range of nanomaterials was considered, and their char-
acterization by DLS and transmission electron microscopy was also given. Metals, their
oxides, as well as carbon-containing materials in an aqueous medium and other media for
culturing cells, both containing and not containing serum, were used as analyzed sub-
stances to determine the toxic effects in solutions. The influence of the surface on the
characteristics of the material is also shown. In the course of toxicological studies, the
change in the agglomeration of nanoparticles and the zeta potential over time was ana-
lyzed. The authors found that many metals, as well as nanosized metal oxides, are capa-
ble of agglomeration, as well as mixing or size reduction. Relevant toxicity data have

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shown that the addition of serum to cell cultures has an effect on particle toxicity in some
cases. This method also has been discovered that ultrasonic waves do not have such a
significant effect on the reduction of agglomeration and the surface charge of the nanopar-
ticle.
DLS method is applicated to define the size, shape, and diffusion coefficient of rod-like na-
noparticles [5]. The intensity of the autocorrelation functions of the light scattered by the
particles in the solution was measured and analyzed to obtain the relaxation rate for de-
caying intensity correlations. These decay rates are related to the diffusion coefficient con-
cerned to the motion of the particle. In the case of nanorods, there are two types of motion
- translational and rotational. By unraveling the relaxation rates corresponding to these two
types of motion, the shape and size of the nanoparticles were characterized. These exper-
iments demonstrate the value of the DLS method as an inexpensive and convenient meth-
od for characterizing nanoparticles of regular shape in a liquid medium, as well as the abil-
ity of DLS to determine the shapes of nanoparticles.
It is noted in [6] that the DLS method is an analytical tool commonly used to measure the
nanoparticles hydrodynamic size and colloids in a liquid medium. The nanoparticles of
gold are unusual light scatters at the plasma surface near resonance length wave. Authors
of this article showed that DRS can be used as a very effective method for bioconjugation
of nanoparticles of gold and biomolecular binding studies. The process of conjugation of
protein A and nanoparticles of gold under different experimental condition, such as the
quality and stability of the prepared conjugates, were exployed and systematically investi-
gated using DLS. At first, it has been shown that DLS can be used as directly and effective
method for the binding of blocks between proteins in solution.
It was shown [7] that the DLS method measures the scattering intensity arising from the
random Brownian motion of particles as a function of the fluctuation time. Information
about the diffusion coefficient and particle size can be obtained from the analysis of these
fluctuations. This article discusses the factors that affect the lower limit of DRS size and
reports on the use of sucrose as a test sample to test this lower limit of the method. Hy-
drodynamic diameters less than 1 nm are obtained using 173° backscatter detection,
which is used to increase the sensitivity of the DLS. The mean peaks (with standard devia-
tions) obtained for intensity and volume data from a series of sucrose concentrations rang-
ing from 5 to 35 wt % were measured as DI (mean = 0.82 nm (0.11 nm)) and DV (mean =
0.62 nm (0.05 nm)) respectively. These results for sucrose suggest that sub-nanometer
measurements are achievable with an accuracy of 0.1 nm. Evidence supporting these re-
sults for sucrose is discussed.
In [8], several methods based on different physical principles were developed to determine
the size of nanoparticles. As a starting point in the certification of nanoparticle reference
materials, the authors evaluated the differences between the results obtained using the
two most commonly methods for determining the size of nanoparticles: dynamic light scat-
tering (DLS) and centrifugal deposition. The main difference between these methods is
their power to resolve multimodal particle size distributions. Due to the separation process
taking place in a disc centrifuge, centrifugal settling has excellent resolution and is able to
resolve modes with a ratio of diameters of only 1.1, while dynamic light scattering is not
able to resolve modes with a diameter less than 4. However, the DLS method is based on
first principles for which calibration is not required, unlike centrifugal settling cases where
the settling rate needs to be calibrated. This paper presents experimental results illustrat-
ing the advantages and disadvantages associated with each method and shows how the
two methods can complement each other in the certification process.

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In the papers [9-11] it have been showed that DLS method more applicated and is an ef-
fective method for the investigation of nanoparticles, theirs size and morphology in labora-
tory analysis/
A perspective is presented detailing current technologies for the characterization of nano-
particles in liquid suspension [12]. The authors describe in detail the technologies involved
and evaluate their application in determining the size and concentration of nanoparticles.
Parameters that can influence the results are also investigated and a causal analysis of
the main factors affecting the measurement of nanoparticle size and concentration by na-
noparticle tracking analysis and DLS is proposed to identify areas where measurement
uncertainties may occur (Figure).

Figure. Methods of DLS analysis depending on particle size and concentration

Dynamic Light Scattering (DLS), also known as Quasi-Elastic Light Scattering or Photon
Correlation Spectroscopy, is a non-invasive, fast, accurate, reliable, promising technology
that is well established for measuring the size and studying the size distribution of mole-
cules in the submicron region. DRS works on the principle of measuring the Brownian mo-
tion of particles and correlates. Particle size measurements with DLS can be performed
within one or two minutes and the measurements have proven to be accurate, reliable and
provide objective information on the shape (flexible coil, rods, cylinders, spheres) of mac-
romolecules (DNA, RNA, polysaccharides, proteins and viruses) . This technology is also
suitable for determining the molecular weight and size of molecules in the range from 10
µm to less than 1 nm and having a molecular weight of less than 1000. DLS has been
used as a promising technology for studying the homogeneity of RNA, proteins and their
complexes. The main application of this technology is milk and other oil-in-water emul-
sions, since milk contains a large amount of colloidal particles, which have the ability to
scatter light well, and the structure of milk is the least affected due to dilution of milk. Alt-
hough DLS has some limitations, such as variations in results due to changes in tempera-
ture, viscosity, and an inability to distinguish between molecules that are closely related, it
is gaining popularity in academic and industrial laboratories because it gives reliable re-
sults in a short period of time [13-15].
It is noted that DLS and size exclusion chromatography are among the most popular
methods for determining the size of a polymer in solution [16]. Considering dendritic and
networked polysilanes as a group of the least soluble polymeric substances, the authors
critically compare and discuss the difference between the sizes of nanoparticles obtained
by both methods. Polymeric nanoparticles are typically in poor solution conditions below

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the theta point and therefore have a globular conformation. Determination of particle sizes
in the presence of attractive interactions is a non-trivial task. The only way to measure the
true size of polymer nanoparticle molecules in this dissolution regime without aggregation
is to conduct an experiment with a dilute solution of globules (below the theta point and
above the miscibility line). Based on the results of our polysilane measurements, the au-
thors concluded that DLS provides more reliable results than exclusive chromatography for
dilute globule solutions. The general implications for measuring the size of polymer nano-
particles in solution are also discussed.
It has been shown that the method of electrochemical particle impact (or “nanoimpact”)
supplements light scattering methods for determining the sizes of both mono- and polydis-
perse nanoparticles [17]. It was found that established methods - DLS and nanoparticle
tracking analysis - allow accurate measurement of the diameter of 30 nm silver particles
that take a spherical shape, but do not accurately determine the size of a sample of a
smaller size of 20 nm. On the contrary, nanoimpacts are highly accurate (error < 5% in ef-
fective diameters) and make it possible to determine the size of both individual silver NPs
"20 nm" and "30 nm" in terms of the number of constituent atoms. Further examination of
the "20 nm” and “30 nm" bimodal sample shows that the electrochemical method resolves
well two very similar sizes, showing the exact size regardless of particle size polydisper-
sity, whereas, due to limitations inherent in light scattering measurements, this is not pos-
sible for DLS and the nanoparticle tracking method.
The presence of plastic particles is a constant environmental problem. Plastics break down
into microplastics (MP) and nanoplastics (NPls) when they are exposed to the environment
and aging. While there is no standard definition for NPls, they are typically 1000 nm in
size. The range of 100-1000 nm is not taken into account and is beyond the detection ca-
pabilities of methods commonly applied to MP. The adaptation of various methods such as
micro-FTIR and micro-Raman spectroscopy to NPls requires more advanced separation
techniques. In addition, other methods such as dynamic light scattering (DLS), nanoparti-
cle tracking analysis (NTA), and transmission electron microscopy (TEM) can measure
NPls, but cannot distinguish them from other nanomaterials present in environmental
samples. The adaptation of these methods is of great importance for the scientific commu-
nity in search of suitable methods for assessing the impact of plastic particles on the envi-
ronment on a global scale [18].
The application of the DLS method for determining the size of non-spherical nanoparticles
using copolarized and cross-polarized scattered light components is limited due to meas-
urement difficulties and problems with inverting scattering data into a direct prediction of
nanoparticle size parameters. In [19], the authors propose a new method, called multipo-
larization DLS, based on time-resolved scattered light intensity measurements at different
angles between the incident and scattered polarized light. A physical model that gives a
relationship between the coefficients of translational and rotational diffusion of particles
and the autocorrelation function of intensity for an arbitrary angle between the incident and
scattered polarizations. An application to Au and Fe2O3 nanorods is described, in particular
for monitoring the size change caused by selective etching. Compared to the depolarized
DLS, the method avoids the measurement of very weak cross-polarized scattered light
components and provides more data for solving the inverse problem of reconstructing the
size parameter from the scattered light intensity.

Conclusion: Dynamic Light Scattering (DLS) is a technique that depends on the interac-
tion of light with particles. It can be used to measure narrow particle size distributions, es-
pecially in the 2-500 nm range. The polydispersity of the sample can skew the results, and
the authors of [20] were unable to see real populations of particles, because large particles

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present in the sample can screen out smaller ones. Although the theory and mathematical
foundations of the DLS technique are already well known, little has been done to experi-
mentally determine its limits. The size and size distribution of artificially prepared polydis-
perse colloids of silver nanoparticles (NPs) were studied using DLS and ultraviolet-visible
spectroscopy (UV-Vis). Polydisperse colloids were prepared from a mixture of chemically
synthesized monodisperse colloids well characterized by atomic force microscopy (AFM),
transmission electron microscopy (TEM), DLS, and UV-visible spectroscopy. An analysis
of the DLS results obtained for polydisperse colloids shows that a few percent of the vol-
ume content of larger NPs can completely hide the presence of smaller ones. The pre-
sented results can be extremely important from the point of view of nanoparticle metrology
and should help to understand the experimental data, especially for those who work only
with DLS and/or UV-Vis.

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Xülasə
A.A. Əliyeva
Nanotexnologiyada işığın dinamik səpilməsi üsulunun tətbiqi

Nanohissəciklər geniş çeşiddə materiallar, tətbiqlər və sektorlarda mühüm funksionallıq

təmin edir. Dinamik işığın səpilməsi (DLS) analizi mikronaltı diapazonda hissəcik ölçüsü
paylama profillərini etibarlı şəkildə ölçməyə imkan verir. Bu üsul suspensiyonlarda nano-
hissəciklərin davranışını öyrənmək üçün xüsusilə faydalıdır. Zeta-potensial məlumatı ilə
birlikdə DLS məlumatları zamanla nanohissəciklərin yığılma meyli haqqında fikir verir. Bərk
hissəciklər kimi, DLS də səthi aktiv maddə molekullarının miselyar strukturlara necə birləş-
məsini "izləmək" üçün əvəzolunmazdır. Bu tənzimləmə səthi aktiv maddənin konsentrasi-
yasına və sadə elektrolit ionlarının konsentrasiyasına görə dəyişir. İkili terapiya və diaq-
nostika (“teranoz”) üçün nəzərdə tutulmuş nanohissəciklərin ölçüsü onların hədəf və qeyri-
hədəf hüceyrə və toxumalarda biopaylanmasını proqnozlaşdırmaq üçün vacibdir. Bioloji
nanohissəciklərin ölçüsü mürəkkəb xəstəliklərdə əsas molekulyar yolların mexanizmlərini
aydınlaşdırmağa kömək edə bilər. Asqıdakı nanohissəciklərin hidrodinamik ölçüsünü ölçən
DLS metodunun istifadəsi mühəndislik və təbii nanohissəciklərin konkret nümunələrini xa-
rakterizə etmək üçün qeyd olunur. Təqdim olunan işdə nanotexnologiyada işığın dinamik
səpilmə metodunun tətbiqi, xüsusən də nanohissəciklərin ölçülərinin müəyyən edilməsi sa-
həsində elmi tədqiqatların nəticələrinin təhlili aparılır.
Açar sözlər: dinamik işığın səpilmə üsulu, nanotexnologiya, nanohissəciklər, zeta potensi-
alı, hissəciklərin paylanması, polidisperslik və hissəcik ölçüsü

РЕЗЮМЕ
А.А. Алиева
Применение метода динамического рассеяния света в нанотехнологии

Наночастицы обеспечивают важную функциональность в широком диапазоне мате-

риалов, приложений и секторов. Анализ динамического рассеяния света (DLS) поз-

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воляет надежно измерять профили распределения частиц по размерам в субмик-

ронном диапазоне. Этот метод особенно полезен для изучения поведения наноча-
стиц в суспензиях. В сочетании с информацией о зета-потенциале данные DLS с те-
чением времени дают представление о тенденции наночастиц к агломерации. Как и
твердые частицы, DLS незаменим для регистрации того, как молекулы поверхност-
но-активного вещества объединяются в мицеллярные структуры. Это расположение
варьируется в зависимости от концентрации поверхностно-активного вещества и
концентрации простых ионов электролита. Отмечено, что использование метода
DLS, который измеряет гидродинамический размер наночастиц в суспензии, харак-
теризует конкретные примеры искусственных и природных наночастиц. В представ-
ленной работе проведен анализ результатов научных исследований в области при-
менения метода динамического рассеяния света в нанотехнологиях, в частности,
для определения размеров наночастиц.
Ключевые слова: метод динамического рассеяния света, нанотехнология, наноча-
стицы, зета-потенциал, распределение частиц, полидисперсность и размер частиц.

Publishing history
Article received: 30.03.2022
Article accepted: 25.08.2022

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MECHANICS AND MACHINE ENGINEERING UDC 550.38

Pp.47-51

INVESTIGATION OF IMPACT STRENGTH OF HYBRID FML COMPOSITES

REINFORCED WITH DIFFERENT NANOPARTICLES
N.A. Gurbanov
Azerbaijan State Oil and Industry University
E-mail: [email protected]

ABSTRACT

In hybrid fiber metal laminated composite materials, 1 mm thick 7075-T6 aluminum sheet
is used as metal matrix element and carbon fiber fabric is used as reinforcement phase
between metal matrix elements. In the first production, pure epoxy resin was used. In the
second production, 0.2%, 1% clay, silica and graphene nanoparticles were added to the
epoxy resin. Hybrid FML composite materials were produced in a hot press device after
stacking in 4/3 stacking order (Metal/Prepreg/Metal/Prepreg/ Metal/Prepreg/Metal). After
the composite materials were produced, the impact test was applied to the composite
samples according to ASTM E23 to determine the impact properties.
Keywords: composite material, epoxy resin, silica, clay, impact test.

Introduction: Nanoparticle reinforced hybrid fiber metal laminated composites are materi-
als with wide engineering applications in the automotive, aerospace, defense and aero-
space industries due to their high strength, lightness, rigidity and high temperature re-
sistance [1-2]. Despite their superior properties and advantages, these materials are sus-
ceptible to damage caused by various factors during production and service [3]. Damage
to composite materials as a result of an impact may occur on the surface that is not ex-
posed to impact, depending on the type of impact, and may begin as delaminations (sepa-
ration between layers) in the internal structure. Often invisible or very poorly visible dam-
age occurs. Almost all plastic matrix composite materials are brittle, so they can only ab-
sorb energy through elastic deformation and some damage mechanisms (matrix breakage,
delamination, fiber breakage, etc.), in other words, plastic deformation has almost no con-
tribution to energy absorption. In this sense, damage resistance refers to the amount of
impact damage that occurs in a composite system. In the laminated composite material, if
there is no reinforcement throughout the thickness, the greatest impact damage will occur
in the transverse direction. One of the most important reasons for this is the low elastic
property of the material in the transverse direction. Therefore, the transverse damage re-
sistance of a composite material is relatively weak. Interlayer stresses (shear and normal)
are the stresses that cause the first ruptures due to the low interlayer strength. The
amount of energy to be transferred to the composite material during the impact will deter-
mine the damage modes that will occur so that the material can absorb this energy. There-
fore, determining the impact velocity is of great importance to predict the damage to be
caused by impact in a laminated composite material [4-7].
In this article, the effects of graphene, silica and clay nanoparticles used in different ratios
on the impact performance of hybrid fiber metal laminated composites were investigated
and positive results were reported.

Objective: The following materials were used for the production of 7075-T6 aluminum ma-
trix hybrid FML composites reinforced with clay, silica and graphene nanoparticles. In the

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production of hybrid FML composite materials, 7075-T6 aluminum sheets cut in 1mm
thickness and 10x10cm dimensions and unidirectional carbon fiber fabric with 300 gr/m2
fiber density were used as the reinforcement phase between the metal matrix elements.
MGS L326 / H265 coded lamination resin set was used as thermoset resin. In addition,
0.2% and 1% of 18 nm thick clay (99.95%), 3 nm thick graphene (99.5%) and 15 nm thick
silica (99.50%) reinforcement to MGS L326 epoxy resin to be used in the production of
nanoparticle reinforced FML has been made.
In this study, hybrid fiber metal laminated composite materials are produced using 1 mm
thick 7075-T6 aluminum sheet and 2 layers of carbon fiber fabric according to the 4/3
stacking procedure (Al / CF 0 ° - CF 0 ° / Al / CF 0 ° - CF 0 ° / Al / CF 0 ° - CF 0 ° / Al ).
The fiber directions are placed parallel to the rolling direction of the aluminum plate. The
order of the produced composite, its symbolic representation, the ratio of epoxy resin and
nanoparticles used are shown in Table.

Table. Schematic view of hybrid FML composites and the ratio of nanoparticles used

Pure Epoxy + Epoxy + Epoxy +

Epoxy GNP Nanoclay Nanosilica

100% wt. % 0.2 wt. % 0.2 wt. % 0.2 wt.

*4 Layers of 7075-T6 Aluminum Sheet (each 100% wt. % 1 wt. % 1 wt. % 1 wt.
layer 1mm)
*3 Layers Epoxy + Carbon Fiber (each layer
0.5mm)

Stacked materials are pressed in a hot press device at 120°C for 3 hours and 1 ton
pressure. After 3 hours, the composite materials are removed from the device and allowed
to cool at room temperature for 24 hours. Samples required for impact testing of hybrid
FMLs were cut from the base plate using the Struers Secotom-50 precision cutting device.
The visuals of the impact test specimens are given in Figure 1.

Figure 1. Images of impact test specimens

Methods: Charpy impact test according to ASTM E23 was applied to determine the
impact strength of nanoparticle reinforced hybrid FML composites at room temperature.
For each group, 3 impact test specimens of 55x10 mm dimensions were used. The impact
test was carried out on a ZWICK brand 450 J impact tester. Impact tests were applied to
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the samples in two different directions, straight and lateral. The visuals of the devices on
which the impact test is applied are given in Figure 2.

Figure 2. Devices used in the impact test

Experimental results and discussion. The impact test results of different nanoparticle
reinforced hybrid FML nanocomposites applied in two different directions (flat and side) at
a speed of 5.23 m/s according to the ASTM E23 standard are shown in Figures 3 and 4. It
was observed that hybrid FML composites with 7075-T6 aluminum matrix and 0.2% clay
nanoparticle reinforced had the highest impact energy with 17.3 J (Flat), 44.3 J (Side)
values. Suitably, 0.2% graphene reinforced FML composites were found to have the
second highest impact energy with a value of 17.1 J (Flat), 37.4 J (Side) (Fig. 2). In lateral
impact tests, plastic deformation of metals, delamination between metal and composite
layer, fiber breaks, matrix damage mechanisms in composite layer stand out as the main
mechanisms effective in absorbed impact energy.
It was observed that there was a parallel increase when we added 1% clay, graphene and
silica nanoparticles to the 7075-T6 aluminum matrix hybrid FML composites. In other
words, 1% clay nanoparticle reinforced hybrid FML composites have been observed to
have the second highest impact energy with 17.3 J (Straight), 44.3J (Side) and 1% gra-
phene reinforced composites with 17.1 J (Straight), 37.4 J (Side) (Fig. 3). It is thought that
clay, graphene and silica nanoparticles added to the epoxy resin increase the impact en-
ergy of hybrid FML composites and contribute to the distribution of stresses in the matrix
by bridging the cracks in the matrix due to the impact force.

Figure 3. Impact test results of hybrid FMLs with 0.2 % clay, graphene
and silica nanoparticle doped
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Figure 4. Impact test results of hybrid FMLs with 1% clay, graphene

and silica nanoparticle doped.

Impact strength of hybrid FMLs can be defined as the ability of materials to absorb impact
energy when subjected to impact loading until deformation or rupture occurs in the
materials. Compared with metallic alloys that absorb energy through elastic-plastic defor-
mation, the composite core in the structure of hybrid FMLs exhibits various fracture me-
chanisms such as fiber splitting, fiber fracture and fiber shrinkage to absorb impact energy
[8]. Due to the high-velocity stress during the impact test, it is difficult to define the order of
the damage mechanisms, but it is possible to speculate by evaluating the fractured surface
images of the specimen after the test.

Conclusion: Charpy impact test results of nanoparticle reinforced hybrid FML composites
applied in two different directions as flat and side at room temperature according to ASTM
E23 standard
When the results of the impact tests applied to the 0.2% and 1% different nanoparticle
reinforced hybrid FMLs in straight and lateral directions were examined, the highest impact
energy was observed in the FML composites with 1% clay, with 19.8 J (Flat), 47.8 J (Side)
values. The lowest impact energy was observed in FML composites with 1% graphene
addition, with 16.9 J (Flat), 36.3 J (Side) values. When we look in general, it is seen that
the addition of nanoparticles at different rates positively affects the impact strength of
hybrid FML composites.

REFERENCES

1. Botelho E.C., Silva R.A., Pardini L.C., Rezende M.C. A review on the development and
properties of continuous fiber/epoxy/aluminum hybrid composites for aircraft structures. //
Mater. Res. 9. – 2006. – Pp.247-256.
2. Banat D., Mania R.J. Comparison of failure criteria application for FML column buckling
strength analysis. // Compos. Struct. 140. – 2016. – Pp.806-815.
3. Rogani A., Navarro P., Marguet S., Ferrero J-F., Lanouette C. Study of post-impact
behaviour of thin hybrid carbon/epoxy and glass/epoxy woven composite laminates under
fatigue tensile loading – Part I: Experimental study. // Composite Structures. 260. – 2021.
– Pp.113-449.
4. Gurbanov N.A., Babanli M.B. Investigation of Effects of Graphene Nanoplatelets
Addition on Mechanical Properties of 7075-T6 Aluminium Matrix Hybrid Fibre Metal
Laminates // Metallophysics and Advanced Technologies. 43. – 2021. – Pp.1589-1599.

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5. Mehtiyev R., Gurbanov N., Ismayilova K. Mathematical Model of Crack Formation and
Growth in Composite Material During Single-Axis Tension. 4th International Conference on
Mathematical and Related Sciences Book of Abstracts. – 2021. – Pp.74.
6. Bahari F., Eslami S.R., Chirani S.A. The Flexural And İmpact Behavior of The Lamina-
ted Aluminum-Epoxy/Basalt Fibers Composites Containing Nanoclay: An Experimental
İnvestigation // Journal of Sandwich Structures and Materials. – 2018. – Pp.1-21.
7. De Cicco D., Asaee Z., Taheri F. Use of Nanoparticles for Enhancing the Interlaminar
Properties of Fiber-Reinforced Composites and Adhesively Bonded Joints-A Review. //
Nanomaterials (Basel). – 2017, 7.
8. Malingam S.D., Jumaat F.A., Subramaniam K., Ghani, F.A. Tensile and impact proper-
ties of cost-effective hybrid fiber metal laminate sandwich structures. // Advances in
Polymer Technology. – 2018, 37. – Pp.2385-2393.

XÜLASƏ
N.A.Qurbanov
Müxtəlif nanohissəciklərlə gücləndirilmiş hibrid FML
kompozitlərin zərbə gücünün tədqiqi

Hibrid fiber metal laylı kompozit materiallarda metal matris elementi kimi 1 mm qalınlığında
7075-T6 alüminium lövhədən, metal lövhələr arasında isə möhkəmləndirici kimi karbon
fiber parçalardan istifadə olunmuşdur. İlk istehsalda saf epoksi qatranından istifadə edil-
mişdir. İkinci istehsalda isə epoksi qatranına müvafiq olaraq 0,2%, 1% nisbətində gil, silisi-
um və qrafen nanohissəcikləri əlavə edilərək hibrid FML kompozit materiallar 4/3 yığma
qaydasında (Metal/Prepreg/Metal/Prepreg/Metal/Prepreg/Metal) yığıldıqdan sonra isti pres
cihazında istehsal edilmişdir. Kompozit materiallar istehsal edildikdən sonra zərbə özülülü-
yünü müəyyən etmək üçün ASTM E23-ə uyğun olaraq kompozit nümunələrə zərbə testi
tətbiq edilmişdir.
Açar sözlər: kompozit material, epoksi rəçinə, silisium dioksid, gil, zərbə özlülüyü.

РЕЗЮМЕ
Н.А. Гурбанов
Исследование ударной вязкости гибридных МВЛ композитов,
армированных различными наночастицами

В композитных материалах с гибридным волокном и металлом алюминиевый лист

7075-T6 толщиной 1 мм используется в качестве элемента металлической матрицы,
а ткань из углеродного волокна используется в качестве армирующей фазы между
элементами металлической матрицы. В первом производстве использовалась чис-
тая эпоксидная смола. Во втором производстве в эпоксидную смолу добавляли
0,2%, 1% наночастиц глины, кремнезема и графена. Гибридные композитные мате-
риалы МВЛ были изготовлены в устройстве для горячего прессования после укладки
в порядке укладки 4/3 (Mеталл/Препрег/Mеталл/Препрег/Mеталл/Препрег/ Mеталл).
После того, как композитные материалы были изготовлены, к образцам композита
было применено испытание на удар в соответствии с ASTM E23 для определения
ударных свойств.
Ключевые слова: композитный материал, эпоксидная смола, кремнезем, глина,
испытание на удар

Publishing history
Article received: 30.08.2022
Article accepted: 02.06.2022
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MECHANICS AND MACHINE ENGINEERING UDC 620.194.2

Pp.52-56

LONG DURABILITY OF THE DAMAGED HOLLOW SHAFT AT TORSION

M.A. Mammadova
Institute of Mathematics and Mechanics of ANAS,
E-mail: [email protected]

ABSTRACT

In modern stage of development of engineering, this calculation involves taking account

new factors. One of the most important ones is damageability of the material, i.e. initiation
and accumulation of various nature defects. In the presence of this phenomenon, destruc-
tion is a process in time consisting of the latent incubation period of destruction and ap-
parent destruction stage accompanied by formation and extension of the zone of the de-
structed part of the material. In this aspect, we consider a problem of a long-term destruc-
tion of a hollow isotropic shaft twisted by a constant moment based on the hereditary theo-
ry of damageability.
A problem of initiation and development of scattered destruction zone in a twisted hollow
shaft with regard to phenomenon of damageability of its material, was solved. An equation
of motion of destruction front was obtained and solved. Regularities of torsional scattered
destruction of a hollow shaft were determined. The curve of destruction front motion was
structured.
Keywords: scattered destruction, damaged shaft, front of destruction, torsion

Introduction: Hollow shafts and pipes are one of the most common structural elements,
machines and mechanisms and one of the basic types of loading is a torque transmitted
by them.
Analysis of life cycle of twisted hollow shafts represents an important stage in the overall
process of calculation and design of constructions, machines and mechanisms. In modern
stage of development of engineering, this calculation involves taking account new factors.
One of the most important ones is damageability of the material, i.e. initiation and accumu-
lation of various nature defects. In the presence of this phenomenon, destruction is a pro-
cess in time consisting of the latent incubation period of destruction and apparent destruc-
tion stage accompanied by formation and extension of the zone of the destructed part of
the material. In this aspect, we consider a problem of a long-term destruction of a hollow
isotropic shaft twisted by a constant moment based on the hereditary theory of damagea-
bility.
Objective: We consider a problem of scattered destruction of an annular hollow shaft
whose cross-section is a concentric ring with inner radius  and outer radius R. Its exter-
nal torque M is assumed to be constant.
Distribution of the shear stress  within the hereditary damage theory will be the same as
for an elastic shaft, more exactly:
M
τ ρ (1)
Jp
Where  – a current radius; J p – a polar inertia moment of the cross-section:

J 
2

π 4
R  r4  (2)

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The greatest stress arises at the external surface ρ  R and equals:

M τ  r4   R 4 
τ max  ; Wk      1 (3)
Wk 2R  r  
 
Here Wk – torsional moment of resistance.
As a destruction criteria we accept:
τ  L  τ  τ 0 , (4)
where τ0 – instantaneous ultimate strength, L is damageability that with a monotonically
increasing load has the same structure as an ordinary integral operator of linear viscoelas-
ticity:
t
L  τ   Lt  ξ  τξ  dξ (5)
0

where Lt  ξ  – a damageability kernel.

The time of primary destruction and destruction front equation is obtained from the de-
struction criteria (4) with regard to the form and level of stress state.

Methods: The primary stress will occur in the place of the greatest shear stress, i.e. at the
external surface of the hollow shaft, when ρ  R . We find the time of primary destruction t1
being the latent destruction period, by substituting formula (3) in destruction criteria (4):
M
Wk
1  L  1  τ 0

Hence, allowing for representation (5) we get:

t1
τ W
0 Lξ  dξ  0M k  1 (6)

For the existence of the latent destruction period a necessary condition is the positivity of
the right hand side of formula (6), where we get restrictions on the value of the torque M:
M  τ 0 Wk (7)
For other values of the torque, destruction will happen instantaneously. Therefore, further
we will assume that condition (7) is fulfilled.
We get a formula for the incubation period when specifying the damage kernel. Below we
give formulas of latent destruction time for three types of damage kernels:
 1 τ W 
 Lt  ξ   L0  const t1   0 k  1
L0  M
 
 1  L τ W
1

 Lt  ξ   L0 e m t   
t1  ln 1  0  0 k  1
 μ  μ  M 
 (8)
 Lt  ξ   L t  ξ   2

 0

 1

0  α  1  1  2  τ W   1α
t1    0 k  1
  0  M
L 
After destruction of the external surface layer, over time there will be formed an expanding
annular destruction zone adjoining to the external surface of the cross-section of the cylin-
drical shaft. The boundary of separation of destructed and not destructed parts is called a
destruction front. The nature of destruction front motion determines intensity of the occur-
ring scattered destruction process. We assume that the material behind the destruction
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front completely loses its load-bearing ability. Then we get the destruction front motion
equation from the destruction criteria (4) with regard to the shear stress formulas (1), (2)
where we preliminarily make the following changes:
ρ
 βt  ;  βξ 
R
(9)
r r
In its essence, the function βt  is a non-dimensional radial coordinate of destruction front
at the current moment, β  is the same coordinate, but at the moment ξ  t antecedent to
the current one.
By means of the radial coordinate of destruction front, the shear stress formula will have
the form:
β t 
 β t ; βξ  
2M
(10)
π  r 3 β 4 ξ   1
We write the destruction criteria (4) in the explicit form:
t
  t ;  t    Lt     t ;  t  d   0 (11)
0

We substitute formula (10) in (11) and introduce the pure variable

r 3 0
g (12)
2M
Then we get the following destruction front motion equation:
 t  t
 t 
  Lt    4 d  g (13)
 t   1 0
4
    1
The desired function  t  has the following structure:
 R
 0  for t  t1
 t    r (14)
   0 t  t1
It is clear that the limit value of the function βt  equals to one. However, there may be a
situation when for some intermediate value of the function βt  , the destruction front speed
determined by the derivative function βt  at the moment of time vanishes. Just this mo-
ment should be considered as final or complete destruction time.
The destruction front motion equation (13) is a second order nonlinear Volterra integral
equation. For the general form of the kernel of the integral term its solution is a difficult
mathematical problem. However, for relatively simple particular types of kernels, there is a
possibility to obtain the solution of the integral equation in the explicit analytic form. This
allows to conduct qualititative analysis of the studied scattered destruction process and
reveal its typical properties. Acting in such a way, we accept the damage kernel as con-
stant, i.e. assume Lt  ξ   L0  const . Further, we will consider the time dimensionless
with respect to the kernel parameter accepting the time t multiplied by L0 . Then the de-
struction front motion equation takes the form:
 t  t
d g
  
 t   1 0     1  t 
4 4
(15)

Differentiate this equation with respect to time. We get the following equation determining
the destruction front propagation velocity:
d  2  4  1

4  5  g  4  1
(16)
dt

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The left hand side of this equation is always negative that provides a decrease of the func-
tion βt  in time, and this corresponds to the physical sense of the studied process. The
denominator of the right hand side does not vanish at any value of . This certifies that the
situation of catastrophic development of destruction process, when the destruction front
motion velocity goes to infinity, is impossible.
To find the destruction front propagation law we should integrate the differential equation
(16). According to the first formula with regard to previously accepted denotations, the ini-
tial condition to it will be:

t1 
g  04  1
1 (17)
0
Integrating equation (16), we get:
3 3 1 1
t  t1  ln  04 11  g  0  
4
 (18)
 3 0  
The requirement of the existence of the incubation period, i.e. realizability of the condition
t1  0 imposes the following restriction:

g  40 (19)
0 1
According to (16) the destruction front motion velocity decreases. Thus, the destruction
front propagates with velocity decreasing monotonically to zero. This time, the destruction
front propagation period is infinitely great.
For obtaining a quality estimation we accept β 0  2 , then according to (19) we accept
g  0.14 . Then from (17) we get t1  0.5 . In the figure we give a curve of the destruction
front propagation for the above values of parameters.

Figure. The curve of destruction front motion: g  0.2 ;  = 2

Conclusion: The regularities of the process of torsional scattered destruction of a hollow

shaft were determined.

REFERENCES

1. Kachanov L.M. Fundamentals of destruction theory. – M: Nauka, 1974. – P.312.

2. SuvorovaYu.V., Akhundov M.B. Long – term destruction of isotropic medium under
complex stress state conditions. // AN SSSR. – 1986, №4. – Pp.40-46.
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XÜLASƏ
M.Ə. Məmmədova
Zədələnmiş valın burulmada uzunmüddətli möhkəmliyi məsələsinin həlli

Texnologiyanın indiki mərhələsində hesablamalar yeni amillərin nəzərə alınmasını tələb

edir. Bu amillərin əsaslarından biri materialların zədələnmə faktorudur, yəni müxtəlif təbiətli
zədələrin əmələ gəlməsi və yığılmasıdır. Bu vaxt dağılma zamandan asılı olaraq zədələn-
mənin gizli inkubasiya periodundan və tam dağılmadan ibarətdir. Dağılma materialın dağıl-
ma zonasının əmələ gəlməsi və genişlənməsi ilə müşayiət olunur. Bu aspektdə burada
zədələnmiş valın burulmada uzunmüddətli möhkəmliyi məsələsinə baxılır. Zədələnmə
prosesi nəzərə alınmaqla sabit moment ilə burulan boru valda səpələnmiş dağılma
hissəsinin yaranması və inkişafı məsələsi həll edilir. Dağılma cəbhəsinin tənliyi alınaraq
həll edilmişdir.
Açar sözlər: zədələnmiş val, dağılma cəbhəsi, burulma, səpələnmiş dağılma

РЕЗЮМЕ
М.А. Маммадова
Долговечность поврежденного полого вала при кручении

Расчеты рабочих ресурсов скручиваемых полых валов представляют собой важный

этап общего процесса расчета и проектирования конструкций, машин и механизмов.
На современном этапе развития техники этот расчет предполагает учёт новых фак-
торов. Одним из важнейших факторов является повреждаемость материала, то есть
явление зарождения и накопления дефектов различной природы. При наличии этого
явления разрушение представляет собой процесс во времени, состоящий из стадии
скрытого инкубационного периода разрушения и стадии явного разрушения, сопро-
вождающейся образованием и расширением зоны разрушенной части материала. В
этом аспекте здесь рассмотрена задача о длительном разрушении скручиваемого
постоянным моментом полого изотропного вала на основе наследственной теории
повреждаемости. Решена задача о зарождении и развитии зоны рассеянного разру-
шения в скручиваемом полом вале с учётом явления повреждаемости его ма-
териала. Получено и решено уравнение движения фронта разрушения, oпределены
закономерности процесса, рассеянного разрушения полого вала при кручении. Пос-
троена кривая движения фронта разрушения.
Ключевые слова: рассеянное разрушение, кручение, напряженно-деформирован-
ное состояние, повреждение, фронт разрушения.

Publishing history
Article received: 28.04.2022
Article accepted: 25.08.2022

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ENERGY AND POWER ENGINEERING UDC 621.313.333

Pp.57-62

EXCITATION REGULATORS FOR SYNCHRONOUS

MACHINES UNDER VARIABLE LOAD
T.D. Veliyeva
Azerbaijan State Oil and Industry University
E-mail: [email protected]

ABSTRACT

In synchronous machines, “strong action” regulators are traditionally used, in which the
control action is formed as a function of the controlled coordinate itself, as well as its first
and second derivatives. The use of derivatives improves the quality of regulation, but the
controller becomes more sensitive to noise and errors in the control channel, which makes
it difficult to implement and operate the controller. The application of optimal excitation
control to improve the quality of control of synchronous machines under variable load is
considered. The results of the synthesis of the optimal controller for a specific synchronous
generator are presented.
Keywords: synchronous machine, load unit, excitation regulator, voltage, magnetic flux,
generator, compensator.

Introduction: Stabilization of the voltage of large industrial load catching units of mod-
ern electrical systems during fluctuations in load current is an important technical prob-
lem, for the solution of which it is possible to use the adjusting abilities of synchronous
machines located in these nodes.
As you know, with rapid changes in the load, the voltage is subject to slight fluctua-
tions. To reduce oscillations, they resort to regulating the magnetic flux of the rotor by
controlling the voltage on the clamps of the excitation winding of synchronous generators
or compensators.
Since the maximum voltage values that can be applied to the excitation winding are lim-
ited, the quality of the voltage depends on the law of the control action in the excitation
regulator.
It should be noted that the electrical load of a large industrial enterprise (load node) is usually
not an ergodic random function. In it, it is possible to distinguish, for example, the periodic
component with a daily period, depending on the distribution of the load on shifts, and other
slowly changing non-random components.
However, the hundred-rate voltage of the enterprise network is most affected not by these
slow changes in the load, but by its fluctuations within the 40÷60 seconds in length, com-
mensurate with the constants of the excitation winding time of the synchronous generators
supplying the node.

Objective: In order to get an idea of the correlation function of the load in intervals of this
length, it is necessary to record your own coupness of the implementation (length of 1÷2
minutes) of the load current of the substation feeding the enterprise. Analysis of load fluc-
tuations at intervals of 50÷60 seconds shows that these fluctuations can be considered a
stationary random process with a sufficient degree of accuracy.
For illustration, Figure 1 shows the implementation of the current for loads in amperes on the
side of the 35 kV substation of the Azerbaijan Pipe Rolling Plant, filmed at 10 hours 40
minutes.
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Figures 2 and 3 show (on a different time scale) two more implementations of the load cur-
rent on the 35 kV side for the stations of the same plant, filmed at 10 hours 35 minutes and
10 hours 42 minutes.

Figure 1. Realization of current for loads on the side of 35 kV substation

of the Azerbaijan Pipe Rolling Plant, removed at 10 hours 40 minutes

Figure 2. Realization of current for loads on the side of 35 kV substation

of the Azerbaijan Pipe Rolling Plant, removed at 10 hours 35 minutes

Figure 3. Realization of current for loads on the side of 35 kV substation

of the Azerbaijan Pipe Rolling Plant, removed at 10 hours 42 minutes

To obtain correlation functions of the load current, the reactions were first centered (the aver-
age value of the implementation was calculated, which was then subtracted from the current
values). After that, for the centered values (t), estimates of correlation functions were calcu-
lated:
T
1
K  (τ)  T  φ(t )φ(t  τ)dt , (1)
0

where T - is the length of the implementation, and then the scores were averaged across
multiple implementations. The experiment showed that correlation functions are well ap-
proximated by analytical expressions of the form

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
K  ( )  K  (0)e cos  (2)

Fig.4 shows the correlation function of the centered component of the load current of the
Azerbaijan Pipe Rolling Plant (averaging for six realizations), and the bar line gives an
analytical approximation of the dependence

0 ,12
K  ( )  380e cos 0,285 (3)

Correlation function (3) corresponds to calculated by formula


2
 0 K 
S ( )  ( ) cos d , (4)

power spectral density

0,095   2
S ( )  25,25 (5)
(0,095   2 ) 2  0,324 2

Figure 4. Correlation function of the centered component

of the load current of the Azerbaijan Pipe Rolling Plant

Methods: Consider a synchronous generator, the transient processes in which are de-
scribed by the equation

(63,69 D 3  34,98 D 2  5,94 D  0,55) x 

 (0,0205 D 3  3,66 D 2  2,33D  0,37)u  (6)
 (13,57 D  11,82 D  6,05 D  1,27) (t ),
3 2

where x – the deviation of the voltage at the generator clamps from the nominal value; и –
deviation of the voltage on the clamps of the generator winding from the value corresponding
to the nominal mode; (t) – the deviation of the load current from the min.
The spectral power density of the function (t) is bound by the formula
1
S ( )  0,00204 (7)
0,1024   2

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That is D   S  ( )d  0,01 and the mean square value of the fluctuations in the load
0
current is 10% of the rated current.
The voltage quality provided by the regulator is evaluated by the value of the func-
tionality <х 2 >.
Since the value and и(t) – limited, the question is raised about the synthesis of a regu-
W ( D)
lator u  1 x , that provides a minimum functional J=т<х 2 >+<х 2 >, where т 2 – a
W2 ( D)
multiplier of the Lagrange body, which is determined in the future.
Algorithm 2 [1] can be used to synthesize the regulator.
Since in this case the spectral power density of the reduced perturbation effect ф1 is
equal to

S ( )  S 13,57( j )3  11,82( j ) 2  6,05( j )  1,27

2

then, given equation (6), we have n = 3, m = 3, p = 3 and q = 1.

Now, for the degrees W1 ( D ) and W2 ( D ) , according to [2], it can be established that the
W ( D)
degree of the numerator of the optimal regulator u  1 x will be three and the degree
W2 ( D )
of the denominator will also be three. Such a regulator is easily implemented, and there-
fore the synthesis task makes practical sense.
Since the inequality р > т + q - 1 is satisfied, the closed system will be stable.
Performing the calculation of the gain coefficients of the regulator on the axis of the new
algorithm 2 for a number of values of the Lagrange multiplier т2 and calculating for
each т 2 value the corresponding values of the values х and u, we make up the follow-
ing table:
Table.

m2 0 4 16 100 625
u 0 0,127 0,196 0,254 0,315
х 0,132 0,108 0,0316 0,0152 0,0965

From the table it can be seen that at т 2 = 0, that is, in the absence of regulation,
the average squared value of the deviation of the generator voltage from the nomi-
nal one is 13.2%.
In the future, with growth, the тг decreases х , at first quickly, then more and more slowly
and slowly.
Therefore, it is rational to dwell on the value of many Lagrange inhabitants т2 = 100; in
this case, the mean square value of the deviation of the voltage of the generator will be
equal to 1.52%, and the optimal regulator will take the form

 159,7 D 3  157,2 D 2  69,5 D  12

u x
13,5 D 3  10,9 D 2  3,7 D  0,549
(8)
 0,274 19,3D  10,3 
 11,8   x
 2,78 D  1 8,82 D 2  3,97 D  1 

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that is, it will be a parallel connection of the simple amplifying, aperiodic, and oscillatory
links with moderate gain coefficients [3].
Analysis of the results. To improve the quality of regulation of synchronous machines,
"strong action" regulators are traditionally used, that is, regulators in which the control effect
is formed in the function not only of the most adjustable coordinate, but also in the function
of its first, and sometimes the second derivative, that is, x, x, x .
The use of derivatives improves the quality of regulation, but at the same time the regula-
tor becomes more sensitive to inevitable interference and errors in the control channel,
which complicates the implementation of the regulator and complicates its operation. Since
interference and error have a higher frequency spectrum than useful signals, the harmful
effects of accidents and interference increase dramatically with increasing order of produc-
tion.

Conclusion: Comparing the structure of the optimal regulator with the structure of tradi-
tional excitation regulators of synchronous machines, the following conclusions can be
drawn:
1. The optimal regulator uses derivatives from x up to the third order and in this sense is a
"stronger regulator" compared to traditional regulators.
2. The optimal regulator is insensitive to co-frequency interference, since its denominator
degree is equal to the degree of the numerator, and therefore high-frequency interference
is not amplified.
3. The optimal regulator includes seven coefficients, so it cannot be found by simple selection
and must be pre-calculated.
4. Since the optimal regulator provides a minimum quality criterion J, the changes in the
latter with small deviations of the parameters of the generator or regulator from the calcu-
lated values will be less than those of regulators of the traditional structure.

REFERENCES

1.Abdullayev N.D., Petrov Y.P. Theory and methods of designing optimal regulators. – Len-
ingrad: Energoatomizdat, 1985. – 240 p.
2.Kazimzada R.Z., Veliyeva T.D. Automation software for the design of optimal ARV syn-
chronous machines of load units. // Problems of Energy. – Baku, 2007, № 2. – Рp.95-100.
3. Makarichev Y.A., Ovsennikov V.N. Synchronous machines. // Samara State Technical
University, 2010. – 156 p.

XÜLASƏ
T.D. Vəliyeva
Dəyişən yükdə işləyən sinxron maşınlarının təsirlənmə tənzimləyiciləri

Sinxron maşınlarda ənənəvi olaraq "güclü hərəkət" tənzimləyicilərindən istifadə olunur,

burada idarəetmə hərəkəti idarə olunan koordinatın özünün, eləcə də onun birinci və ikinci
törəmələrinin funksiyası kimi formalaşır. Törəmələrin istifadəsi tənzimləmə keyfiyyətini
yaxşılaşdırır, lakin nəzarətçi idarəetmə kanalındakı müdaxilə və səhvlərə daha həssas
olur, bu da nəzarətçinin həyata keçirilməsini və idarə edilməsini çətinləşdirir. Dəyişən yük
altında sinxron maşınların idarə edilməsinin keyfiyyətinin yaxşılaşdırılması üçün optimal
təsirlənmə tənzimləyicinin tətbiqi nəzərdən keçirilir. Xüsusi sinxron generator üçün optimal
nəzarətçinin sintezinin nəticələri təqdim olunur.
Açar sözlər: sinxron maşın, yük qovşağı, təsirlənmə tənzimləyici, gərginlik, maqnit sahə,
generator, kompensator.
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РЕЗЮМЕ
Т.Д. Велиева
Регуляторы возбуждения синхронных машин при переменной нагрузке

В синхронных машинах традиционно применяют регуляторы «сильного действия», в

которых управляющее воздействие формируется как функция самой управляемой
координаты, а также ее первой и второй производных. Использование производных
повышает качество регулирования, но контроллер становится более чувствитель-
ным к шумам и ошибкам в канале управления, что затрудняет реализацию и экс-
плуатацию регулятора. Рассмотрено применение оптимального управления возбуж-
дением для повышения качества управления синхронными машинами с переменной
нагрузкой. Представлены результаты синтеза оптимального регулятора для кон-
кретного синхронного генератора.
Ключевые слова: синхронная машина, узел нагрузки, регулятор возбуждения, на-
пряжение, магнитное поле, генератор, компенсатор.

Publishing history
Article received: 04.03.2022
Article accepted: 25.08.2022

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ECONOMY AND MANAGEMENT UDC 336.519.86

Pp.63-73

APPLICATION OF ECONOMIC MODELING TO EVALUATE

THE EFFICIENCY OF BANKING
M.O. Nagiyev
Azerbaijan State University of Oil and Industry
E mail: [email protected]

ABSTRACT

A number of approaches to assessing the effectiveness of banks has been discusser. An

algorithm has been developed that can be used to determine the level of efficiency of a
banking enterprise, and risk zones have been identified. The factors required to calculate
efficiency have been identified. Based on the results of extensive research, an efficiency
finding algorithm has been developed, on the basis of which it is possible to compile a
rating table to determine the efficiency class for each enterprise. In particular, this work is
valuable for sustainable work in terms of the factors that make up the activities of an
individual institution.
The establishment of a bank's innovation management mechanism to increase the effici-
ency of all banking activities is based on generally accepted principles of enterprise mana-
gement, complemented by the principle of organizational concentration of innovative ideas
and the principle of limited innovation project [1]. The principles of customer focus and
initiative are always taken into account in connection with the customer-oriented strategy
for the development of the banking business. The implementation of the principles of mea-
surability and efficiency is related to the need to create a system of indicators that can be
used to assess the effectiveness of banking. With the application of innovations, the influ-
ence of various factors plays an important role in the overall efficiency of the bank.
The article analyzes traditional (financial), probabilistic and qualitative methods of as-
sessing the effectiveness of branches through the application of banking innovations. The
advantages and disadvantages of the application of banking innovations were assessed,
as well as the effectiveness of all types of banking innovations. After further study of the
possibilities of using banking innovations, it was concluded that the BSC method is expedi-
ent in establishing an effective banking management mechanism. The article also iden-
tifies the importance of indicators for the formation of the banking system, which contribute
to the effectiveness and competitiveness of the application of innovative products and
technologies in the retail segment of the banking business.
Keywords: banking, efficiency assessment, finance, DEA (operating environment ana-
lysis) methodology, resource parameters, output parameters, efficiency margin, economic
modeling

Introduction: In modern conditions, efficiency is becoming an important factor in the

accelerated socio-economic growth of the national economy. It is planned to achieve a
high level of socio-economic development of our country by increasing efficiency, streng-
thening its international competitiveness and making the country one of the leaders in the
world economy.
Since economic activity is carried out in constant interaction with the environment, the
external environment, the subject of activity is constantly changing, the above concept of
efficiency is complemented by significantly different views on what the outcome is and

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what efforts are made. This is reflected, among other things, in a number of specific effici-
ency concepts, as well as in efficiency assessment approaches. The most common appro-
ach to assessing effectiveness, understood as the ratio of effort and results, is the resour-
ce approach. Under this approach, effective action involves achieving maximum results
from available resources or achieving certain results using minimum resources. To assess
the technical efficiency of production - in the form of performance indicators that charac-
terize the production process, regardless of the estimated cost of the result and the means
of production spent to achieve it, and used to assess economic efficiency – income/cost or
product/cost ratios. The resource approach is still the most common approach to asses-
sing the effectiveness of a company in the modern world, although some advantages of
this approach, all the simplicity of logic, all the problems of efficiency assessment, especi-
ally in modern conditions are not satisfacorily solved [2].
Data Envelopment Analysis, abbreviated as DEA, is a methodology for comparative ana-
lysis of the performance of complex technical, economic and social systems. This appro-
ach began in the 1970s and 1980s in the works of A. Charnes, V. Cooper, E. Road, and R.
Banker. At present, the DEA methodology covers a wider range of concepts and capabiliti-
es than the calculation and analysis of the efficiency of complex facilities.
DEA methodology is deeply connected with mathematical economics, system analysis,
multi-criteria optimization, allows you to build a multidimensional economic space, find the
best ways of development by simulating objects and different situations, calculate the most
important quantitative and qualitative characteristics of behavior. Classical methodologies
and approaches have been used to achieve a similar goal and to obtain reliable estimates
for the present study. The results of such methods should also be analyzed, as they allow
to determine the extent to which a particular method can be applied to assess the effecti-
veness in general and the performance of the banking sector in particular.
Modern economic relations represent a complex system of economic relations in which the
activities of an individual enterprise or firm depend on and influence the activities of other
firms. Also, the production process of an individual enterprise almost always consists of a
series of sub-processes or stages, and the final efficiency is the product of the efficiency of
these stages and their interaction [3].
The basis for measures to increase the efficiency of the bank's activities is a thorough as-
sessment of efficiency. There are a number of well-founded methods for assessing effici-
ency in economic analysis. At the same time, the development of the economy as a whole,
and in particular the significant complexity of the set of inter-object relations, predetermi-
nes the emergence of new methodological methods, including those based on the use of
economic and mathematical modeling methods.

Methods: One of the directions of development of the methodology of application of

economic and mathematical modeling for the assessment of the efficiency of the bank's
activity has been the boundary methods for the assessment of the efficiency obtained so
far. These methods allow comparing the performance of each individual and other subjects
with the rest of the set under consideration, and are represented by two groups of met-
hods: non-parametric and stochastic. Correct comparison of the results obtained by the
methods of different groups from the very beginning remains a constant problem, one of its
specific issues is the possibility of establishing an adequate analytical approximation of the
efficiency limit in the non-parametric case. Another aspect of the comparability of these
groups of methods is that the results obtained by applying stochastic methods to objects
with complex internal structures are almost incomplete. By developing research in this
direction, first of all, it is necessary to find the right mathematically and economically justi-
fied formulation and solution of evaluation and comparison problems. At the same time, a

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number of new problems need to be solved in terms of determining the relationship bet-
ween efficiency .
DEA - analysis of the operating environment. The DEA method can also be chosen as a
tool to assess the effectiveness of banking financing. DEA calculations are often verified
using the Malmquist index.
DEA - analysis of the operating environment is based on the application of linear program-
ming. As previously described, the method is often used to measure service efficiency, but
initially its creation involved assessing production efficiency and productivity.
The method itself is based on the construction of an effective boundary, which measures
the effectiveness of the other units studied. This is illustrated in Figure 1.
A maximum of two approaches are used in DEA analysis. CCR (Charnes-Cooper-Rhodes
model) - the first model. A stable production scale is considered when setting up a CCR.
Each model can be focused on Input or Output, which reflects the effectiveness of which of
the indicators should be evaluated. The difference between the CCR and BCC models is
whether the scale of production is constant.

Figure 1. Establishing an effective boundary

That is, in one case, the result is a fixed instantaneous assessment. Efficiency is projected
for the current period, as well as efficiency that is able to take into account future producti-
vity growth.
The advantage of non-parametric methods is that there is no assumption of a functional
form for the boundaries, although there is no general equation (connection) for output and
input (for example, the regression equation).
In investigating the current issue, the DEA is compared with the most effective examples
of all systems, as shown in Figure 1. In optimization (maximization /minimization) it can be
characterized as a method of determining the extreme point. The method begins with the
assumption that if a decision-making unit can maintain production at a certain level in
order to be efficient using a certain amount of revenue, then another unit (firm) must keep
production and costs at the same level. The study of operational efficiency often uses reg-
ression analysis and the construction of a production function with stochastic boundaries.
The following advantages of the DEA method have been identified:
- there is no need to clearly state the production function;
- it is possible to explain the relationship of the studied indicators in more detail when using
alternative methods;
- it is possible to use several inputs and outputs;
- measurements input and output can be any unit of measurement;
- the researcher does not impose a weight limit for indicators;
- it is possible to evaluate the analysis of sources of inefficiency for the enterprise / system.
The Malmquist Index (MI) is a two-way index that can be used to compare the perfor-
mance of technologies between industries. In this case, it can be used to compare effici-
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ency [4]. The name comes from Professor Stan Malmquist, who developed the idea for the
index. Its other name is Malmquist Productivity Index (performance index). The concept of
production function is the basis of the Malmquist index. The dependence of the index
indicators is related to the maximum possible production in relation to the input.
Using the DEA methodology, it is possible to analyze the comparison of approaches in the
study of the costs of maintaining and improving the efficiency of banking activities. There
are many examples of the application of these methods separately, which should allow a
more complete assessment of the advantages and disadvantages of each of these
methods. In the same study, two methods and completely identical information were used,
which allows us to form an understanding of in which cases and for which problems the
DEA method prefers the elements of regression analysis, and vice versa.
The DEA methodology has some advantages over the specified specification only. In
general, the choice of methodology is at the discretion of the researcher, as the reliability
and completeness of the data obtained through certain regressions depends entirely on
the accuracy and correct use of the data [5].
A type of approach to assessing the effectiveness of banks has been considered. The
bank has developed an algorithm that can be used to determine the level of efficiency of
the enterprise, identified risk zones. The factors required to calculate efficiency have been
identified. Based on the results of extensive research, an efficiency finding algorithm has
been developed, on the basis of which it is possible to compile a rating table to determine
the efficiency class for each enterprise. In particular, this work is valuable for sustainable
work in terms of the factors that make up the activities of an individual institution.
It is also important to pay attention to the factors that are perceived as input (input factors)
and output (output factors - indicators of the enterprise).
The establishment of the bank's innovation management mechanism to increase the effi-
ciency of all banking activities is based on the generally accepted principles of enterprise
management, complemented by the principle of organizational concentration of innovative
ideas and the principle of limited innovation project. The principles of customer focus and
initiative are always taken into account in connection with the customer-oriented strategy
for the development of the banking business. The implementation of the principles of
measurability and efficiency is related to the need to create a system of indicators that can
be used to assess the effectiveness of banking. With the application of innovations, the
influence of various factors plays an important role in the overall efficiency of the bank.The
purpose of this article is to develop methods and techniques for the implementation of
innovative development strategies of the bank's branches, whose economic efficiency
increases as a result of the application of innovative products, services and management
methods [6].
The following methods are used in world practice to assess the efficiency of banks.
1) DEA MCDM methodology – world experience in measuring efficiency and Data
Envelopment Analysis methodology.
2) Branch efficiency – measuring the effectiveness of branches on various criteria with the
principles of DEA.
3) Number of branches in the area – determining the number of branches in a given area,
including whether a large branch or a small branch is more effective.
4) ROA – factors not considered in the Return to Assets method.
5) Factors affecting the effective operation of the bank through the application of
innovations.
These factors directly affect the fair evaluation of the performance of bank branches in
terms of efficiency. These indicators are as follows:
 branch potential;

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 standby ratio;
 workload;
 service quality;
 sales indicators.
In the world practice, various methods are used to measure the efficiency of an innovative
bank. Each of these methods is very important for the assessment of the bank's branches,
the bank's innovative activity in general and the future successful development of the
bank.
MCDM Multiple Criteria Decision Making is a set of multidisciplinary analysis and solution
methods used in the world practice, used by enterprises and institutions of different
directions, which determine a single degree of effectiveness for them, taking into account
different criteria [7].
Data Envelopment Analysis (DEA) – this method uses a matrix method to assess the
efficiency of banks, the specific weights are determined automatically.
Other similar models – this method uses simple mathematical methods to calculate the
efficiency of banking.
Weighted Product Model – normalization is done through force calculation.
Weighted Sum Model – normalization is carried out by linear calculation.
Results obtained. Table 1 gives a comparison of conventional branches with effective
branches and scale.

Table 1. Comparison and scale of performance on conventional branches

Branch Loan
Number of
portfoli Rental cost Profit
employees
o

Alpha (α) 15M 5k 10 1M

Beta (δ) 17M 7k 8 1.4M

Gamma (γ) 16M 6k 11 1.2M
Delta (σ) 19M 8k 12 1.8M
Zetta (ς) 9M 3k 7 0.8M

As can be seen from Table 1, the activity of the conventional Beta (δ) branch is more ef-
ficient. Because the final results of a beta branch are more efficient, the figures for the
above-mentioned indicators are taken as a scale for analyzing the performance of other
branches.
Thus, as a result of research and analysis, the adoption of the following provisions is
considered necessary.
Beta affiliate scale:
A) how much the bank's resources should be reduced while the profits of other branches
(results obtained on the given indicators) remain the same.
B) how much the profits of other branches should increase in accordance with the indi-
cators given in Table 1, while the resources of other branches remain at the same level.
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DEA | Data Envelopment Analysis Method.

The DEA calculation methodology was developed in 1978 by professors A.Charnes,
W.Cooper, E.Rhodes, who work in prestigious scientific institutions of the United States
and are the authors of a wide range of scientific theoretical knowledge in this field. This
method of calculating efficiency by scientists allows to automatically determine the specific
gravity of efficiency. In 1984, R.Banker, A.Charnes and W.Cooper redesigned and
modified this calculation method and developed a new method for calculating efficiency,
the VRS (Variable Return to Scale) format.
Table 2. shows the automatic determination of specific gravity for efficiency (Example # 1).

Table 2. Automatic determination of specific gravity for efficiency (Example # 1)

Filial A B C D E F G H
Number of employees 2 3 3 4 5 5 6 8
Sales 1 3 2 3 4 2 3 5

Sales/ Employees 0.5 1 0.667 0.75 0.8 0.4 0.5 0.625

Figure 2. Shows the change in efficiency depending on the number of employees and
sales.

Sales

Limit of effectiveness

A2

The number of employees

Figure 2. Changes in the efficiency of bank branches depending

on the number of employees and sales

As is known from the form of the study, when calculating the efficiency, the number of
employees is taken as input, and sales is taken as output. To measure the effectiveness of
the bank's branches, the sales figure per employee (sales / employee) is calculated.
Thus, depending on the 2D graph, the relevant points are identified and it becomes clear
that the most effective branch is B branch. Depending on the schedule, each branch that

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falls within a given efficiency limit is considered effective. A1 and A2 are projections of A
on the efficiency limit.
Depending on the above number of employees and the schedule of changes in the effici-
ency of bank branches depending on sales, it is clear that branches E, D and C are effici-
ent branches. The threshold of efficiency also crosses them accordingly. Branches that
achieve a single result with less resources are considered more efficient. Other branches
are not considered effective because they are located outside the specified dependency
schedule.
Branches E and D are considered referent clusters for branch A. Projection of branch A
anywhere on the ED section is considered effective.
Table 3 shows the change in efficiency in bank branches depending on the number of
employees and sales (Example # 2).

Table 3. Variation of efficiency depending on the number

of employees and sales (Example # 2)

Branch
A B C D E F G H I
(conventional) signs
Number of
4 7 8 4 2 5 6 5.5 6
employees (x1)
Branch area (x2) 3 3 1 2 4 2 4 2.5 2.5
Sales (y) 1k 1k 1k 1k 1k 1k 1k 1k 1k

CRS (crste). Output Orientated. As can be seen from Table 3, 4 branches are effective
(R2, C1, C4, C6). Column F shows the efficiency ratios of the branches. For ineffective
branches to be effective, the following must be paid: the number of branches, the number
of employees and the assets (A, B, C) should remain the same and increase to the figure
in the Profit (D) Project (E) (CRS (crste) on the scale of effective branches.

Input Orientated.
It turns out that the effective branches remain the same (R2, C1, C4, C6). Column E
shows the projection of assets. For inefficient branches to be effective, the following
results must be obtained: Profit (D) must remain the same and Assets (C) must decrease
to the figure (E) in the Projection (on the scale of effective branches). The number of
branches and the number of employees are calculated in a similar way.
Scale Efficiency.
Column G shows the efficiency figures using the Variable Return to Scale Technical
Efficiency method. Column H shows the number SE (Scale Efficiency).
SE is calculated by the ratio of crste to vrste.
Figure 3 shows the change in the efficiency of bank branches depending on the number of
employees and sales.

Conclusion:
CCR – regional bank branches are less efficient than city bank branches.
BCC – the efficiency of regional banks is growing.
SE – profit ratios of all city bank branches are higher than the average, and half of the
branches of regional banks are lower.

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x2/y

Limit of effectiveness

x1/y

Figure 3. Changes in the efficiency of banking activities depending

on the number of employees and sales

CCR – constant Return to Scale.

BCC – variable Return to Scale.
There are two main directions of the DEA methodology:
CCR (Charnes Cooper Rhodes) or CRS (Constant Return to Scale) method.
Constant scale effect - in this method, the proportional increase in inputs leads to an
increase in output with a linear dependence. It is called the BCC (Banker Charnes Cooper)
or VRS (Variable Return to Scale) methodology.
Variable scale effect method - the change of inputs in the calculation of efficiency under
this method leads to a disproportionate change in output. With this method, the number of
effective dmu can be much higher.
Figure 4 shows the change in the efficiency limit depending on the resource Input
(resource) and output (output) parameters.
How much the output should increase - the efficiency of the activity - how much the results
should increase while the resources of the inefficient branch remain the same on the scale
of the effective branch. How much resources (input) should be reduced - How much
resources should be reduced while the results of an inactive branch remain the same on
the scale of an effective branch.
As we can see in the graph, there are points just below the efficiency curve. If the ratio
were to be expressed by a point above the curve, it would be considered more efficient
and the curve itself would move beyond the new ratio.
Criteria that determine the innovative activity of the bank and affect the efficiency of the
bank's branches - GTK, birkart, debit card, Deposit, BirBank, Waiting Time, No show,
service time, profit, assets, FTP, rent, 'fee expenses, other costs, number of customers,
number of employees, branch potential, workload, efficiency of bank branches based on
GRS, Loan Sales, Perspective and Financial Perspective method were determined and it

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Limit of effectiveness

Limit of effectiveness

Figure 4. Resource efficiency variation depending

on resource Input and output parameters

was found that the results obtained by Financial Perspective method (total effection) is hig-
her. The specific weight of the bank's branches on efficiency was determined automati-
cally. Depending on the number of employees and sales in the bank's branches, the
change in the efficiency of the bank's activity was calculated. Depending on the resource
input and output parameters, the efficiency limit is determined.

REFERENCES

1. Lewis H. F. Network DEA: efficiency analysis of organizations with complex internal

structure. / Lewis H, Sexton T. // Computers and Operations Research. – 2004. – Vol.31. –
P.1365-410.
2. Liang L. Data envelopment analysis efficiency in two-stage networks with feedback. /
Liang Liang [h jip.] II HE Transactions. – 2011. – Vol.43. – P.309-322.
3. Liang L. DEA Models for Two-Stage Processes: Game Approach and Efficiency Decom-
position / L. Liang, W. D. Cook and J. Zhu // Naval Research Logistics. – 2008. – Vol.55,
№7. – P.643-653.
4. Lotfi F.H. A new two-stage data envelopment analysis (DEA) model for evaluating the
branch performance of banks / F. Hosseinzadeh Lotfi [h ^p.] // African Journal of Business
Management. – 2012. – Vol.6(24). – P.7230-7241.
5. Lotfi F. Ranking of DMUs on Interval Data by DEA // F. Hosseinzadeh Lotfi [h AP-] // Int.
J. Contemp. Math. Sciences. – 2007. – Vol.2, №4. – P.195-201.
6. Liu J. Data envelopment analysis 1978-2010: A citation-based literature survey /.Liu J.
S. // Omega. – 2012. DOI:10.1016/j.omega.2010.12.006.
7. Liu H. A Comparison of Three-Stage DEA and Artificial Neural Network on the Operatio-
nal Efficiency of Semi-Conductor Firms in Taiwan / Hsiang-Hsi Liu, Tser-Yieth Chen,
Yung-Ho Chiu, Fu-Hsiang Kuo // Modern Economy. – 2013. – Vol.4. – P.20-31.

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XÜLASƏ
M.O. Nağıyev
Bank fəaliyyətinin səmərəliliyinin qiymətləndirilməsi üçün
iqtisadi modelləşdirmənin tətbiqi

Bankların fəaliyyətinin səmərəliliyinin qiymətləndirilməsinə xas olan yanaşmaların bir növü

nəzərdən keçirilmişdir. Bank müəssisəsinin səmərəlilik səviyyəsini müəyyən etmək üçün
istifadə edilə bilən bir alqoritm işlənib hazırlamış, risk zonaları, səmərəliliyin hesablanması
üçün lazım olan amillər müəyyən edilmişdir. Geniş tədqiqatın nəticələrinə əsasən, səmərə-
liliyin tapılması alqoritmi hazırlanmışdır ki, bunun əsasında hər müəssisə üçün effektivlik
sinfini müəyyən etmək üçün reytinq cədvəli tərtib etmək mümkündür. Xüsusilə, bu iş ayrı-
ayrı qurumun fəaliyyətini təşkil edən amillər baxımından davamlı iş üçün dəyərlidir. Bütün
bank fəaliyyətinin səmərəliliyini artırmaq üçün bankın innovativ fəaliyyətinin idarə edilməsi
mexanizminin qurulması innovativ ideyaların təşkilati konsentrasiyası prinsipi və məhdud
innovasiya layihəsi prinsipi ilə tamamlanan müəssisə idarəetməsinin ümumi qəbul edilmiş
prinsiplərinə əsaslanır [1]. Bank biznesinin inkişafı üçün müştəri yönümlü strategiya ilə əla-
qədar olaraq müştəri diqqəti və təşəbbüskarlıq prinsipləri həmişə diqqətə alınır. Fəaliyyətin
ölçülə bilənlik və effektivlik prinsiplərinin həyata keçirilməsi bank fəaliyyətinin səmərəliliyini
qiymətləndirmək üçün istifadə oluna bilən göstəricilər sisteminin yaradılması zərurəti ilə
bağlıdır. İnnovasiyaların tətbiqi ilə bankın işinin ümumilikdə səmərəli fəaliyyətində müxtəlif
növ amillərin təsiri mühüm rol oynayır. Məqalədə bank innovasiyalarının tətbiqi sayəsində
filialların işinin səmərəliliyin qiymətləndirilməsinin ənənəvi (maliyyə), ehtimal və keyfiyyət
üsulları təhlil edilir. Bank innovasiyalarının tətbiqi üstünlükləri və çatışmazlıqları, o cümlə-
dən bank innovasiyalarının bütün növlərinin effektivliyi qiymətləndirilmişdir. Səmərəli bank
fəaliyyətinin idarə edilməsi mexanizminin qurulmasında BSC üsulu məqsədəuyğundur.
Məqalədə həmçinin bank biznesinin pərakəndə seqmentində innovativ məhsul və texnolo-
giyaların tətbiqinin səmərəliliyinin və rəqabət qabiliyyətinin artırılmasına töhfə verən göstə-
ricilərin bank sisteminin formalaşdırılması üçün əhəmiyyətli olması müəyyənləşdirilmişdir.
Açar sözlər: bank fəaliyyəti, səmərəliliyin qiymətləndirilməsi, maliyyə, DEA (əməliyyat mü-
hitinin təhlili) metodologiyası, resurs parametrləri, çıxış prametrləri, effektivlik sərhədi, iqti-
sadi modelləşdirmə

РЕЗЮМЕ
М.О. Нагиев
Применение экономического моделирования для оценки
эффективности банковской деятельности

Рассматривается ряд подходов к оценке эффективности банков. Разработан алго-

ритм, с помощью которого можно определить уровень эффективности банковского
предприятия, выделены зоны риска. По результатам обширных исследований раз-
работан алгоритм определения эффективности, на основании которого можно со-
ставить рейтинговую таблицу для определения класса эффективности для каждого
предприятия. В частности, эта работа ценна для устойчивой работы с точки зрения
факторов, составляющих деятельность отдельного учреждения. Создание механиз-
ма управления инновациями банка для повышения эффективности всей банковской
деятельности основывается на общепринятых принципах управления предприятием,
дополненных принципом организационной концентрации инновационных идей и
принципом ограниченного инновационного проекта [1]. Реализация принципов изме-
римости и эффективности связана с необходимостью создания системы показате-
лей, которые можно использовать для оценки эффективности банковской деятель-

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ности. При применении инноваций важную роль в общей эффективности банка игра-
ет влияние различных факторов. Анализируются традиционные (финансовые), ве-
роятностные и качественные методы оценки эффективности деятельности филиа-
лов за счет применения банковских инноваций. Оценены преимущества и недостат-
ки применения банковских инноваций, а также эффективность всех видов банков-
ских инноваций. После дальнейшего изучения возможностей использования банков-
ских инноваций был сделан вывод о целесообразности метода БСК в создании эф-
фективного механизма банковского управления. Также в статье определена важ-
ность показателей формирования банковской системы, которые способствуют эф-
фективности и конкурентоспособности применения инновационных продуктов и тех-
нологий в розничном сегменте банковского бизнеса.
Ключевые слова: банковское дело, оценка эффективности, финансы, методология
DEA (анализ операционной среды), ресурсные параметры, выходные параметры,
запас эффективности, экономическое моделирование.

Publishing history
Article accepted: 22.04.2022
Article received: 25.08.2022

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 Ünvan: AZ1010, Bakı, Azadlıq prospekti, 20
Telefon: (99412) 598-44-77; Faks: (99412) 598-65-61
Elektron poçtu: [email protected]

Jurnal 1999-cu ilin iyun ayından nəşr olunur