Journal of Natural Science and Technologies

NaSTech
JOURNAL OF NATURAL
SCIENCE AND TECHNOLOGIES
Volume:1 Sayı: 1 December 2022
ISSN: 2822-681X
www.journalofnastech.com
Journal of Natural Sciences and Technologies
Volume 1 Number 1 December 2022
NaSTech
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Volume: 1 / Number: 1 / December - 2022

CONTENTS
RESEARCH ARTICLES

3D PRINTED PAVING STONES: A LAB-SCALE RESEARCH 1

Volkan ARSLAN, Zekeriya DOĞAN
AN INVESTIGATION OF MOLECULAR SPECTROSCOPY WITH GEOMETRIC ALGEBRA 7
Baghdad Abdulhameed Abdullah AL-BADANI, Abidin KILIÇ
JUSTIFICATION OF THE CHOICE OF CATALYST FOR THE OXIDATION OF C3- C4 ALDEHYDES INTO ACIDS 19
AND THEIR MODIFICATION
Elmira HUSEYNOVA, Ulkar SHIRALIYEVA, Nasiba IMANOVA, Ziba BAGIROVA, Kamala ISMAYILOVA, Saida
NADJAFOVA

NUMERICAL AND EXPERIMENTAL INVESTIGATION ON THE REPAIR IMPACT OF ARROW-SHAPED AND 24

HEXAGONAL GLASS-EPOXY COMPOSITE PATCHES
Mohammadjavad RANJBARAN, Seyed Masoud HOSSEINI
INVESTIGATION OF FRACTURE PREVENTION EFFECTS OF COMPOSITE PATCHES REPAIR ON CRACKED 38
ALUMINUM PLATES EXPERIMENTAL AND NUMERICAL STUDY
Mohammadjavad RANJBARAN
THE EFFECT OF ADDING ARTIFICIAL NOISE ON THE SUCCESS OF A DEEP LEARNING NETWORK 51
Utku KAYA
FRACTAL AND MULTI-FRACTAL ANALYSES OF THE GEOMAGNETIC FIELD VARIATIONS CAUSED BY THE 52
EARTHQUAKE ON JANUARY 24, 2020 IN TURKEY
Andriy ONISHCHENKO, Leonid CHERNOGOR, Oleg LAZORENKO
APPLYING OF THE NEW GENERATION PLASTIC ADDITIVES TO THE KITCHEN APPLIANCES: 56

INVESTIGATION OF STRUCTURAL AND THERMOSTATIC PROPERTIES OF ORGANOMETALLIC MN (II) AND
CU (II) STREAT- BORATE COMPLEXES
İlkan KAVLAK
FLEXIBLE PRINTED STRUCTURES QUALITY MODELS FOR MOBILE ROBOT PLATFORM 57

Iryna ZHARIKOVA, Viktoriia NEVLİUDOVA, Olena CHALA
ROBOT GROUP INTERACTION TECHNOLOGY USING A CLOUD SERVER 85

Igor NEVLIUDOV, Shakhin OMAROV, Serhii TESLIUK, Serhii NOVOSELOV, Oksana SYCHOVA
A STUDY ON AIR QUALITY NEAR SOLID WASTE TREATMENT PLANTS AMONG UNIVERSITY POPULATION: 93
ADANA CASE
Tugce PEKDOGAN
COMPARISON OF ENERGY EFFICIENCY STUDIES OF TURKEY AND GERMANY 100

Fatih Burak ÖZKANLI, Zafer DEMİR
MOLECULAR STRUCTURE, NBO AND TD-DFT ANALYSIS OF 4-METHYL-3-FURALDEHYDE BASED ON DFT 113
CALCULATIONS
Nihal KUŞ
ELECTROMAGNETIC ENERGY CONSERVATION BY BIQUATERNIONS 124
Nur ULUHAN, Abidin KILIÇ
PREPERATION OF MCM-48 LOADED WITH LAVENDER OIL AND VITAMIN E UNDER SUPERCRITICAL 135
CARBONDIOXIDE CONDITIONS AND ITS USE IN PEEL FORMULATION
Derya KILIÇ, Emine KUTLU, Muhammad Asım ALİ, Fatih Mehmet EMEN, Ruken Esra DEMİRDÖĞEN
SYNTHESIS OF PYRIDINE DERIVATIVE POLYMERIC COPPER COMPLEX WITH METAL-AZID BONDS 143
Fatih Mehmet EMEN, Ruken Esra DEMİRDÖĞEN
DEVELOPMENT OF AN ECO-FRIENDLY EFFICIENT RECOVERY METHOD FOR NICKEL CATALYST FROM 151
INDUSTRIAL WASTES
Ruken Esra DEMİRDÖĞEN, Fatih Mehmet EMEN
2022, 1(1), pp. 1-6, DOI: 10.5281/zenodo.7241339
3D PRINTED PAVING STONES: A LAB-SCALE RESEARCH
Volkan ARSLAN1,*, Zekeriya DOĞAN2

1,2
Department of Civil Engineering, Faculty of Engineering, Zonguldak Bulent Ecevit University, Zonguldak, Turkey
ABSTRACT
Recent developments lead to changes in the construction industry as well as in many other industries. Three dimensional (3D)
printing technology emerges as a new production method that has become popular in the construction industry. Up to date, the
manufacturing industry has been utilized 3D printing technology in order to provide automation, production acceleration and waste
reduction. However, 3D printing technology is relatively a new concept in the construction industry.
The main methods for producing with 3D printers are (i) additive manufacturing method, (ii) contour work, (iii) concrete printing
and (iv) D-shaped process. In addition to the production methods, the mixtures used in 3D printing process also have a significant
impact on the production quality. Therefore, design of printable mixture should be investigated carefully.
The main objective of this study is to investigate production process of concrete paving stones using 3D printing technology.
However, 3D printers which can print concrete mixtures are rare. Therefore, a 3D printer was designed and built through purchasing
of necessary equipment from several suppliers. Suitable concrete mixtures was also be prepared by utilizing construction materials
to reach an applicable solution for concrete paving stones. The obtained results present a new method in concrete paving stones
production and a 3D printer which is suitable for concrete printing. For the future studies, different materials can be printed through
modification of 3D printer and preparation of new mixtures.
Keywords: 3D printer, construction technology, construction industry
1. INTRODUCTION
Recent developments in the world of science and technology have resulted in the emergence and
development of new design, fabrication and constriction techniques [1]. Additive manufacturing techniques
have gained a solid presence in many areas of industry over the past 30 years [2]. 3D printing (3DP) of
concrete structures results in higher precision, safer working conditions, faster construction, and lower cost
of construction due to avoiding the costs associated with formwork and labor [3].
The construction industry has traditionally relied on two-dimensional (2D) drawings to convey material
properties, performance details and location information. However, with the impact of technological
developments on the construction industry, working with 3D models has gained popularity [4]. Another
alternative to 3D modeling is the use of advanced 3D solid modeling techniques combined with digital
fabrication methods [5]. This method later turned into productions using the 3D printer technique. The 3D
printer technique draws attention in the construction industry due to its advantages over traditional
manufacturing methods [6-7].
2. LITERATUR REVIEW
In the literature, there are studies examining the mixture designs and mechanical properties of concrete
prints made with 3D printers. In addition to this, there are also studies conducted in order to investigate
production process of bricks/briquettes from clay and ceramic materials. Moreover, researchers investigate
the technical properties of these materials such as strength and thermal insulation [2-8]. However, there is
no study in the literature on the mechanical or design properties of the concrete paving stones. Concrete
paving stones can be produced in various geometric shapes and have a wide range of applications in terms
of 3D printing. As can be seen in the literature review presented in this section, most of the studies on
concrete production with 3D printers have been carried out theoretically.
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2022, 1(1), pp. 1-6, DOI: 10.5281/zenodo.7241339
Most of the past studies was conducted on the constructability and mechanical properties of 3D printed
concrete. Paul et al. [9] designed a mixing ratio for 3D printing using cement, and the 28-day compressive
strength of the produced concrete was measured as 36-57 MPa and the bending strength as 10 MPa. Le et
al. [10] developed a high strength fiber reinforced concrete with a compressive strength of 92 MPa and a
flexural strength of 11 MPa. Ma et al. [6] used copper waste to develop a printable cementitious mix with
good workability and 50 MPa compressive strength. Ting et al. [11] evaluated the effects of material
parameters on extrudability and constructability of concrete. Here, material parameters such as glass-binder
ratio, fineness modulus and nano-clay content were investigated using the mixture design diagram. Gomaa
et al. [12] and Alqenaee and Memari [3] focused on creating a 3D printable, environmentally friendly clay-
based mix. As a result, a printable clay-based cob mix design in which the components have sufficient
strength for construction was developed, Hojati et al. [13] conducted a study aiming to replace the cement
in the mixtures with other cementitious alternatives and to design sustainable mixtures suitable for 3D
printing. In the study, the concrete components were designed to be suitable for printing. After that the
mixture evaluated in terms of print quality and mechanical performance. Ghanbari-Ghazijahani et al. [1]
target to design a material converted into filaments for printing from waste wood and polylactic acid. They
tested this material against breaking under three-point bending structurally through 3D printed fourteen
composite beams. Overall, they noted promising results for the development of various 3D-printed
structural materials.
The number of studies on building materials produced with 3D printers is less than studies examining the
design and mechanical properties of mixtures. As mentioned above, studies were generally on the behavior
of concrete mixes. In addition, there are studies on building elements or construction materials. Alhumayani
et al. [14] compared the environmental impacts of large-scale 3D printer manufacturing according to two
different types of construction materials, concrete and cob. In the study, reinforced concrete wall, cob wall,
3D-printed concrete wall and 3D-printed cob wall were compared in terms of environmental effects. As a
result, cob wall has the lowest impact on global warming, while concrete wall has the highest impact.
However, a concrete wall produced with a 3D printer has 50% less negative impact than a concrete wall.
The most important factor here is the use of steel in the traditional concrete wall. Alkhalidi and Hatuqay
[15] investigated sustainable, energy efficient and low cost housing production with 3D printers. They
focused more on the thermal comfort of the occupants than on the durability of the 3D-printed buildings.
As a result, they have presented a guideline adapted to different climatic conditions to create an energy-
efficient, comfortable 3D-printed living environment. Tahmasebinia et al. [16] aimed to determine
sustainable performance criteria for buildings produced using 3D printers. In this study, minimizing the
effect of waste generation was investigated through a model designed in computer environment. According
to the results, it was understood that the tensile stresses formed in the recycled high-density polyethylene
concrete composite remained within the expected limits. In addition, the geometric composition of the
exterior of the structure helps to create passive insulation against heat ingress. Marais et al. [17] tried to
measure the thermal performance of 3D-printed lightweight foam concrete and high-performance concrete
elements. The results obtained presents that 3D-printed hollow walls tend to perform better when fabricated
with materials with higher thermal conductivity. Materials with lower thermal conductivity perform better
as void-free walls. Gebhard et al. [18] researched the structural response and crack modeling and kinematics
of various reinforcement approaches for 3D printed beams. Consequently, it was observed that the post-
tensioned beams broke brittle due to the crushing of the concrete and deformations during bending. Beams
with bonded conventional reinforcement, on the other hand, showed multiple bending and shear cracks that
allowed the interlayer shear reinforcement to be activated. Zhu et al. [19] experienced the bending behavior
of 3D-printed composite beams with different geometric properties. All these beams showed a ductile
behavior and provided good shape uniformity. Also, the ultimate bending load of the beams was greatly
influenced by the geometric properties. This shows that the structural elements must be adapted to the
required geometric properties to obtain the best mechanical performance in terms of compressive strength.
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2022, 1(1), pp. 1-6, DOI: 10.5281/zenodo.7241339
Most of the current literature in this field focus on printing cement-based concrete. In the past studies, there
is no study on the production process of 3D printed concrete paving stones. However, very little research
has been done on building materials produced with 3D printers. It is understood that majority the past
studies were aimed to investigate concrete mixtures by using different materials. However, studies
examining mixtures of clay and mud brick are also substantial. Finally, most of the research on
manufacturing with 3D printing has been carried out on a laboratory scale.
This study is the first attempt in researching 3D printing process of concrete paving stones. Moreover,
traditional concrete paving stone production will be compared with 3D printed ones. Finally, this study may
be beneficial for researcher to investigate different construction materials.
3. MATERIALS AND METHOD
The mechanical part of the 3D concrete paving printer to be manufactured in the study was designed with
inspiration from delta FDM printers.
2.1. 3D Printer Mechanical Part
The printer chassis will be formed with 30x30 aluminum sigma profiles (Figure 1). Plastic parts produced
from FDM (Melted Filament Production), stainless steel bolts and nuts printers will be used in the
connection stage. Flexible plastic elevations will be attached to the printer's feet to prevent mechanical
vibration.
Figure 1
The movement in the axes will be provided by three Nema 17 step motors utilizing the delta arm design.
The ground on which the paving stone will be produced will not perform axis movement. Double extruder
will be used to make the first contact of cement mortar and chemical during the printing process. Flow
settings in each extruder will be made with mechanical and software calibrations. Extrusion materials will
be directed to the extrusion stage through hoses from a separate chassis independent of the printer. Cement
mortar and accelerating admixture will be extruded using stepper motor and archimedean screws.
2.1.1. Software and calibration
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2022, 1(1), pp. 1-6, DOI: 10.5281/zenodo.7241339
The software of the printer will be implemented with an open-source Marlin software to be suitable for
development by third parties. In the calibration phase, open-source computer supported Repetier Host
program will be used. Stages such as step settings of the axes, speed, and acceleration will be tested with
measuring instruments during the calibration phase and will be processed into the software through the
Repetier Host program. As mentioned above, the extrusion flow calculations will be tested until the
optimum values are reached during the calibration phase. The optimum values obtained will be transferred
to the software.
2.1.2. Security
An emergency button will be placed on the 3d printer to cut the electricity of the system will be in case of
any unexpected situation. A fuse will be installed in the power supply to protect the mainboard. The power
supply is selected as 12V 15A. In this way, the printer will consume a maximum of 180W per hour.
2.1.3. Production
The. stl (standard triangle language) file format of the paving stone designed during the production phase
will be sliced with the open source G-code (program language of CNC machines) generator using simply
program and then will be saved to the SD card. Production will be started via the control panel by inserting
the SD card into the printer. In addition, G-codes such as speed, extrusion flow rate can be intervened via
the control panel.
2.1. Concrete Mixture Design
It is important to obtained satisfactory results from 3D printed concrete paving stones in terms of durability
of concrete. The strength variable of cement-based binder building materials is mostly associated with the
composite. This shows that the printing quality, writing speed, and adherence between the layers of the
concrete mixture will be important. A quick setting of concrete may cause cold joint may be encountered
between the layers and the distribution channels of the hydration liquid in the total mass may be blocked.
A concrete mixture which sets too slow, may cause collapse of concrete due to the weight of the upper
layers. To determine this optimum pressure setting duration, the effects of a standard cement mortar mixture
and accelerating admixtures in certain proportions will be measured with an automatic vicat apparatus.
Amount and percentage of accelerating admixtures used have an important effect to maintain consistency
of concrete mixture through the printing process. Therefore, cement mortar and accelerating admixture will
be injected from separate extruders. The addition of the remainder of the chemical that will provide the
correct setting time will be during the exit of the cement mortar from the extruder and setting reactions will
be initiated on the application surface. Moreover, the pumping speed of accelerating admixture will be
calibrated in accordance with the printing speed via software. In this case, it is essential that the cement
mortar and the chemical can be pumped separately, and both can be intervened externally. In this study,
concrete mortar mixture ratios were designed in accordance with the mixing ratios specified in TS EN 196
1 coded standard. Accordingly, the concrete mortar will consist of 450 gr of cement, 1350 gr of aggregate
and 225 gr of water. Finally, 3D printed concrete will have an opportunity to be compared in accordance
with related standards.
4. RESULTS AND DISCUSSION
4.1 3D Printed Paving Stones
The most critical stage of the work is the 3D printing of the concrete paving stones. In this stage, concrete
paving stones will be produced in accordance to TS 2824 EN 1338, using the designed 3D printer and the
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2022, 1(1), pp. 1-6, DOI: 10.5281/zenodo.7241339
prepared mixtures. In this process, it is expected that the mortar can be pumped, shaped, adhered to one
another without losing its shape, and set. If it is noticed that a mixture with the desired properties cannot be
created, changes will be made in the design of the mixture, and the process will be repeated until the desired
concrete paving stones are obtained.
4.2 Performance Tests
It is planned to perform pressure tests in accordance with TS EN 12390-3 to determine the compressive
strength of the produced concrete paving stones. The samples of printed concrete will be taken from
different sides. Then, 3D printed samples will be tested after curing at 21±2 °C for 28 days... In order to
determine the flexural strength, tests will be performed on control samples and 3D printable mortar samples
in accordance with TS EN 12390-5. The machines and equipment required to carry out the above-
mentioned tests are available in the Construction Materials Laboratory of the Faculty of Engineering of
Zonguldak Bülent Ecevit University.
5. CONCLUSION
The main aim of this study was to build a 3D printer to produce 3D printed paving stones in a lab size scale.
For this reason, a new concept of 3D printer which can print concrete-based mixtures will be designed.
After that concrete paving stones will be produced in several geometric shapes. Finally, mechanic, and
economic properties of 3D printed concrete paving stones were analyzed.
Future research will be carried out to find the relation between mixture design, printing behavior and
mechanical properties of construction materials for printing. Moreover, possibility of printing different
construction materials will be investigated to explore application in the construction industry.
ACKNOWLEDGEMENTS
The authors thank the financial supports provided by Zonguldak Bulent Ecevit University. This study is
based on an on-going research project which is financially supported by Zonguldak Bulent Ecevit
University Scientific Research Projects (BAP) Coordination Unit under the grant number 2022-37891158-
01.
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[13] Hojati M, Li Z, Memari A M, Park K, Zahabi M, Nazarian S, Duarte J P, Radlińska A. 3D-printable
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6
JOURNAL OF NATURAL SCIENCES AND TECHNOLOGIES
2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
AN INVESTIGATION OF MOLECULAR SPECTROSCOPY WITH GEOMETRIC

ALGEBRA
Baghdad Abdulhameed Abdullah AL-BADANI1,*, Abidin KILIÇ2
Department of physics, Faculty of Science, Eskişehir Technical University, Eskişehir, Turkey
ABSTRACT
In this study Geometric Algebra was used to create a general and practical method for obtaining the operators of the kinetic
energy of the molecular vibration-rotation of polyatomic molecules. On the other hand, these polyatomic molecules' precise
intrinsic kinetic energy operators include a metric tensor. The elements of this metric tensor were expressed as the mass-
weighted sum of measuring vector inner product vectors compatible with the molecule's nucleus. Whereas, the vibrational and
rotational measuring vectors that appear in the metric tensor for any geometrically defined coordinates of the shape and frames
of the body were easily determined using geometric algebra. The current method (geometric algebra) generates molecular
vibration-rotation kinetic energy operators that are in perfect agreement with earlier studies.
Finally, we have used the Lagrangian Formulation where the component of kinetic energy was expressed in the form of
generalized velocities.Using geometric products, we discovered the relation between the covariant metric tensor and the
contravariant metric tensor.
Keywords: Geometric Algebra, Operator of the kinetic energy, covariant metric tensor, Rotational measuring vectors,
Vibrational measuring vectors
1. INTRODUCTION
Algebra is the branch of mathematics that deals with general statements of relations, utilizing letters and
other symbols to represent specific sets of numbers, values, vectors, etc., in the description of such
relations. There are basic rules by which an expression can be algebraic. These basic rules are
!(# + %) = !# + !% Distributive property
!(# + %) = (# + %) Commutative property
!(#%) = #(!%) = %(!#) Combination property
! + 0 = !, !⋅1=! Identity property
! + (−!) = 0, ! ⋅ 1! = 1 Inverse property
Where !, # and % are arbitrary numbers.

Geometric algebra is a numerical technique that simplifies the description of geometric concepts and
procedures [1]. Geometric algebra also called "Clifford algebra" and sometimes called "hyper complex
numbers" to describe a generalization of the complex number and the quaternions, was first introduced
by William Kingdon Clifford in 1878, in his article "Grasman's Application of Extended Algebra" in
the American Journal of Pure and Applied Mathematics [2].
Clifford was much more affected by Grassmann's research and utilized it as a starting point for
establishing geometric algebra and combining external and internal products into a distinct engineering
product, a new product form [3].
Geometric algebra is also an algebra because it provides the basic rules for algebra. Geometric algebra
makes simple definitions with some special rules used for the product of vectors. It is an algebra that
extends real number systems and is an ideal language for physics, often used in mathematical physics.
Clifford Algebra contains the elements of area and volume, thanks to the basic elements it contains.
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2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
The expression of geometric algebra,

! ..⃗ = !
...⃗ # ...⃗ ∙ ..⃗
# + ...⃗ ..⃗
! ∧ # (1)
a ∙ ...⃗
Here ..⃗ b is the dot product and is a scalar expression. The expression a ...⃗ is the outer product.
..⃗ ∧ b
The outer product expression is denoted by the wedge sign “ ∧ “. The outer product is neither a scalar
nor a vector. It is a new element called the bivectors.
Clifford Algebra has three orthogonal unit base vectors 4̂! , 4̂" , 4̂# . Since these unit basis vectors are
perpendicular to each other, 4̂! " = 4̂" " = 4̂# " = 1 .
The oriented plane area of the square with sides e! and e" is expressed by the product 4! 4" , that is a
new type of quantity known as a bivector. As shown in figure 1. Write for short e! " = 4! 4" .
Figure 1. Express the Bivectors
1.1. Relations and Geometric Transformations

In geometrical algebra, every geometric point being expressed as a vector, and each geometric parameter
may be explained in terms of its exceptional qualities without the need of any external coordinate frames.
..⃗, for instance, may be divided into parallel and orthogonal components. Figure 2. Depicts
Any vector 7
the computation of the component of 7 ..⃗in the direction of 8
..⃗ when the two vectors form an angle of 0 <
θ < 180 degrees.
Figure 2. Decomposition of !
##⃗ vector to components along and perpendicular to a vector %
##⃗
%
The parallel variable is the scalar multiple of the unit vector |'|.
" "
s∥ = |s| cos θ |$| = |s||r| cos θ |$|! (2)
In other words, the parallel component s∥ is the scalar product s ∙ r = |7||8| cos θ multiplied by the
'
vector r )! =|'|! , also known as the vector r⃑ inverse. As a result
% (3)
s∥ = ( s ∙ r) |'|! = ( s ∙ r ) 8 )!
The perpendicular component 7* is defined as the difference
s* = s − s∥ = s − ( s ∙ r ) 8 )! = (sr − s ∙ r ) r )! = (s ∧ r ) r )! (4)
The reflection of 7 across the line u as shown in figure 3(a). Is acquired by sending 7 = 7∥ + 7* to 7 + =
7∥ − 7* where s∥ = (s ∙ u)u)! . The mirror image u+ of u for s is then
s+ = usu)! (5)
We may represent the dot and outer products in Eq (2) in regards of the angle between both the vectors C.
! (6)
s
.⃗ ∙ . r⃗ = " ( s
.⃗ r
.⃗ + r⃗ s
.⃗) = | s
.⃗| |r⃗ | cos θ
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2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
! (7)
s
.⃗ ∧ r⃗ = " ( s
.⃗ r
.⃗ − r⃗. s⃗ ) = i| s
.⃗| |r⃗ | sin θ
Eqs. (6) and (7) how to construct the geometric product of unit vectors, which results in a useful formula
for rotating a vector in a plane. If the unit bivector for the longitudinal plane the unit vectors . s⃗ and . r⃗ is
F then the geometric product is represented as [4]
.⃗ = cos θ + i sin θ = e,-
. s⃗ r (8)
The e,- exponential, commonly known as a two-dimensional rotor.

As seen in figure 3(b), multiplying a vector s by the rotor produces a new vector s+ , which is the old
vector rotated in the F plane by the angle C.
s+ = s e,- = s cos θ + sF sin θ (9)
Since the unit bivector F ant commutes with every vector s in the e! e" plane, the rotated vector can also
be expressed as:
s cos θ + si sin θ = s cos θ − is sin θ = e),- s (10)
Furthermore, we have
- - (11)
cos θ + i sin θ = (cos " + i sin " )"
And the rotated vector also has the form G )! as where
- - (12)
y = e, ." And y )! = e), ."
The same Eq (8) applies to the rotation of any Multivector I (a vector, a bivector, etc., or any
combination thereof).
If Multivector I rotates across a bivector angle φ , then I+ is obtained by sandwiching the multivector
I between rotation plane exponentials.
0 0 (13)
I+ = 4 )/ ." I 4 / ."
(a) (b)
Figure 3. (a) Reflection of ! along - ;( b) Rotation of vector ! in the plane .
1.2. Internal Coordinate Gradients

In geometric algebra, the gradients K1 L/ are the vector derivatives of the coordinate L/ with respect to
the spatial position vector x2 , that is
K1 L/ = N3" L/ (14)
The vector derivative operator ∇2 is expressed in some coordinates using the chain rule as
N (15)
K1 = P(K1 L/ )
NL/
/
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2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
Where we utilize the subscript Q in the vector round as to underline that these conclusions apply to
several vector elements x! , x" , … .
Much of the calculations for gradients resemble those of the usual scalar calculus. For example, If F and
G are vectors, the vector differentiation is distributive
K1 (U + V) = K1 U + K1 V (16)
Furthermore, if γ = γXx2 Y seems to be a scalar-valued function, therefore

K1 (ZV) = (K1 Z)V + Z K1 V (17)
If U = [( \1 ), the definitions of its divergence and curl are as follows
]F^1 [ = K1 ⋅ [ (18)
By using geometric product definition we can write
K1 [ = K1 ⋅ [ + K1 ∧ [ = K1 ⋅ [ + FK1 × [ (19)
As a result, the scalar component of the Eq (19) is the divergence, and the other component is the curl.
Because the last form is restricted to three dimensions, it is better to conceive of the curl as the bivectors
element of the vector derivative. [5].
In general, the vector derivative K1 U , F is constructed for all elements U, not only vectors and scalars
K1 U = K1 ⋅ U + K1 ∧ U (20)
Eqs (16) and (17) provide distributive vector differentiation but, in practice, the operator of the vector
derivative doesn't quite actually commute with Multivector, so the product rule should be phrased as
K1 (UV) = K`1 Ù V + K`1 U V̀ (21)
2. THE SCHRODINGER EQUATION FOR MOLECULES

Materials are composed of atoms, which also are composed of electrons and nuclei. To the highest extent
imaginable, the wave function which represents molecule with a nuclei and b electrons characterizes
the molecule's status. When studying the interior motions of molecules, we must consider the
movements of a substantial amount of charged particles related to each other. All molecular
characteristics, such as energy state and molecular geometry, may potentially be determined using the
wave function that exists in the Schrodinger equation.
d+V
XΤ dYΨ = ΕΨ (22)
Where Τd is the operator of the kinetic energy, V

d is the operator of the potential energy, Ψ is the wave
function and Ε is the energy.
When the Schrodinger equation is solved, many wavefunctions Ψh and their related energies Ε4 are
obtained, which adequately characterize the movements of the constituent particles of the molecule.
Every Ε4 is an energy amount which the molecule can still have, also known as a level of energy that
the molecule may hold [1].
If the required boundary conditions are considered. The operator of the kinetic energy Τ d and the operator
d both are affected by the locations of electronΧ56! , Χ56" , … , Χ567 s as well as
of the potential energy V
the locations of nuclei Χ! , Χ" , … , Χ5 .
If electrons and nuclei are represented as points charges and relativity influences and spin are ignored,
the operator of the potential energy and the operator of the kinetic energy can be represented as
567 " (23)
ℎ" ∇1
d =−
Τ P
8k " l1
18!
567 567 (24)
4" Ζ1 Ζ:
d=
V PP
8km9 oΧ1 − Χ: o
1 1;:
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2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
Where ∇1 denotes to the vector derivative operator with respect to the position Χ1 , ℎ represents Planck
constant, l1 is the mass of the particle Q, 4 is the unit charge (4 = 1.6019 × 10)!< ∁) , Ζ1 is the
charge number of the particle Q(it is −1 for an electron) and (m9 = 8.854 × 10)!" v )! w " x)! ) is the
vacuum permittivity.
2.1. Approximation of Born-Oppenheimer
Analytical solutions to the Schrodinger equation exist just for two-body systems such as that of the
hydrogen atom, and it is complicated to solve it analytically for molecules containing more than two
particles; nevertheless, some assumptions must have been made in order to identify approximate
solutions.The Born-Oppenheimer approximation is one of these simplifications.
The effect, the electrons' motion can be interpreted as if the nuclei were stationary in space, and the
electronic Schrodinger equation can be solved separately for each value of the nuclear coordinates. That
is, there is an approximate wavefunction that describes electron motions independently of a second
wavefunction that describes nuclei motions.
The Schrodinger equation, which is dependent on both nuclei and electron coordinates, is written as
d= + V
XΤ d= YΨ= + XΤ
d4>?@ + V
d4>?@ YΨ4>?@ = Ε= Ψ= + Ε4>?@ Ψ4>?@ (25)
The mathematical analysis of nuclear movements is simplified through separating nuclear movements
into vibrational, rotational, and translational modes.We may get the translational, vibrational, and
rotational modes and energies of the molecule under inquiry by resolving the Schrodinger [1].
d4>?@ + V
XΤ d4>?@ YΨ4>?@ = Ε4>?@ Ψ4>?@ (26)
2.2. The Representation of Coordinates

Each atom in a group of a atoms that are just not related to each other can move around freely in three
dimensions. To characterize their movement, 3a coordinates are essential .To describe the molecule's
shape, a system of 3a − 6 translationally and rotationally invariant internal coordinates L/ is utilized.
Three translationally invariant angles of Euler z, C, {, may be utilized to determine the rotation of the
entire molecule.The angles of the Euler have been used to connect the orientations of many an
orthonormal fixed axis system of molecule {}!+ , }"+ , }#+ } to a normal orthonormal space-fixed frame
{}! , }" , }# }.
}/+ = A }/ (27)
Where R is the rotor that was described by
% % % %
= 4 /BC# ⁄" 4 /EC$ ⁄" 4 /FC#⁄" = 4 /BC#⁄" 4 /EC$⁄" 4 /FC# ⁄" = 4 /FC# ⁄" 4 /E4! ⁄" 4 /BC# ⁄" (28)
When h" is determined by the formula
}# × }#+ (29)
h" =
|}# × }#+ |
The position of the molecule may be parametrized using three Cartesian coordinates. The location of
the molecule can be parametrized by three Cartesian coordinates
G (30)
x1 Å1
Ä=P
Ç
18!
From Eq (30), Μ is the molecule's mass, and it's written as
5 (31)
Μ = P x1
1
The chain rule describes the vector derivative operator ∇1 as
#5 (32)
(I& ) N
∇1 = P 41
NL/
/
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2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
From Eq (32), L/ denotes the internal coordinates, which are understood that
L#K)L = {, L#K)M = C, L#K)# = z
/%&'( = 0) , /%&') = 0( , /%& = 0% (33)

(I& )
41 is the measurement vector that corresponds to the nucleus Q and coordinates L/ of the molecule.
(I ) (34)
4 & = K1 L/
1
(I )
The term "measuring vector" 41 & comes from the fact that the vector takes the measure of the rate of
NO"
change in the coordinate L/ XΧ1 Y for any given rate of change NP
of the nuclear position Χ1 as [6]
G
]L/ (I ) ]Å1
= P 41 & ⋅ (35)
]Ñ ]Ñ
1
By geometric algebra, internal coordinates may be discussed in terms of nucleus position vectors. Their
gradients can then be obtained with algebraic expressions by modifying the atomic position vectors.
After that, we'll utilize this knowledge to characterize the operator of the kinetic energy of a polyatomic
molecule.
Each fixed location vector for body can be rotated to the fixed location vector for space as seen from
Eq (28) ,if we have a fixed location vector for body 71+ is rotated to the fixed location vector for space
71 = Χ1 − Ö by
71 = A 71+ (36)
Where is the rotor that is influenced by the axes of body.
Each option of the body's axes provides a reference orientation in which the body's axes coincide with
the fixed frame of space. The change of the molecule orientation for a given shape is equivalent to the
change in the orientation of the body's axis, but it is independent of any specific option of body frame.
But, if the molecule is deformed (that is if the shape in the initial and final is changed), the rotation of
the molecule would be determined by the choice of the body's axis [7].
3. OPERATORS FOR KINETIC ENERGY IN POLYATOMIC MOLECULES IN TERMS OF
GEOMETRIC ALGEBRA
We used geometric algebra to obtain a representation of the operator of the kinetic energy for an atomic
molecule a, at least in principle, by directly expressing the operator of a gradient in terms of generalized
coordinates or by components of operators of the quasi momentum such as the operator of the angular
moment .
For an atomic molecule a the expression of the operator of the kinetic energy
5
ℎ" 1 "
d (4>?@) = −
Τ P ∇ (37)
8k " x1 1
1
Where x1 is the mass of the atom Q. the operator of kinetic energy reads as
5 #5
ℎ" 1 (I' ) N
d=−
Τ PP ∇1 ⋅ 41 (38)
8k " x1 NLQ
1 Q
The Eq (38) may be written in a number of different ways, one of which is a ” contravariant metric
tensor Ü(I& I' ) ” such that the Ü(I& I' ) is giving in the form
5
(I& I' )
1 I' I&
Ü =P 4 ⋅4 (39)
x1 1 1
1
The official results of the classical tensor analysis show that [22]
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2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
5
1 RI S N 1 N )!⁄" (I I ) N
P ∇1 ⋅ 41 ' = )!⁄" P á Ü & ' (40)
x1 NLQ á NL/ NLQ
1 /
Where á = ]4Ñ Ü(I& I' ) is the contravariant metric tensor determinant.The operator of the kinetic energy
is as follows
#5
ℎ" N 1 Ná )!⁄" (I I ) N
d (4>?@)
Τ = − " P( + )!⁄" ) Ü & ' (41)
8k NL/ á NL/ NLQ
/Q
To be more specific, it is assumed that all integrations are done over the volume-element ]à =
)!⁄"
â]L! ]L" …, where â = o]4Ñ Ü(I& I' ) o = á )!⁄" , where â is called Jacobian.
If the volume element ]àT = ä]L! ]L" …, is used instead of the volume element ]à = â]L! ]L" …, the
corresponding operator of kinetic energy ãåT is provided as [8].
(4>?@)
ãåT = â!⁄" ä )!⁄" ãå (4>?@) ä !⁄" â)!⁄" (42)
The vibrational and rotational degrees of freedom are completely isolated from translation.
If we have the matrix [é] with elements [é]/Q = Ü(I& I' ) as follows:
(/4P)
êé U 0 ë
(P'V4@)
(43)
0 é
This Martic is split into a translational and internal block .
The measurement vectors for the coordinates of cartesian of the center of mass can be written as
5
(O ) x: }/ ⋅ Χ: x:
41 & = ∇1 Χ/ = P ∇1 = } (44)
í í /
:
The shape and rotational coordinates' translational invariance (abbreviated as I! = {, I" = C, and I# =
z for short),is
∑1 ∇1 L/ = 0 And ∑1 ∇1 I/ = 0
(45)
When Eqs (43), (44) and (45) are taken into account, The internal and translational parts can be
combined to form the operator of the kinetic energy.
î (4>?@) = Τ
Τ d (/4P) + Τ
d (P'V4W@) (46)
The internal part
#5)#
ℎ" N 1 Ná )!⁄" (I I ) N
d (/4P)
Τ =− " P( + )!⁄" ) Ü & ' (47)
8k NL/ á NL/ NLQ
/Q
The translational part

#
ℎ" N"
d (P'V4W@)
Τ = − "P " (48)
8k NΧ/
/8!
It is common to represent the rotational portion of each gradient operator in the forms of the components
of the fixed body ï̂/ = }/+ ⋅ Ιó of the angular momentum operator Ιó , rather than the partial derivative
X
operators XY ,from the [9] we can see the relation
&
#
N N N (Z )
X∇1 {Y + X∇1 CY + X∇1 zY = P 41 & ï̂/ (49)
N{ NC Nz
/
(Z( )
The measuring vectors 41 are obtained as
(Z( )
41 = ∇V ò(! ⋅ ∇1 }/+ ) ⋅ }Q+ ô (50)
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2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
(Z )
Where 41 ( related to the nucleus Q and the äth part of the angular momentum operator Ιå.The kinetic
energy operator's internal component in Eq (47) can be written succinctly as
#K)#
ℎ"
d (/4P) = −
Τ "
P Γå/A Ü(I& I' ) ΓåQ (51)
8k
/Q
[̂
The ΓåQ refers to component of the body-frame ℏ& of the overall angular momentum operator for degrees
X
of rotational freedom (F = 1, 2, 3) and partial derivative operator for shape coordinates XI for degrees
&)#
of vibrational freedom F = 4,5, … 3a − 3.
X
The Γ/A is called ”adjoint” and is the same as ΓåQ for degrees of rotational freedom and it is +
XI&)#
$
$ %
X^ !
á +! XI for the shape coordinates (F = 4,5, … 3a − 3), where (á + = ]4Ñ Ü(/Q) ) is the determinant of
&)#
the contravariant metric tensor [10].
The contravariant metric tensor Ü(/Q) or ÜRI& I'S with elements of vibrational is
! (I&)# ) (I')# )
Ü(/Q) = ∑K
1 _ 41 ⋅ 41 for (F, û = 4,5, … ,3a − 3) (52a)
"
! (I& ) RI' S ! (52b)
ÜRI& I'S = ∑K
1 _ 41 ⋅ 41 = ∑K
1 _ (∇1 L/ ) ⋅ (∇1 LQ ) for (F, û = 1,2, … ,3a − 6)
" "
The contravariant metric tensor Ü(/Q) or ÜRZ' I&S with Elements of Coriolis are
! (I&)# ) (c )
Ü(,`) = ∑b
2 e ⋅ e2 + for (F = 4,5, … ,3a − 3) and û = (1,2,3) (53a)
a* 2
! (Z' ) (53b)
ÜRZ' I& S = ∑K
1 _ 41 ⋅ K1 L/ for (i = 1,2, … ,3N − 6) and û = (1,2,3)
"
The contravariant metric tensor Ü(/Q) or ÜRZ& Z' S with the elements of rotational is
! (Z& ) (Z' )
Ü(/Q) = ÜRZ& Z'S = ∑K
1 _ 41 ⋅ 41 for F, û = (1,2,3) (54)
"
(Z )
The Euler angles' gradients are applied to the measurement vectors of rotational 41 & as follows:
(Y' ) (Z& )
K1 IQ = 41 = ∑#/8! 41 †)!
/Q (55)
Α)! )! )! +
/Q is the element of the matrix's inverse as Α/Q = [Α]/Q , that's the matrix is [Α]/Q = h/ ⋅ }Q , h/ is the
d ×d% d# ×d%#
vectors of nodal lines (n! = υ# , n" = fd# ×d#% f = g,h -
and n# = υ+# ).
# #
The matrix [Α] is

7Fh C 7Fh z 7Fh C %•7 z %•7 C
[†] = §
%•7 z − 7Fh z 0 ¶ (56a)
0 0 1
The inverse of the matrix [Α])! is
7Fh z %•7 C 7Fh z
⎡ %•7 z − ⎤
⎢ 7Fh C 7Fh C ⎥
[†])! = ⎢%•7 z %•7 C %•7 z⎥ (56b)
⎢ 7Fh C − 7Fh z − 7Fh C ⎥
⎣ 0 0 1 ⎦
As a result, It is possible to write
K # K #
1 (Y' ) (Y,) 1 (Z& ) (Z() )! )!
Ü (Y' Y, )
=P 41 ⋅ 41 = P P 4 ⋅ 41 †/Q †T@ = P Ü(Z& Z( ) †)! )!
/Q †T@ (57)
x1 x1 1
1 /T 1 /T
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2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
K # K #
1 (Y' ) (I,) 1 (Z& ) (I,) )!
Ü (Y' I, )
=P 41 ⋅ 41 = P P 4 ⋅ 41 †/Q = P Ü(Z& I, ) †)!
/Q (58)
x1 x1 1
1 /T 1 /
Where L@ is a coordinate for a shape.
)!
Since the determinant of [Α])! is ]4Ñ[†])! = W/4 E , the determinants of the two contravariant metric
tensor ]4ÑÜ(I& I' ) = á and ]4ÑÜ(/Q) = á + are related as follows
á + = (sin C)" á (59)
(where L#K)L , L#K)M , and L#K)# indicate to the Euler angles( { , C, z) respectively, and L#K)" , L#K)! ,
and L#K indicate to the center of mass coordinates (Χ! , Χ" , Χ# ) respectively).
4. LAGRANGIAN FORMULATION AND COVARIANT MEASURING VECTORS
The component of kinetic energy for the classical Lagrangian L = T − V is expressed in the form of
generalized velocities L/∙ , as for conservative systems (given to time-independent or no limitations at all)
[11].
T
1
ã = P L/∙ ÜI& I' L/∙ (60)
2
/Q
Where ä is the number of active coordinates and ÜI& I' is the covariant metric tensor can be determined
by
K
(1) (1)
ÜI& I' = P x1 4I& ⋅ 4I' (61)
1
(1)
Where 4I& The covariant measuring vectors which can be determined by the following equation
(1) N\1
4I& = (62)
NL/
It is essential to develop the ability to relate the characteristics of covariant measurement vectors to those
of contravariant measurement vectors. In the following, we will only analyze the unconstrained state
wherein the number of available coordinates is ä = 3a.
First, if Ñ = LQ is used in equation (35), the result is
5 K
NL/ (I ) NΧ1 NΧ1
= P 41 & ⋅ =P ⋅ ∇ L = Ø/Q (63)
NLQ NLQ NLQ 1 /
1 1
1 if F = û
Where Ø/Q = ∞
0 if F ≠ û
As a result, the constraint between covariant and contravariant measurements vectors is determined as
follow
K
(1) (I' )
P 4I& ⋅ 41 = Ø/Q (64)
1
Second, by utilizing the representation of ∇1 in equation (33), it is demonstrated that
#5 #5
(I ) NΧ: (I ) (:)
∇1 ( ≥'̅ Χ: ) = Ø:1 P 41 & ≥'̅ = Ø:1 P 41 & ≥'̅ 4I& (65)
NL/
/ /
Where ≥'̅ is an 8-blade that isn't affected by Χ: , with 8 = 0, 1, 2, 3. From the geometric product
( ≥'̅ Χ: ) is give as
( ≥'̅ Χ: ) = (−1)'6! ≥'̅ ⋅ Χ: + (−1)' ≥'̅ ∧ Χ: (66)
And
∇1 Χ: ⋅ ≥'̅ = Ø:1 8≥'̅ (67)
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2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
∇1 Χ: ∧ ≥'̅ = Ø:1 (3 − 8)≥'̅ (68)

By substituting the equations (68), (69) into (66) , yeilds
#5
(I& ) (:)
P 41 ≥'̅ 4I& = Ø:1 (−1)' (3 − 28)≥'̅ (69)
/
Where there are a number of special cases can be obtained from equation (68), by setting ≥'̅ = 1 (so
8 = 0) the identity
#5
(I& ) (:)
P 41 4I& = 3Ø:1 (70)
/
By changing the Eq (69) into a combination of inner and outer components
#5
(I& ) (:)
P 41 ⋅ 4I& = 3Ø:1 (71)
/
#5 (72)
(I& ) (:)
P 41 × 4I& = 0
/
Moreover, if the inner products are explained by means of geometric products and Eq (70) is applied, it
is easy to show that
#K
P Ü(I& I( ) Ü(I( I' ) = Ø/Q (73)

T
Eq (73) is the relation between the covariant metric tensor and contravariant metric tensor by means of
geometric products.
5. RESULTS AND CONCLUSIONS
Clifford's and many others' objective was to make geometric algebra helpful in many branches of
science. Because the algebra applied may provide for unexpected solutions to some problems. In this
regard, David Hestenes' efforts to make geometric algebra a science language beyond algebra in Physics
should be mentioned.
This study demonstrates that a general and practical method for obtaining rotational measuring vectors
(Z( )
¥41 µ using geometrical algebra has been developed, which gives its internal products with other
rotational measuring vectors and with gradients coordinates for vibration, the operator of the kinetic
energy of vibration and rotational of polyatomic particles.
The conclusions of this study will allow us to write the energy expressions of polyatomic molecules
much more compactly using Clifford Algebra, which will simplify our computations.
Clifford's Algebra enables us to better grasp nature and its realities. We can harness the power of
mathematics for physics by employing this algebra. While Clifford Algebra is useful in robotics and
dynamical systems, we now know that it also holds true in the enigmatic world of quantum physics.
Everything may be understood in terms of the movements of polyatomic molecules if operators exist.
We can make sense of the outcomes of applying mathematics to physics by employing operators.
REFERENCES
[1] Kanatani, K. Understanding Geometric Algebra: Hamilton, Grassmann, and Clifford for Computer
Vision and Graphics. New York :CRC Press, (2015).
[2] Kılıç, A., Özdaş, K.and Tanışlı , M. An Investıgatıon Of Symmetry Operatıons Wıth Clıfford
Algebra. Acta Physica Slovaca , (2004), 54(3), 221-232.
[3] Doran,C. And Lasenb, A. Geometric Algebra for Physicists, Cambridge: University Press, (2003).
16
2022, 1(1), pp. 7-18, DOI: 10.5281/zenodo.7241363
[4] Pesonen,J.and Halonen,L.Volume-elements of integration: A geometric algebra approach.The

Journal of Chemical Physics, (2002), 116(5), 1825-1833.
[5] Pesonen, J. Application of geometric algebra to theoretical molecular spectroscopy. Helsingin
yliopisto, (2001), 8-36.
[6] https://chem.libretexts.org/@go/page/151777 (Accessed : 01.04. 2020).
[7] Pesonen ,J. Vibration–rotation kinetic energy operators: A geometric algebra approach. Journal Of
Chemıcal Physıcs, (2001),114(24), 10599 – 10607.
[8] Gruber,G.R. Quantization in generalized coordinates-II. International Journal of Theoretical Physics
, (1972), 6 (2), 31-35.
[9] Doran,C., Hestenes,D., Sommen, F.and Van Acker, N. Lie Groups as spin groups. American
Institute of Physics, (1993), 34(8), 3642.
[10] Borisenko, A.I.,Tarapov, I.E. Vector and tensor analysis with applications. New York: Dover
Publications, (1979).
[11] Hestenes, D. New foundations for classical mechanics. Kluwer Academic Publishers, (1999),99
(2), 350-360.
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2022, 1(1), pp. 19-23, DOI: 10.5281/zenodo.7241379
JUSTIFICATION OF THE CHOICE OF CATALYST FOR THE OXIDATION OF C3-

C4 ALDEHYDES INTO ACIDS AND THEIR MODIFICATION
Elmira HUSEYNOVA, Ulkar SHIRALIYEVA, Nasiba IMANOVA, Ziba BAGIROVA,

Kamala ISMAYILOVA, Saida NADJAFOVA
Scientific Research Institute "Geotechnological Problems of Oil, Gas and Chemistry", ASOİU, Baku, Azerbaijan
ABSTRACT
The catalysts used to oxidize unsaturated aldehydes into the corresponding acids are complex oxide systems. The main
component of such oxide systems is molybdenum. Molybdenum itself, without additives, is not used as an independent catalyst.
The most widespread use as an additive is phosphorus, which markedly increases the stability of the molybdenum catalyst.
Significantly improve the properties of the catalyst named the presence of vanadium as well, an important role played by such
elements as copper, antimony, tungsten, iron, tellurium, and bismuth. The presence of these elements brings the yield of acrylic
acid to an average of 95% and methacrylic acid up to 68%.The use of heteropolyacids as oxidation catalysts is advantageous
because they possess a particular set of properties necessary for processes in catalysis. The use of heteropolyacids as oxidation
catalysts is beneficial because they contain a special set of required properties for processes in catalysis. High thermal stability
in the solid-state uses heterogeneous catalysts in oxidation reactions with a wide temperature range. An essential role in the
effective use of phosphormolybdenum heteropoly acids is played by their preparation methods, which involve the synthesis
based on ammonium salts of phosphorus and molybdenum and on phosphormolybdenum acid. Each series of experiments is
represented by samples of catalysts with a wide range. A characteristic point in the formation of the desired catalytic system is
the activation of the catalyst. For polycomponent systems, it is difficult to assess the contribution of each introduced component
or modify the additive that affects the activity and selectivity of the catalyst. The formation of a two-phase system of zinc
molybdate and the ammonium salt of the heteropoly acid appears to be the decisive condition for increasing the activity of the
multi-component catalyst when zinc is introduced into its composition. One should pay attention to the number of water
molecules in the heteropolyanion sphere and in the channels between them. The catalyst of the proposed composition provides
a high yield of the target product.
Keywords: heteropoly acid, acrolein, methacrolein, oxidation, thermal stability.
1. INTRODUCTION
Processes to produce acrylic and methacrylic acids and corresponding aldehydes by gas-phase catalytic
oxidation have been developed since the early 1980s [1]. The intensity of development has increased in
recent years. The leading countries are Japan and the USA; they account for three-quarters of the filed
patents for acrolein and methacrolein oxidation catalysts.
Catalysts for the oxidation of unsaturated aldehydes into acids [2] are complex oxide systems.
Molybdenum is a mandatory component in most of them (90%). Individual molybdenum oxide is not
used as a catalyst; as a rule, it is used in combination with other elements. The addition of phosphorus
is widely used, increasing contact stability.
About half of all molybdenum-containing catalysts (45%) are contacts containing vanadium. They
provide high conversion of acrolein to acrylic acid up to 80% and selectivity of the process up to 90%.
Methacrylic acid yield in the oxidation of methacrolein is lower - up to 60%, selectivity 70-75%.
Additions of copper, antimony, tungsten, iron, tellurium, and bismuth considerably improve the
properties of vanadium-molybdenum catalysts. On a complex V-Mo catalyst containing W and Cu and
at least one of the metals: Sb, Fe, Ni, Co, Bi, acrolein is almost wholly oxidized into acrylic acid (96.3%),
methacrylic acid yield-68.5%. Cobalt molybdates, often with additions of elements of V and VII groups
of the periodic system, constitute a notable group among molybdenum-containing catalysts.
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2022, 1(1), pp. 19-23, DOI: 10.5281/zenodo.7241379
Active catalysts for the oxidative transformation of acrolein and methacrolein into acids are Mo-As-
oxide systems with various additives, the best of which are nickel, palladium, and platinum. However,
the substantial arsenic toxicity and high cost of noble metals make these catalysts unpromising for
industrial application.Recently, preference is increasingly given to catalytic systems based on
phosphorus molybdenum heteropoly acid with additives of ammonium ions, alkali metals, vanadium,
tungsten, and antimony. The use of heteropolyacids (HPA) as oxidation catalysts seems promising
because HPAs possess a unique set of valuable catalyst properties. They are polynuclear complexes of
MoVI, WVI and VV that can also include many other elements as central atoms or ligands.
The intensity of new developments in the gas-phase catalytic oxidation of unsaturated C3-C4-aldehydes
into the corresponding acids contributes to the design of catalytic systems with specific, pre-formulated
properties. Such properties have at this stage of research phosphormolybdenum heteropoly acid with the
addition of ammonium ions, alkali metals, vanadium, tungsten, and antimony as oxidation catalysts with
the formation of the two-phase system of zinc molybdate and ammonium salt of heteropoly acid, as
HPA are multi-electron oxidizers and simultaneously strong acids.
2. METHODS
HPAs are multi-electron oxidizing agents and simultaneously strong bronsted acids. Oxidation-
reduction reactions and acidic properties of HPAs can be changed in a reasonably wide range by
changing the composition of HPAs. This circumstance turns out to be extremely important because
selective oxidation of unsaturated C3-C4-aldehydes into acids requires the presence of centers of
optimal acid and oxidative strength on the catalyst surface. HPAs have a sufficiently high thermal
stability in the solid-state. This creates an opportunity to use them as heterogeneous catalysts of
oxidation reactions.
Among various HPAs the acids and salts belonging to the saturated 12-row have the most significant
#$
importance for catalysis. They contain heteropolyanions (HPN) of the composition XX M !" O()*
%& or
X #$ X ()*
X M!") + V O%& . Representatives of series 12 are highly stable, and their properties have been
sufficiently studied [3]. The HPA molecules of the 12th row of the indicated species have a Keggin
structure with Td symmetry, which has been reliably established due to numerous X-ray studies of GPC
crystal hydrates [3]. This structure includes a central tetrahedron XO4, surrounded by 12 octahedrons
MO6, having common edges and vertices (O atoms).
X is the central atom (SiIV, GeIV, PV, AsV etc.);
x- degree of oxidation;
M- metal ion (MoVI, WVI)
The radius of HPA molecule~6Å [4].
Since the ionic radius of Oa- significantly exceeds the radii of MVI and Xx, the state of O in HPA is close
to densely packed [3]. The HPA molecule contains the following types of chemical bonds: 12 quasilinear
and 12 corners M-O-M bonds, four X-O-M bonds with bridging O atoms, and 12 M=O bonds with
terminal O atoms. In these bonds, the coordination number of the oxygen atom is 2,2,4, and 1,
respectively [3]. Thus, the HPA contains the main elements of the structure of Mo, W, and V oxides.
The most active and selective in the processes of oxidation of aldehydes into the corresponding acids
were Mo HPAs Mo (P Mo12, Si Mo12). The results of research on cesium salts of different molybdenum
heteropoly acids [5] showed that the systems based on cesium salt of phosphorus molybdenum
heteropoly acid are the most effective in acid formation reaction. Cesium contributes to an increase in
the yield of methacrylic acid, mainly due to an increase in selectivity. Introduction of additives of such
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2022, 1(1), pp. 19-23, DOI: 10.5281/zenodo.7241379
elements as V, W, Fe, Co, Ni, and Cr oxides, which turned out to be most active in the oxidation of
methacrolein to acids, increase the activity of cesium salt of phosphonomolybdenum heteropoly acid.
In works [5, 6], the possibility was studied, and basic principles of modifying HPA-based catalysts by
alkali metals were shown. It was shown that the catalytic properties of heteropoly compounds (HPC),
namely the systems Mx P MO12( M-Li, Na, K, Cs; x=1,3,7) depend on the charge radius and coordination
number of the introduced cation and its concentration.
It has been established that the presence of the Keggin cell [3] is a prerequisite for obtaining highly
active systems based on phosphorus molybdenum acid salts. The activity and stability of the catalyst are
related to the stabilization of the structure with wide channels in the volume of the HPC, occurring at
the introduction of large radius cations. The real possibility of increasing the efficiency of catalysts
based on HPC by varying the coordination number has been shown [6].
Taking into account other features of the introduced cation, it is possible to directionally change the
catalytic properties of the HPA. Thus, the use of the features of the HPC structure, taking into account
the nature, concentration, and properties of the introduced elements and modifying additives, opens up
tremendous possibilities for the design of heterogeneous catalysts of given compositions with given
properties. This is a new, promising, but still little studied direction in heterogeneous catalysis.
Studies in this area will undoubtedly be of interest not only for the theory of catalysis but also of great
practical importance for increasing the efficiency of catalytic processes of organic synthesis. Firstly,
processes of gas-phase catalytic oxidation of unsaturated aldehydes into corresponding acids.Having
justified the choice of heteropolyacids and, in particular, phosphormolybdenum acids as good catalytic
systems for the oxidative conversion of unsaturated С3-С4- aldehydes into corresponding acids, the
introduction of various modified additives is of interest [2]. Such an approach to the study of
phosphoromolybdenum catalytic systems will significantly affect the structure and, consequently, the
properties of heteropolyacids. The way of their preparation also plays an important role. We synthesized
catalysts by two methods: a) based on ammonium salts of P and Mo) from phosphormolybdenum acid.
In each series, the composition of the samples varied in a wide range and corresponded to the general
formula:
Cs0,1-1,5 W0,05-1,5 Cu0,01-0,6 Cr0,05-0,4 Zn1-5 P1 Mo12 V0,05-0,6 (NH4)1-6 O40,5-55,1
A characteristic of both series of catalysts is the need for their activation. In the first hours of operation,
the catalyst has low activity (degree of conversion of aldehyde <30%), which increases more than 3
times in steady-state mode. Steady-state mode is reached for a long time (35-40 h at 310˚C), decreasing
with increasing activation temperature (1-2 h at 360˚C).
The activity of samples in each series weakly depends on the composition of synthesized catalysts. For
polycomponent systems, it is complicated to estimate the contribution of one or another component or
modifying additive to the activity and selectivity of the catalyst. Such an attempt was made for simpler
catalysts synthesized from ammonium phosphate paramolybdate, ammonium vanadate, and zinc nitrate
by precipitation from a standard aqueous solution and prepared based on phosphormolybdenum
heteropoly acid [2]. It was shown that regardless of the preparation method, the catalysts are single-
phase systems with the structure of the ammonium salt of phosphorus molybdenum acid.The
introduction of vanadium does not affect the structure of the catalyst because V5+ ions, being a structural
analog of Mo6+, can partially replace them in the lattice of the solid body with preservation of the
structure. In this case, as shown [3], the rate of formation of selective oxidation products increases due
to the acceleration of the oxidation-reduction processes of the catalyst due to charge transfer:
Mo5+ + V5+ →Mo6+ +V4+
The addition of zinc in small amounts (Zn1) has no effect on the selectivity of the catalyst concerning
the target reaction; only the phase of the ammonium salt of Zn is found in the structure of the sample,
and the amount of zinc molybdate phase is insignificant. With increasing the additive concentration
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2022, 1(1), pp. 19-23, DOI: 10.5281/zenodo.7241379
(Zn2, Zn3), the selectivity of transformation of methacrolein into methacrylic acid increases noticeably,
further increasing Zn content in the catalyst (Zn3). However, it reduces its activity and selectivity.
The formation and presence of a two-phase system consisting of zinc molybdate ZnMoO4 and
ammonium salt of heteropoly acid is the decisive condition for increasing the activity of multicomponent
catalyst when zinc is introduced into its composition. The electron paramagnetic resonance (EPR) study
of the catalyst formation from ammonium paramolybdate, ammonium phosphate, ammonium vanadate,
and zinc nitrate (1 series) led to the conclusion that the formation of Keggin cells occurs at the stage of
sample thermal treatment- vanadium ions compete with molybdenum ions for positions in the
ammonium sublattice. These processes become more complicated in the presence of Zn ions. A zinc
molybdate precipitate is formed during synthesis, and some vanadium ions are captured by this structure.
Then, when the sample is heated, the ammonium salt of phosphate and ammonium ions, initially in
solution, gradually forms. During this slow growth, more regular and larger crystals of the heteropoly
compound are formed. The activating effect of zinc molybdate, which is not an oxidation catalyst, is
that its crystals serve as a matrix on which the HPC is formed. In addition, a two-phase system is
stabilized in the finished catalyst, which provides an increase in its activity.The second series of catalysts
prepared based on phosphormolybdenum acid are single-phase systems without zinc molybdate. As
known [2], the central structural unit of phosphormolybdenum heteropoly acid catalyst is Keggin cell.
The introduction of alkali metal ions of equal radius changes the way of Keggin cell packing. The
introduction of Cs contributes to some simplification of the Mo=O bond.
The properties and structure of HPCs strongly depend on the number of water molecules in the outer
coordination sphere of the heteropolyanion (HPN) and cations and the channels between the individual
HPNs. When samples are calcined to 300-380 ˚C, most of the water is removed, and the structure of
dehydrated samples becomes dependent on the radius of the introduced cation. Naturally, the presence
of large radius cations, including Cs, allows largely preserving the "openwork" porous structure even
with almost complete dehydration [4]. It was found [1] that the initial activity and selectivity of
phosphorus molybdenum catalysts increase when they are modified with alkali metals. The maximum
effect is observed when Cs are introduced. Such catalysts appear to be particularly resistant to
deactivation during operation. The stability of modified samples increases with the increasing radius of
alkali metal. We determined the optimal concentration of Cs ions: 1<x<3. At x>3 the selectivity
decreases sharply, and at x=7 the activity decreases.
Tungsten is an oxygen-containing element; tungsten ions in the composition of the catalyst increase its
surface acidity and, consequently, its oxidative activity. Chromium and copper salts of
phosphormolybdenum heteropoly acid also contribute to the activity and selectivity of the samples [2].
The results of tests of the synthesized phosphorus molybdenum-based heteropoly acid catalysts of both
series (differing in the method of preparation) with a wide variety of sample compositions during gas-
phase oxidation of methacrolein and methacrylic acid allowed to establish the optimal ratios of catalyst
components and clarify its general empirical formula:
Cs0,2-1 W0,1-1 Cu0,1-0,5 Cr0,07-0,4 Zn2-4 P1Mo12V0,1-0,5(NH4)1-4 Ox
4. CONCLUSION
The developed catalyst of this composition provides a sufficiently high yield of the target product, in
our case, during the oxidation of acrolein and methacrolein into the corresponding acids.
REFERENCES
[1] Grimalyuk B. Oxidation of methacrolein in the gas phase on heterogeneous catalysts. Diss.
Candidate of Chemical Sciences Lvov 1989; 148s.
[2] Staroverova I., Kutyrev M., Khvtistashvili L. Kinetics and catalysis vol. 27, no. Z.M., 1986 C; 691-
697.
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2022, 1(1), pp. 19-23, DOI: 10.5281/zenodo.7241379
[3] Huseynova E., Mamedova Z., Mustafayeva R., Analysis of experimental studies in the development
of the theoretical foundations of the process of isobutene oxidation on oxide catalysts Oil refining and
petrochemistry, No. 4, Moscow, 2016.
[4] Guliyeva A., Huseynova E., Salakhova Y., Mustafayeva R., Mamedova Z. Modification and study
by the planning method of the experiment of tin-antimony oxidation of isobutylene to methylacrolein,
Natural and mathematical sciences in the modern world. Collection of articles of the XXVII
International Scientific and Practical Conference Novosibirsk, 2015.
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
NUMERICAL AND EXPERIMENTAL INVESTIGATION ON THE REPAIR IMPACT OF

ARROW-SHAPED AND HEXAGONAL GLASS-EPOXY COMPOSITE PATCHES
Mohammadjavad RANJBARAN1, Seyed Masoud HOSSEINI2

1
Graduate student (Islamic Azad University of Hamedan, Department of Mechanical Engineering, Hamedan, Iran)
E-mail: mohammadjavadranjbaran@yahoo.com
2
Undergraduate student (Islamic Azad University of Hamedan, Department of Mechanical Engineering, Hamedan, Iran)
E-mail: masoud.hosseini1372@gmail.com
Abstract
Composites as materials with superior characteristics have proved their effectiveness in maintaining of damaged components,
especially in aeronautical applications. Within the current research, the arrow-shaped and hexagon glass-epoxy composite patches
with fibers orientations angles of 0,90 and -45,45 are employed with the aim of repairing the cracked aluminum alloy 7075
specimens. Total number of 28 one-sided repaired aluminum samples with 30 mm of crack length situated within the center, are
prepared to undergo uniaxial tensile loading using the 600 KN santam testing machine. Additionally, to the experimental tests, the
Abaqus software is employed so on simulate the testing conditions numerically with XFEM (Extended finite element method)
technique. Findings indicate that the arrow-shaped composite patches have higher efficiency of repair and sturdiness compared to
ones with hexagonal geometry. Also, by decrease in measurements of the repair patch geometry, the upper tensile load is handled.
Specimens repaired with glass-epoxy composites fibers orientation angle of -45,45 degree are extended more, but can withstand
lower tensile loading.
Key Words: glass-epoxy composite, Arrow-shaped, Hexagon patch, crack, extended finite element method, aluminum alloy 7075,
uniaxial tensile test,
1. INTRODUCTION
Makwana and shaikh revealed that the composite patch as an honest method of repair and reinforcement decreases the
strain and its intensity [1]. Hosseini et el. concluded glass-epoxy patch repair doubled the fatigue lifetime of two-sided
patched specimens [2]. The Composite patching was considered an on spot practical technique for repairing common
and regular damages within the aluminum aircraft structures [3]. Impacts of moisture, temperature besides other
contributing environmental factors determined to be the varied reasons directly influencing the repair durability of
adhesive patching joints [4]. Also, Composite patching proved its capability for underwater repair applications of
aluminum structures under tensile and bending loading [5]. Khalid Saeed and Muhammad Abid studied the
performances of bonded composite patch as compared to metallic ones on aluminum alloy 2024 samples. They
concluded that the fatigue lifetime of the specimens repaired by bonded composite patches enhanced approximately
for quarter-hour [6]. Yu Zhiqiang et el. focused on the adhesive repair modification of cracked aluminum samples
using carbon-aramid fiber/epoxy sandwich composite patch. It absolutely was found that the composite sandwiches
with 3 layers of fibers increased the effectiveness of repair for both tensile and bending loads 86% and 190%
respectively [7]. The composite patch repair on aluminum alloy 7075 specimens using graphite-epoxy at high stress
levels when applying constant load caused delay in their fatigue life [8]. The rectangular shaped patches found to be
more practical compared to oblique and elliptical geometries {[9], [10]}. The present study has numerically and
experimentally investigated the comparison of the features of arrow-shaped and hexagonal glass-epoxy composite
patches on repairing cracked aluminum alloy 7075 specimens.
1.1 Methodologies
In the experimental part, the 600 KN Santam testing machine is employed to perform real tensile loading on the
samples (Figure.1). Also, Abaqus software is used to numerically analyze and simulate the testing conditions.
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
Figure 1: The 600 KN Santam Testing Machine
1.1.2 Experimental Method

Twenty-eight cracked specimens made of aluminum alloy 7075 with the width and length of 80 and 150 mm were
subjected to uniaxial tensile loading. These samples were repaired by glass-epoxy composite patches with hexagonal
and arrow-shaped geometries that had 0,90 and -45,45 fibers orientations angles. Repair patches themselves were
prepared in different height, length and alpha angle measurements. Alpha indicates the half of an angle between both
adjacent sides in the left and right directions. SL has been allocated for the length sides of both arrow head and
hexagonal composite patches. In addition, L represents the horizontal distance as the length and H indicates the height
of the patches (Table.1). Repaired aluminum panels were positioned vertically between the lower and upper crossheads
in the load-cell of the testing machine (Figure.2). The required information relating to shape and size of the samples
such as: length, width, area and also the loading type were taken into account using the operating user’s software of
the Santam testing machine. Maximum tensile load and extension obtained from the experimental tensile tests before
the failure for each specimen were monitored (Table.1). Also, the Force-Displacement curves were plotted.
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
Table 1: Measurements and Specifications for Aluminum Samples
Horizontal Vertical Glass Fibers

Alpha Side Maximum Maximum
Specimen Geometry Length L Length H Orientations
Angle Length Tensile Load Displacement
Number Type (mm) Angle
(Degree) (mm) (mm) (degree)
(Newton) Extension (mm)
1 Hexagonal 50 18 35 28 0,90 13759 3.403
2 Hexagonal 52 28 55 45 0,90 12434 3.362
3 Hexagonal 55 35 60 58 0,90 13935 3.327
4 Hexagonal 64.5 32 40 58 -45,45 14627 3.690
5 Hexagonal 64.5 33 42 60 0,90 8505 2.445
6 Hexagonal 64 33 45 60 -45,45 9418 2.363
7 Hexagonal 60 33 50 60 -45,45 8638 2.515
8 Hexagonal 30 13 35 12 0,90 14303 3.690
9 Hexagonal 30 13 35 12 -45,45 9167 2.927
10 Hexagonal 20 18 52 12 -45,45 11713 3.940
11 Hexagonal 20 18 50 12 0,90 8167 2.347
12 Hexagonal 20 18 52 12 -45,45 10786 3.010
13 Hexagonal 45 20 45 32 0,90 13935 3.608
14 Hexagonal 40 22 55 28 0,90 12052 3.280
15 Hexagonal 40 22 55 30 -45,45 11904 3.267
16 Hexagonal 40 22 50 28 -45,45 11434 3.176
17 Arrow 22.89 18 53 12 0,90 11684 3.224
18 Arrow 33 22 55 24 0,90 8373 2.442
19 Arrow 45 25 60 36 -45,45 12670 3.362
20 Arrow 46.5 28 60 42 0,90 12096 3.280
21 Arrow 60 23 35 40 0,90 13965 3.608
22 Arrow 70 30 35 54 0,90 13479 3.526
23 Arrow 62.5 30 42 54 0,90 13935 3.533
24 Arrow 60 32 60 54 -45,45 12567 3.362
25 Arrow 57 22 38 42 0,90 15039 3.772
26 Arrow 65 28 35 48 -45,45 13361 3.444
27 Arrow 65 30 40 56 -45,45 9462 2.656
28 Arrow 65 30 40 5.6 0,90 12684 3.362
Figure 2: Positioning the Sample in the Load-cell
26
2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
1.2.1 Numerical Simulation

The Abaqus software version 6.14 2021 was employed to numerically analyze and simulate the uniaxial tensile
loading conditions for the aluminum samples repaired and reinforced by glass-epoxy composite patches. Extension
displacements obtained from the real experimental tests at failure point in which the specimens were no longer able
to withstand the maximum tensile load was used to precisely determine the highest level of loading in numerical
simulations by XFEM (Extended Finite Element Method). Two-dimensional sketches of the optimum hexagonal and
arrow head composite patches with capacity of withstanding the maximum tensile load were designed (Figures 3&4).
Figure 3: The 2D Sketch of the Hexagonal Composite Patch Used for Repairing the Aluminum Specimen Number 4
Figure 4: The 2D Sketch of the Arrow-shaped Composite Patch Used for Repairing the Aluminum Specimen Number 25
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
1.2.2 Property Determination

Real specifications of aluminum alloy 7075 from the literature such as the Young’s Modulus and Poisson’s Ration
were applied for the panel (Table 2).
Table 2. Material Characteristics of Aluminum Alloy 7075
Layer Name Poisson’s Ratio Young’s Modulus

Aluminum alloy 7075 0.33 71.7 (GPa)
Also, the engineering constants for the glass-epoxy composite patch considered as Table 3 shows.
Table 3. Glass-Epoxy Material Specifications
E1 E2 E3 G12 G13 G23 Nu12 Nu13 Nu23

40e9 10e9 10e9 3.8e9 3.8e9 3.4e9 0.30 0.30 0.40
The glass fibers orientation angles of the plies for hexagonal and arrow-shaped composite patches used to repair the
samples number 4 and 25 are -45,45 and 0,90 respectively (Figures 5 & 6).
Figure 5: The Orientation of Plies for Hexagonal Patch in Specimen Number 4
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
Figure 6: The Orientation of Plies for Arrow-shaped Patch in Specimen Number 25
1.2.3 Assembling
After defining the location of the crack, composite patches were employed to repair the cracked samples number 4
and 25 (Figures 7 & 8).
Figure 7: The Assembled Specimen Number 4 Repaired with Hexagonal Glass -Epoxy Composite Patch
Figure 8: The Assembled Specimen Number 25 Repaired with Arrpw-Shaped Glass-Epoxy Composite Patch
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
1.2.4 Meshing
The Composite patches with hexagonal and arrow head geometries were partitioned and meshed by applying 0.2
and 2 for absolute value and the approximate global size respectively (Figures 9 & 10).
Figure 9: The Meshed and Partitioned Hexagonal Glass-Epoxy Composite Patch
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
Figure 10: The Meshed and Partitioned Glass-Epoxy Arrow-shaped Composite Patch
After meshing the composite repair patches, they were installed on the cracked specimens (Figures 11&12). It should
be noted that the linear S4R and S3 element types were allocated for meshing the partitioned rectangular and triangular
geometries of the repair patches. Also, hex technique was used to mesh the aluminum plate.
Figure 11: The Fully-Meshed Repaired Cracked Aluminum Specimen Number 4
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Figure 12: The Fully-Meshed Repaired Cracked Aluminum Specimen Number 25
1.2.5 Loading and Boundary Conditions

The top and end sets were created to simulate the testing conditions during which the lower crosshead of the testing
machine was fixed and only the upper head was moving and operating along Y direction. Displacements considered
for samples number 4 and 25 are 3.690 and 3.772 mm respectively (Figures 13 & 14).
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
Figure 13: Loading and Boundary Conditions for Specimen Number 4 Repaired with Hexagonal Patch
Figure 14: Loading and Boundary Conditions for Specimen Number 25 Repaired with Arrow-shaped Patch
1.2.6 Visualization
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
Lastly, the simulated uniaxial tensile loading tests were performed for the repaired aluminum samples number 4 and
25. The results of numerical simulations of Misses stress distribution for both specimens and their Force-Displacement
linear graphs were monitored and reported (Figures 15, 16, 17 & 18).
Figure 15: Misses Stress Distribution for Specimen Number 4 Repaired with Hexagonal Patch
Figure 16: Misses Stress Distribution for Specimen Number 25 Repaired with Arrow-shaped Patch
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
Figure 17: The Force-Displacement Curve for Specimen Number 4
Figure 18: The Force-Displacement Curve for Specimen Number 25
2. Results
1. Findings showed that the glass-epoxy composite patches with arrow head geometry are superior to the ones
with hexagonal shape.
2. Samples number 4 and 25 had the highest level of durability of repair and withstanding uniaxial tensile
loading.
3. By decrease in the measurements of the patch, the efficiency of the repair significantly rose.
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2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
4. Patches with fibers orientation angle of -45,45 degree had the maximum displacement extension while the
ones with 0, 90 angle of fibers orientation handled the maximum tensile loading.
3.Discussion and Conclusions

In this study the repair impacts of arrow-shaped and hexagonal composite patches with different glass fibers
orientation angles on cracked aluminum alloy 7075 plates were investigated. The 600KN Santam testing machine was
employed to perform the experimental tensile tests. Then, each of cracked specimen was numerically simulated with
Abaqus software using the extended finite element method. The validation of experimentally obtained results indicated
the least error percentage in comparison to numerical ones. It has been found out that composite patching technique
highly enhances the durability of repair in aluminum structures. To conclude, with the aid and contribution of
technology, failure of the damaged aluminum components and repairing them are highly predictable under most of
the conditions.
Declarations
Ethical approval and consent to participate:
Not applicable.
Consent for publication:
Not applicable.
Availability of data and materials:

All the required data are provided as within tables and also numbered sections explaining how the procedure or
process was conducted.
Competing interest:
The author states no conflict of interests as the only creator of the manuscript.
Funding:
The author states no funding involved
Author’s contributions:
The author states that the design of the study, collection, analysis and interpretation of data in writing the manuscript
belongs to him.
Acknowledgements
Mohammadjavad Ranjbaran is a graduate student at the mechanical engineering department of Islamic Azad
University of Hamedan, Iran.
References
[1] Alpesh H. Makwana & A.A. Shaikh. The role of patch hybridization on tensile response of cracked panel repaired with hybrid composite
patch: experimental and numerical investigation The Journal of Adhesion: 2021, Volume 97, Issue 1, 53-87.
[2] K. Hosseini, M. Safarabadi, M. Ganjiani, E. Mohammadi & A. Hosseini. Experimental and numerical fatigue life study of AL plates reinforced
by glass-epoxy composite patches in different stress ratios. The international journal of Mechanics Based Design of Structures and Machines: 2021,
Volume 49, Issue 6, 894-910.
[3] Z. P Marioli-Riga, G J. Tsamasphyros, G. N. Kanderakis Design of Emergency Aircraft Repairs Using Composite Patches. Journal of
Mechanics of Composite Materials and Structures: 2001, Volume 8, Issue 3,199-204.
36
2022, 1(1), pp. 24-37, DOI: 10.5281/zenodo.7241395
[4] S. Budhe, M. D. Banea & S. de Barros Bonded repair of composite structures in aerospace application: a review on environmental issues.
Journal of Applied Adhesion Science: 2018, Volume 6, Article number 3.
[5] R. W. Bianchi, Y. W. Kwon, E. S. Alley Composite Patch Repair for Underwater Aluminum Structures. Journal of Offshore Mechanics and
Arctic Engineering:2019, Volume 141, Issue 6.
[6] Khalid Saeed, Muhammad Abid. Crack growth performance of aluminum plates repaired with composite and metallic patches under fatigue
loading. Institute of Electrical and Electronics Engineers. Fourth International Conference on Aerospace Science & Engineering (ICASE):2015.
[7] Xiaoyan Liu, Jiacheng Wu, Jiaojiao Xi, and Zhiqiang Yu. Bonded Repair Optimization of Cracked Aluminum Plate by Microwave Cured
Carbon-Aramid Fiber/Epoxy Sandwich Composite Patch. Materials (Basel): 2019, Volume 12, Issue 10, 1665.
[8] M. Benachour, F.Z Seriari, N. Benachour and M. Benguediab. Beneficial Patch Repair Effect on Fatigue crack Growth of Al-Alloy 7075.
Applied Mechanics and Materials:2012, Volume 225, 158-164
[9] Baghdadi Mohammed, Serier Boualem, Salem Mokadem, Zaoui Bouchra, Kaddouri Khacem. Modeling of a cracked and repaired Al 2024T3
aircraft plate: effect of the composite patch shape on the repair performance. Frattura ed Integrita Struttuarle: 2019: Volume 50, 68-58.
[10] Leonel Echer, Carlos Eduardo de Souza, Rogerio Jose Marczak. A Study on Best Conventional Shapes for Composite repair patches. Material
Research: 2021, Volume 24, supply2.
37
2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
INVESTIGATION OF FRACTURE PREVENTION EFFECTS OF COMPOSITE

PATCHES REPAIR ON CRACKED ALUMINUM PLATES EXPERIMENTAL AND
NUMERICAL STUDY
Mohammadjavad RANJBARAN
Graduate student (Islamic Azad University of Hamedan, Department of Mechanical Engineering, Mussivand,
Hamedan, Iran)
E-mail: mohammadjavadranjbaran@yahoo.com
Abstract
Nowadays, composite materials are extensively applicable in various aspects including automotive, marine and most importantly
aeronautical engineering because of their excellent characteristics. Innovative maintenance using materials with extraordinary
features has led to contributing of composites with the goal of extending their lives services. Glass-epoxy composites are lifesaver,
inexpensive and highly practical for repairing the damaged components of aeronautical structures. The present study has employed
composite patching technique to repair 50 centrally cracked rectangular aluminum plates subjected uniaxial tensile loading
experiment. The 600 KN Santam testing machine used for performing tensile tests. Then, the force-displacement linear graph for
each sample was plotted and monitored by its user’s software. Next, the Abaqus finite element software simulated the same testing
conditions on developed 3D- models using XFEM method. Finally, the numerical and experimental results indicated 0.0266 error
percentage between the real and simulated tensile loading tests. In addition, specimens repaired by composite patches whose glass
fibers orientations angles are 0,90 proved to have the best optimum performance while those that were repaired by patches with
fiber orientations angle -45, +45 had the maximum displacement extension before failure.
Key Words: glass-epoxy composite patching, crack, extended finite element method, aluminum alloy 7075, uniaxial tensile test
1. INTRODUCTION
Makwana and shaikh revealed that the composite patch as an honest method of repair and reinforcement
decreases the strain and its intensity [1]. Hosseini et el. concluded glass-epoxy patch repair doubled the
fatigue lifetime of two-sided patched specimens [2]. The Composite patching was considered an on spot
practical technique for repairing common and regular damages within the aluminum aircraft structures [3].
Impacts of moisture, temperature besides other contributing environmental factors determined to be the
varied reasons directly influencing the repair durability of adhesive patching joints [4]. Also, Composite
patching proved its capability for underwater repair applications of aluminum structures under tensile and
bending loading [5]. Khalid Saeed and Muhammad Abid studied the performances of bonded composite
patch as compared to metallic ones on aluminum alloy 2024 samples. They concluded that the fatigue
lifetime of the specimens repaired by bonded composite patches enhanced approximately for quarter-hour
[6]. Yu Zhiqiang et el. focused on the adhesive repair modification of cracked aluminum samples using
carbon-aramid fiber/epoxy sandwich composite patch. It absolutely was found that the composite
sandwiches with 3 layers of fibers increased the effectiveness of repair for both tensile and bending loads
86% and 190% respectively [7]. The composite patch repair on aluminum alloy 7075 specimens using
graphite-epoxy at high stress levels when applying constant load caused delay in their fatigue life [8]. The
rectangular shaped patches found to be more practical compared to oblique and elliptical geometries {[9],
[10]}.This study has taken an additional step to analysis the effectiveness of the arrow-shaped composite
patch repair experimentally and numerically.
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
1.1 Methodologies
Both experimental and simulation methods were undertaken to provide accurate and precise data for
further analysis of the research.
1.1.2 Experimental Method
In this part of the study, the uniaxial tensile loading test was done on 50 rectangular aluminum alloy 7075
panels of 80 mm width, 150 mm length and 1 mm thick by employing the 600 KN santam testing machine
(Figure 1) Each specimen with central crack lengthening 30 mm underwent tensile loading with the speed
of 0.2 mm per minute to the failure spot. Single-sided arrow-shaped glass -epoxy composite patches
reinforced the cracked panels. Plates positioned vertically between the lower and upper crossheads with 50
mm of gage length in the load-cell (Figure 2). In the next step, the user software of the testing machine was
customized with desired geometry, area, length, width, thickness of samples and the required loading type.
Fig.1. The 600 KN Santam Testing Machine Fig.2. Specimen Positioning in the Load-Cell
English alphabets A to Q were assigned to each category of specimens characterized by following

specifications. Alpha is half of an angle between two adjacent right and left sides. SL has been allocated
for the length sides of arrow head composite patches. In addition, L represents the horizontal distance as
the length and H indicates the height of each composite patch repairs. Table 1 shows the measurements for
different patch categories.
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
Table 1. Measurements for Different Sample Categories
Category Alpha Angle Side Length Horizontal Length L Vertical Length H

(degree) (mm) (mm) (mm)
A 50 30 60 40
B 30 20 55 13
C 53 25 50 40
D 53 25 45 45
E 61.35 30 45 55
F 36 23 55 27
G 40 10 26 13
H 30 13 40 13
I 20 20 55 13
J 40 20 45 25
K 35 23 55 26
L 52 35 65 55
M 40 20 45 25
N 36 23 55 27
O 49 18 55 27
P 20 15 50 10
Q 20 18 50 12
For safety reasons, the security shield of the testing machine was then closed. Tests conducted for several number
of specimens of each category to increase the accuracy of experimental results. As tests were being performed, the
Force-Displacement curve was plotted by the testing machine user software. The maximum tensile force and extension
for all specimens repaired by composite patches with 0,90 to -45, 45 glass fibers orientations were obtained to the
failure point (Table 2).
Table 2. Experimental Results for Specimens
Fibers Orientations Max Tensile Load Max Displacement

Category Specimen Number
(degree) (Newton) Extension (mm)
A 1 0,90 14583 4.561
A 2 -45,45 11911 3.535
B 1 -45,45 11139 3.250
B 2 0,90 11492 3.343
C 1 0,90 12258 3.642
C 2 -45,45 12258 3.357
D 1 0,90 12405 3.663
D 2 -45,45 11904 3.520
D 3 -45,45 13067 3.673
D 4 -45,45 12302 3.379
D 5 -45,45 12272 3.288
E 1 0,90 12537 3.720
E 2 -45,45 12464 3.705
E 3 -45,45 11640 3.461
F 1 -45,45 11154 2.794
F 2 0,90 10668 3.165
F 3 -45,45 11213 3.346
F 4 0,90 11242 3.336
G 1 0,90 12096 3.618
G 2 -45,45 14406 4.203
G 3 -45,45 13185 3.909
G 4 0,90 9962 2.897
H 1 0,90 9741 2.882
H 2 0,90 9933 2.998
H 3 -45,45 11125 3.297
H 4 -45,45 15583 6.093
I 1 0,90 10345 3.075
I 2 -45,45 11728 3.445
I 3 0,90 12155 3.637
I 4 -45,45 12155 4.756
J 1 0,90 11610 3.465
J 2 -45,45 12464 3.672
J 3 0,90 15936 4.741
K 1 0,90 10036 2.999
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
K 2 -45,45 11654 3.468

K 3 -45,45 9624 2.853
L 1 0,90 10153 3.043
L 2 -45,45 11345 3.395
M 1 -45,45 8182 2.472
M 2 0,90 8288 2.462
M 3 -45,45 13188 3.897
N 1 0,90 11581 4.510
N 2 -45,45 13405 3.997
N 3 0,90 11213 3.353
N 4 0,90 10786 3.188
O 1 -45,45 13479 3.951
O 2 0,90 14759 4.344
O 3 -45,45 11301 3.337
P 1 -45,45 10271 3.012
P 2 0,90 10536 3.102
Q 1 0,90 10271 3.026
Q 2 -45,45 9830 2.869
1.2. Numerical Simulation
1.2.1 Design of Part

Abaqus finite element software version 6.14 2021 was employed to numerically simulate the tensile loading test.
The three-dimensional solid and shell extrusion features were used for the aluminum panel and crack with 30 mm of
length. It should be noted that in accordance with experimental results of specimen number 3 of category J, the design
of this repair patch considered to have the best and optimum geometry for simulation using the shell planar base
feature (Figures 3, 4 & 5).
1.2.2 Property
Fig.3. 2D Plate Sketch
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Fig.4. The Crack Sketch
Fig.5. The Patch Sketch
Determination
Real specifications of aluminum alloy 7075 from the literature such as the Young’s Modulus and Poisson’s Ration
were applied for the panel (Table 3).
Table 3. Material Characteristics of Aluminum Alloy 7075
Layer Name Poisson’s Ratio Young’s Modulus

Aluminum alloy 7075 0.33 71.7 (GPa)
Also, the engineering constants for the glass-epoxy composite patch considered as Table 4 shows.
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
Table 4. Glass-Epoxy Material Specifications
E1 E2 E3 G12 G13 G23 Nu12 Nu13 Nu23

40e9 10e9 10e9 3.8e9 3.8e9 3.4e9 0.30 0.30 0.40
The condition during which the crack propagated within the aluminum plate and caused failure was reported at
maximum principal stress and displacement extension of 524 and 4.741 respectively. The composite layup feature
was used in order to set the orientations of patch plies. Then, the plies each thickening 0.5 mm with 0 and 90 rotation
angles were positioned. Next, axis 3 (Z) as the local material orientation system was chosen for the composite patch
normal (Figure 6).
1.2.3
Fig.6. The Orientation of Patch Plies

Assembling
At this stage, two surfaces titled as the slave and master were assigned to the back of the patch and front of the plate
to define the bond between them in interaction module. The central crack positioned with 25 mm of length from each
right and left edges on the plate. To repair the specimen, the composite patch placed on the central crack with 17.5
mm of distance from both sides (Figures 7& 8).
Fig.7. Positioning of the Crack
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
Fig.8. Central Crack on the Plate
1.2.4 Step
The general static procedure and 1 second as time period considered. To apply the extension speed of real testing
conditions, 0.2 and 0.002 were chosen for the initial and minimum increment size.
1.2.5 Meshing
To mesh the plate, the hex element shape with linear geometric order was selected. Also, 0.2 absolute value and 2
as the approximate global size were further applied. It should be noted that the employed element shape for the plate
was C3D8R (Figure 9).
Fig.9. The Meshed Plate
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
Partitioning divided the composite patch into two triangular in each side and a separate rectangle in the middle. The
structured meshing technique with quad element shape and the linear type of element S4R allocated for the meshing
of
rectangular geometry in the center. In addition, the Tri shape and the S3 element type with the same mesh method
were assigned to the triangular geometries (Figures 10, 11& 12).

Fig.10. Partitioning of Patch
Fig.12. Fully-Meshed andMeshing

Fig. 11. RepairedofCracked
Patch Aluminum Plate
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
1.2.6 Interactions
The plate front surface was constrained to the back of the patch to create the bond using shell-to-solid coupling
feature. The XFEM method was then consequently enabled for the simulation of crack propagation in the specimen
(Figures 13 & 14).
Fig.13. Bonding of Patch on the Surface of the Plate
Fig.14. The Defined Domain for Crack Propagation
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405

1.2.7 Loading
To define the loading conditions, two sets were created for the end and top of the aluminum plate by node selection.
For the boundary conditions, the top-set subjected to Y direction as the only moving degree of freedom. The end-set
was considered to be Encastre to simulate the fixed lower crossheads in the testing machine (Figure 15).
1.2.8- Job
In the job module, the simulated repaired plate with glass-epoxy composite patch was submitted for further
analysis.
1.2.9- Visualization
The requested field outputs using the numerical results of the simulation are shown as in figure 16.
Fig.15: Defining Boundary Conditions for Tensile Testing
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
Fig.16. The Distribution of Misses Stress in Cracked Specimen

The force versus displacement extension graph for the composite patch with the optimum performance of repair was
then plotted (Figure 17).
Fig.17. The Force-Displacement Curve for the Specimen Number 3 of Category J
The maximum tensile force and extension for specimens of different categories were obtained numerically. To
investigate the data validity, the error percentage was calculated by comparing the experimental and numerical results
(Tables 5& 6).
Table 5. Comparison of the Numerical and Experimental Results for Sample Categories A to J
Maximum
Category & Specimen Maximum Numerical
Experimental Tensile Error Percentage
Number Tensile Load
load
A1 14620 14583 0.0026
A2 11920 11911 0.0008
B1 11329 11139 0.0168
B2 11520 11492 0.0025
C1 12280 12258 0.0018
C2 12280 12258 0.0018
D1 12410 12405 0.0005
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
Category & Specimen Maximum Numerical Tensile Maximum Experimental

Error Percentage
Number Load Tensile Load
K1 10121 10036 0.0084
K2 11712 11654 0.0050
K3 9630 9624 0.0007
L1 10257 10153 0.0102
L2 11440 11345 0.0084
M1 8386 8182 0.0244
M2 8339 8388 0.0059
M3 13220 13188 0.0025
N1 11600 11581 0.0017
N2 13570 13405 0.0122
N3 11330 11213 0.0104
N4 10770 10786 0.0015
O1 13480 13479 0.0001
O2 14760 14579 0.0123
O3 11380 11301 0.0070
P1 10390 10271 0.0115
P2 10580 10536 0.0015
Q1 10340 10271 0.0067
Q2 9840 9830 0.0019
D2 11940 11904 0.0031
D3 13130 13067 0.0048
D4 12334 12302 0.0026
D5 12280 12272 0.0007
E1 12520 12537 0.0014
E2 12460 12464 0.0004
E3 11710 11640 0.0060
F1 11180 11154 0.0024
F2 10710 10668 0.0040
F3 11280 11213 0.0060
F4 11360 11242 0.0104
G1 12260 12096 0.0134
G2 14556 14406 0.0104
G3 13210 13185 0.0019
G4 9969 9962 0.0008
H1 9809 9741 0.0070
H2 10204 9933 0.0266
H3 11240 11125 0.0103
H4 15610 15583 0.0018
I1 10450 10345 0.0101
I2 11729 11728 0.0001
I3 12360 12155 0.0166
I4 12190 12155 0.0029
J1 11730 11610 0.0103
J2 12469 12464 0.0005
J3 16089 15936 0.0096
Table 5. Comparison of Numerical and Experimental Results for Sample Categories K to Q

2. Results
1. The data validation between the results obtained from experimental tests and numerical simulations showed
maximum 0.0266 of error percentage for XFEM method.
2. The composite patches with glass fibers orientations angles of 0,90 significantly increased the durability of
the repair up to 1593 newton.
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2022, 1(1), pp. 38-51, DOI: 10.5281/zenodo.7241405
3. Cracked specimens repaired by patches with -45, 45 degree of glass fibers orientations extended more
meanwhile they failed by rise in tensile force.
3.Discussion and Conclusions

In this study the impacts of composite patch repair with different glass fibers orientation angles on cracked aluminum
alloy 7075 plates were investigated. The 600KN Santam testing machine was employed to perform the experimental
tensile tests. Then, each of cracked specimen was numerically simulated with Abaqus software using the extended
finite element method. The validation of experimentally obtained results indicated the least error percentage in
comparison to numerical ones. It has been found out that composite patching technique highly enhance the durability
of repair in aluminum structures. Taking everything into consideration, with the aid and contribution of technology,
failure of aluminum components is highly predictable under most of the conditions.
References
[1] Alpesh H. Makwana & A.A. Shaikh. The role of patch hybridization on tensile response of cracked
panel repaired with hybrid composite patch: experimental and numerical investigation The Journal of
Adhesion: 2021, Volume 97, Issue 1, 53-87.
[2] K. Hosseini, M. Safarabadi, M. Ganjiani, E. Mohammadi & A. Hosseini. Experimental and numerical
fatigue life study of AL plates reinforced by glass-epoxy composite patches in different stress ratios. The
international journal of Mechanics Based Design of Structures and Machines: 2021, Volume 49, Issue 6,
894-910.
[3] Z. P Marioli-Riga, G J. Tsamasphyros, G. N. Kanderakis Design of Emergency Aircraft Repairs Using
Composite Patches. Journal of Mechanics of Composite Materials and Structures: 2001, Volume 8, Issue
3,199-204.
[4] S. Budhe, M. D. Banea & S. de Barros Bonded repair of composite structures in aerospace application:
a review on environmental issues. Journal of Applied Adhesion Science: 2018, Volume 6, Article number
3.
[5] R. W. Bianchi, Y. W. Kwon, E. S. Alley Composite Patch Repair for Underwater Aluminum Structures.
Journal of Offshore Mechanics and Arctic Engineering:2019, Volume 141, Issue 6.
[6] Khalid Saeed, Muhammad Abid. Crack growth performance of aluminum plates repaired with
composite and metallic patches under fatigue loading. Institute of Electrical and Electronics Engineers.
Fourth International Conference on Aerospace Science & Engineering (ICASE):2015.
[7] Xiaoyan Liu, Jiacheng Wu, Jiaojiao Xi, and Zhiqiang Yu. Bonded Repair Optimization of Cracked
Aluminum Plate by Microwave Cured Carbon-Aramid Fiber/Epoxy Sandwich Composite Patch. Materials
(Basel): 2019, Volume 12, Issue 10, 1665.
[8] M. Benachour, F.Z Seriari, N. Benachour and M. Benguediab. Beneficial Patch Repair Effect on Fatigue
crack Growth of Al-Alloy 7075. Applied Mechanics and Materials:2012, Volume 225, 158-164
[9] Baghdadi Mohammed, Serier Boualem, Salem Mokadem, Zaoui Bouchra, Kaddouri Khacem. Modeling
of a cracked and repaired Al 2024T3 aircraft plate: effect of the composite patch shape on the repair
performance. Frattura ed Integrita Struttuarle: 2019: Volume 50, 68-58.
[10] Leonel Echer, Carlos Eduardo de Souza, Rogerio Jose Marczak. A Study on Best Conventional Shapes
for Composite repair patches. Material Research: 2021, Volume 24, supply2.
50
2022, 1(1), pp. 52-55, DOI: 10.5281/zenodo.7243656
THE EFFECT OF ADDING ARTIFICIAL NOISE ON THE SUCCESS OF A DEEP

LEARNING NETWORK
Utku KAYA1,*
1
Vocational School of Transportation, Eskişehir Technical University Eskisehir, Turkey
ABSTRACT
Image pre-processing methods have a significant impact on increasing the success of the deep learning network. For deep learning
networks to be successful, a large amount of data is needed. Obtaining these datasets is a challenging task that requires effort and
observation. Therefore, the researchers aim to increase the success of the deep learning network by modifying the existing images
and making it more prepared for new test images. In this way, they artificially increase the number of images in the data sets by
using methods such as modifications to the colour bands, adding noise, and histogram equalization. In this study, the change in
success rates of the network will be investigated in detail by adding different noise types to the data set used to train the deep
learning network.
Keywords: Image Pre-processing, Deep Learning, Skin Segmentation
1.INTRODUCTION
One of the most constraining things in the field of deep learning is the scarcity of data sets. Today, hardware
and software are sufficient for deep learning analysis. But collecting, organizing, and labelling data sets is
a very difficult task. In addition, group imbalances between datasets also affect the success of the network.
For example, when it is desired to classify a rare disease; The data of unhealthy people are very few
compared to the data of healthy people. Therefore, the deep learning network will tend to detect even
unhealthy people as healthy people. Researchers are conducting various studies to solve this class imbalance
problem. [1-5] Rahman, Shaza M., and Ajith Abraham have a review article that summarizes these studies.
[6] In these types of studies, data sets are generally increased artificially by applying various image pre-
processing methods. These methods are called SMOTE. Images in datasets can be reproduced by applying
multiple image pre-processing methods. For example, taking a mirror image is one of them. Mirroring
usually aims to augment the dataset without distorting the original image. If the mirror image of each image
in the dataset is saved, it is possible to get 2 times more data. In addition, rotating the images at a certain
rate will enable the network to be robust against images taken at new different shooting angles. Such image
pre-processing methods do not have much negative impact on the original training set. Artificial data
augmentation removes data set imbalances and increases the amount of data. It should be noted that data
augmentation does not always improve the network. (Like adding noise) Incorporating artificial versions
of the original data into the network causes the network to drift away from the original images and fail.
This is called the overfitting problem. There is a limit to this artificial image augmentation. In this study,
noise, one of the image pre-processing methods called “noise addition”, will be discussed.
One of the factors that reduce the success of the deep learning network is noise. There is noise in each
image in the dataset used in the network. Noise is generally the undesirable effect in the image depending
on the magnetic effects in the external environment, the shaking of the shooting camera, and the amount of
light. Noise is not a fixed attribute that is easily detected like colour. There is random noise in each image.
Training the deep learning network without interfering with noisy images will cause difficulties and errors
in detecting images with different noise structures and ratios.
One of the aims of this study is to increase the amount of data by adding random noise and to observe the
effect of different noise models on the success of the network. In this way, it is to guide the researchers
working on this subject by showing the effect of artificial image augmentation methods on network success
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2022, 1(1), pp. 52-55, DOI: 10.5281/zenodo.7243656
2. METHODS
In this paper, the skin segmentation problem was chosen as a case study. Distinguishing human skin from
images is a very difficult and interesting process. This research area attracts the attention of researchers. [7-
8] The deep learning network and datasets that are used for skin segmentation should be well designed. The
challenges in skin segmentations are people's gender, race, hair colour, skin colour, shifts in the photograph
taken, ambient light, and most importantly, noise. Because of these difficulties, it is possible to see high
success changes in the smallest changes.
There are many datasets in the literature to be used for skin segmentation. In this study, the Pratheepan
dataset will be used, which contains a few amounts of data.[9] The success of a dataset containing such
little data is extremely low. This dataset has been deliberately chosen to demonstrate the success of image
augmentation.
The dataset contains a total of 156 images and labelled images. By adding different types of noise to these
images, the amount of data set would be increased, and the success changes would be observed by inserting
them into a simple deep learning semantic network. Figure 1. shows the original image and an image with
random noise.
Figure 1. A sample image from the dataset (Left=original, Right=with random noise)
Finding the optimal data augmentation rate is one of the goals. The main reason for calling it “optimum
data augmentation” is that adding random noise to the data set and increasing its amount does not always
increase the network’s success. On the one hand, the amount of data sets increases, and the network is more
prepared for new test images, on the other hand, the network moves away from the original images. This
causes a problem called overfitting and reduces the success of the network. This situation can be seen in
Tables 1 and 2. Such effects will be discussed next.
Table 1. Description of groups
Type of data Tested with
Group 1 Original images Original images
Group 2 Original images+ İmage Original images

with random noise
Group 3 İmage with random noise İmage with random noise
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2022, 1(1), pp. 52-55, DOI: 10.5281/zenodo.7243656
Table 2. Success rates of different groups

Accuracy IoU MeanBFScore
Group 1 Skin 0.87995 0.32534 0.49909
Nonskin 0.72796 0.71428 0.67123
Group 2 Skin 0.44926 0.23996 0.26468
Nonskin 0.86296 0.79423 0.7486
Group 3 Skin 0.0017216 0.0017093 0.030271
Nonskin 0.99889 0.86531 0.82596
In the study, 156 original images in the Pratheepan dataset were used to train the deep learning network.
The same network has been tested with the original images and is named “Group 1”. Image pre-processing
methods were not applied to Group 1 images. The definition of each group is given in Table 1. For Group
1, The success metrics are very low as expected because the data set is very small for deep learning
applications. In Table 2, skin and nonskin achievements for group 1 may seem high, but the IoU score is
very low for the skin. The IoU score is a metric that shows how much the ground truth predicted result
overlaps with each other. That is why IoU is a useful parameter that shows success very clearly. In Group
1, IoU success is sufficient for Nonskin, but it is not seen that it is very successful for the skin.
In Group 2, 156 original images and their noise-added versions were included. The deep learning network
is trained with 312 images. After the training network, images were tested with the original images. The
skin IoU score decreases slightly compared with Group 1, but an increase in the nonskin’s IoU is visible.
Although adding noise to images and moving the data set far from its original state, there does not appear
to be a serious decrease in success rate. On the contrary, even if the success rate drops, the network will be
better prepared for new noise-containing test images. The decrease in skin detection success is something
that can be sacrificed for this cause.
In Group 3, there are only images with random noise added. The network trained with this dataset will be
tested again with noisy images. In other words, the deep learning network is completely deprived of the
original images. This will result in the network having a very difficult time recognizing the new incoming
images. The already unsuccessful results are not surprising. The network fails
CONCLUSION
In this study, noise addition, which is one of the methods of increasing datasets artificially, has been
investigated. Adding noise to images makes the network more prepared for new images. The deep learning
network is trained with three different datasets and each one is discussed. It has been examined how much
the success rates decrease as the dataset moves away from its original state. Although the network is
prepared for the upcoming noisy images, the success of detecting existing original images has decreased.
This is something that can be sacrificed. In the next study, different datasets will be tested with images from
different sources. The optimum rate of adding noise to these datasets to avoid overfitting and increase
success will be investigated.
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CONFLICT OF INTEREST
The authors stated that there are no conflicts of interest regarding the publication of this article.
REFERENCES
[1] M. Gaoa , X. Honga, S. Chenb and C. J. Harrisb,” A combined SMOTE and PSO based RBF classifier
for two-class imbalanced problems,” Neurocomputing, vol. 74, pp. 3456–3466, 2011
[2] F. Fernandez-Navarro, C. Hervas-Martinez and P. A. Gutierrez,” A dynamic over-sampling procedure

based on sensitivity for multi-class problems,” Pattern Recognition, vol. 44, pp. 1821–1833, 2011
[3] M. A. Mazurowski, P. A. Habas , J. M. Zurada , J. Y. Lob , J. A. Baker and G. D. Tourassi, Training

neural network classifiers for medical decision making: The effects of imbalanced datasets on
classification performance, Neural Networks, (21) pp.427-436, 2008.
[4] Cohena, M. Hilariob , H. Saxc , S. Hugonnetc and A. Geissbuhlera, “Learning from imbalanced data in
surveillance of nosocomial infection,” Artificial Intelligence in Medicine, vol. 37, pp. 7—18, 2006
[5] H. Yua, J. Nib and J. Zhaoc, “ACOSampling: An ant colony optimization-based undersampling method
for classifying imbalanced DNA microarray data,” Neurocomputing, vol. 101, pp. 309–318, 2013
[6] Rahman, Shaza M., and Ajith Abraham. "A review of class imbalance problem." Journal of Network
and Innovative Computing 1.2013 (2013): 332-340.
[7] Phung, Son Lam, Abdesselam Bouzerdoum, and Douglas Chai. "Skin segmentation using color pixel
classification: analysis and comparison." IEEE transactions on pattern analysis and machine intelligence
27.1 (2005): 148-154.
[8] Phung, Son Lam, Douglas Chai, and Abdesselam Bouzerdoum. "Adaptive skin segmentation in color
images." 2003 IEEE International Conference on Acoustics, Speech, and Signal Processing, 2003.
Proceedings.(ICASSP'03).. Vol. 3. IEEE, 2003.
[9] Al-Tairi, Zaher Hamid, et al. "Skin segmentation using YUV and RGB color spaces." Journal of
information processing systems 10.2 (2014): 283-299.
[10] Phung, Son Lam, Abdesselam Bouzerdoum, and Douglas Chai. "Skin segmentation using color and
edge information." Seventh International Symposium on Signal Processing and Its Applications, 2003.
Proceedings.. Vol. 1. IEEE, 2003.
[11] Gasparini, Francesca, and Raimondo Schettini. "Skin segmentation using multiple thresholding."
Internet Imaging VII. Vol. 6061. SPIE, 2006.
[12] http://cs-chan.com/downloads_skin_datase
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FRACTAL AND MULTI-FRACTAL ANALYSES OF THE GEOMAGNETIC FIELD

VARIATIONS CAUSED BY THE EARTHQUAKE ON JANUARY 24, 2020 IN
TURKEY
Andriy ONISHCHENKO1*, Leonid CHERNOGOR2, Oleg LAZORENKO3

1
Physics Department, Faculty of Automatics and Computerized Technologies,
Kharkiv National University of Radioelectronics, Kharkiv, Ukraine
2
Space Radiophysics Department, School of Radiophysics, Biomedical Electronics and Computer Systems,
V. N. Karazin Kharkiv National University, Kharkiv, Ukraine
3
General Physics Department, School of Physics, V. N. Karazin Kharkiv National University, Kharkiv, Ukraine
ABSTRACT
Fractal and multi-fractal properties of the Earth’s magnetic field time variations caused by the earthquake took place on January
24, 2020 in Turkey were investigated. Using Dynamical Fractal Analysis method proposed by the authors for both (D and H)
horizontal components of geomagnetic field, the time dependences for the Hurst fractal dimension were obtained. With usage
of the Wavelet Transform Module Maxima method and the Multi-Fractal Detrended Fluctuation Analysis method, the set of
traditional and original multi-fractal numerical characteristics was estimated. Combining the fractal and multi-fractal analyses
results with ones for the time-frequency structure, obtained the Continuous Wavelet Transform application, the set of
disturbances caused by the earthquake was discovered. For these disturbances, all needed time-frequency, fractal and
multifractal characteristics were estimated. The disturbances were shown to be fractal ultra-wideband processes with complex,
non-stationary multi-fractal structure. Two promising candidates for the role of earthquake precursors were revealed. One
possible earthquake precursor in both horizontal components of the geomagnetic field time variations seems to be detected.
This precursor was shown to be registered 25.5 hours before the earthquake event. Being be found in time variations of the
multi-fractal characteristics only for both horizontal components of the geomagnetic field, another possible earthquake
precursor took place 0.5 hours before the earthquake event. The so-called transition of the multi-fractal process to the mono-
fractal mode was detected. For both precursors, the time-frequency, fractal and multifractal characteristics were estimated.
Keywords: Fractal Ultra-Wideband Process, Fractal Analysis, Multi-Fractal Analysis, Geomagnetic Field Time Variations,
Earthquake
1. INTRODUCTION
According the non-linear paradigm formulated in the late 1970s by prof. L. F. Chernogor, many
processes in open, non-linear, dynamical systems, which caused by impact of a non-stationary, powerful
source, are appeared to be short-time, non-linear, ultra-wideband (UWB) and fractal ones [1 – 3]. A
powerful earthquake is namely such source, and the Earth – atmosphere – ionosphere – magnetosphere
(EAIM) system is namely such system. All subsystems in the EAIM system strongly interact with each
other and, therefore, the significant disturbances in the magnetosphere caused by the powerful
earthquake impact can be found. Moreover, the corresponding perturbations in the EAIM system were
appeared to be global. This fact is fully explained by the phenomenon of appearance of the large-scale
and global perturbations in the EAIM system caused by a non-stationary, powerful source influence.
Such phenomenon had been discovered in the former Soviet Union in the late 1980s by the scientific
group led by prof. L. F. Chernogor [1 – 3].
Therefore, the geomagnetic field time variations caused by a powerful earthquake can be registered by
the magnetometers very far from the source. These signals are expected to be both UWB and fractal
ones. Thus, the theme of the paper seems to be actual, topical and interesting.
The purpose of this paper is to investigate the fractal and multi-fractal properties of these signals with
usage of the fractal and multi-fractal analysis methods, which are able to research a non-stationary fractal
structure of a signal.
*Corresponding Author: andrey.onishchenko@nure.ua

Receiving Date: ... Publishing Date: ...
2022, 1(1), pp. 56-61, DOI: 10.5281/zenodo.7248487
2. EARTHQUAKE EVENT AND EXPERIMENTAL DATA
An earthquake with a magnitude of 6.7 and a duration of 15 s occurred at 17:55:14 (hereafter universal
time, UT) on January 24, 2020 near the Sivridge city, Elazig province, Turkey, where about 4 thousand
people live. 1,547 people were injured by the earthquake, and 35 people died. The coordinates of the
epicenter are as follows: 38.4° N. w., 39.1° east. d. The depth of the earthquake was 10 km [4].
Basing on data on the space weather state during the earthquake [4], it can be maintained that this day
was magnetically quiet. This allows to hope that the cause of the studied variations of the Earth's
electromagnetic field is really this earthquake, and therefore the detected effects can be associated with
it. The experimental data were obtained with the unique magnetometer-fluxmeter placed on the
Radiophysical Observatory of the V. N. Karazin Kharkiv National University (Grakovo, Kharkiv
Region, Ukraine) [5].
A thorough analysis of the time-frequency structure of wave processes that occurred in the geomagnetic
field during the powerful earthquake of January 24, 2020, was performed in [4]. Therefore, here we will
focus specifically on the study of the fractal properties of these identified processes. In our research, the
time variations of the geomagnetic field (horizontal D- and H-components) were analyzed as they
occurred from 15:00 to 21:00 on the eve of the earthquake (January 23, 2020), on the day of the
earthquake (January 24, 2020) and in the day after the earthquake (January 25, 2020).
3. FRACTAL AND MULTI-FRACTAL ANALYSIS METHODS
In our investigations, the fractal analysis is represented by the Dynamical Fractal Analysis (DynFA) [6]
which includes the Hurst fractal dimension calculated in sliding window in time domain and the
Continuous Wavelet Transform (CWT) [7].
The multi-fractal analysis is connected with usage of the Wavelet Transform Modulus Maxima
(WTMM) [7] and the Multi-Fractal Detrended Fluctuation Analysis (MF DFA) [8]. Using these two
methods, the set of the multi-fractal characteristics of a signal analyzed are estimated.
In addition to the traditional characteristics such as the minimal (αmin) and the maximal (αmax) values of
the multi-fractal spectrum function f(α), it’s width (Δα) and the maximum location (α*) known also as
the ‘Generalized Hurst Exponent’, the three new ones were proposed. Let’s consider them.
By the definition, the asymmetry coefficient of the multi-fractal spectrum function is given by the
relation:
α"#$ − α∗
!! = log (1)
α∗ − α"&'
Practical experience suggests that real multi-fractal spectra are often appeared to be asymmetric. The
new numerical characteristic given by the relation (1) allows to take this into account. If Kf=0, a multi-
fractal spectrum is symmetric; if Kf>0, a multi-fractal spectrum maximum is shifted to the left; if Kf<0,
it is shifted to the right. It is important that if a multi-fractal to a monofractal simplifies, Kf=0.
The second new multi-fractal characteristic introduced in the paper is called as ‘the relative multi-fractal
width’. By the definition, it is given by the relation:
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2022, 1(1), pp. 56-61, DOI: 10.5281/zenodo.7248487
Figure. Results of multi-fractal analysis (MF DFA method) of time variations of the geomagnetic field on January 23, 2020
(D-component): (a) is the signal in time domain, (b) is αmin(t), (c) is αmax(t), (d) is Δα(t), (e) is α*(t), (f) is µα(t), (g) is Kf(t), (h)
is fα(t), (i) is the CWT SDF; and on January 24, 2020 (H-component): (j) is the signal in time domain, (k) is αmin(t), (l) is αmax(t),
(m) is Δα(t), (n) is α*(t), (o) is µα(t), (p) is Kf(t), (q) is fα(t), (r) is the CWT SDF. The CWT SDF was obtained with the fourth
order Daubechie’s wavelet usage. The vertical dashed line shows the moment of the earthquake. The horizontal dotted lines
denote the corresponding values estimated with the WTMM method usage for the whole signal investigated.
Δα
µ( = (2)
α∗
The relation (2) is an analogue of the relative bandwidth, which is used to describe, in particular, the
UWB signals [9].
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2022, 1(1), pp. 56-61, DOI: 10.5281/zenodo.7248487
The third new multi-fractal characteristic is a multi-fractal support dimension, which is defined as a
value of the multi-fractal spectrum function f(α) calculated for α=α*, that is fα=f(α*).
In our investigations, all estimations of the disturbance time-period parameters for signals analyzed were
performed in the period range T = 15…1000 s, as well as namely this period range had been used in [4].
4. ANALYSIS RESULTS
Using the DynFA as a fractal analysis method, we obtained such results. About half an hour before the
earthquake, the Hurst dimension DH(t) began to increase from approximately 1.5 to 1.9. The maximum
of the function DH(t) coincided with the beginning of the earthquake, after which it began to decrease.
Its second maximum, slightly smaller in magnitude, was observed approximately 70 minutes after the
beginning of the earthquake and is most likely associated with the aftershock. From a physical point of
view, this means that the fractal process half an hour before the earthquake significantly changed its
character: from almost purely random (DH(t)=1.5) it became strongly anti-persistent (DH(t)=1.9). It
should also be noted that this happened almost synchronously for both components of the geomagnetic
field. Instead, in order to find out whether the obtained effects are a regularity for large earthquakes,
many more similar events should be investigated in the future.
The main information about time changes of the multi-fractal characteristics of the studied signals was
provided by the MF DFA method. Being strongly limited by the approved paper volume, as the
examples, we introduce the results of multi-fractal analysis of time variations of the geomagnetic field
on January 23, 2020 (D-component) (Figure, a – i) and on January 24, 2020 (H-component) (Figure, j –
r) only. On the graphs of time dependences of multi-fractal characteristics, the corresponding values of
these characteristics, obtained by the WTMM method, are shown by horizontal dashed lines. This is
quite convenient, because it demonstrates how the local value of the characteristic deviates from what
is obtained immediately for a whole signal analyzed. The spectral density function (SDF) of the CWT
(Figure, i, r) allows to show all peculiarities of the time-period structure of the signal analyzed.
Let's start with January 23, 2020, that is, the day before the earthquake. For the D-component of the
geomagnetic field (Figure, a), two main disturbances were detected: the first from 16:30 to 18:00, the
second from 19:30 to 21:00 (Figure, i). During the first of them (16:30 – 18:00 UT), an increase of the
αmin(t) from approximately 0.1 to 0.3 (Figure, b), a sharp increase followed by a drop in the values of
the αmax(t) (Figure, c), Δα(t) (Figure, d) and α*(t) (Figure, e) in the ranges of 0.6 – 1.3, 0.4 – 1.2 and 0.3
– 0.7 respectively, an almost linear decrease of the µα(t) (Figure, f) from 2.0 to 0.6, as well as the
formation of a significant local minimum of the Kf(t) (Figure, g) in the range from 0,5 to -1.4 were
observed. The authors [4] associate this disturbance with the precursor of the earthquake, which
appeared approximately 25.5 hours before the event itself. The second wave disturbance is associated
with an increase in magnetic activity [4]. The following features of multi-fractal characteristics were
revealed for it. An increase of the αmin(t) (Figure, b) approximately from -0,1 to 0.1, a sharp increase
followed by a drop in the values of αmax(t) (Figure, c), Δα(t) (Figure, d) and α*(t) in the ranges of 0.8 –
1.2, 0.6 – 1.2, and 0.35 – 0.55, respectively, an almost linear decrease of the µα(t) (Figure, f) from 2.5
to 1.2 were obtained. For the H-component of the geomagnetic field, all multi-fractal characteristics
slightly fluctuated near their average values for the entire six-hour period.
On the day of the earthquake (January 24, 2020), for the D-component of the geomagnetic field for
disturbances observed from 19:10 to 20:25 and associated with the magnetic effect of the earthquake,
the changes of the αmin(t) in the range from 0.0 to 0,2, the increasing of the αmax(t) from 0.6 to 1.0, of the
Δα(t) from 0.5 to 0.9 and of the α*(t) from 0.3 to 0.55 were registered. In the same period of time, for
the H-component (Figure, j), the insignificant variations of the αmin(t) (Figure, k), αmax(t) (Figure, l) and
Δα(t) (Figure, m), the formation of a time maximum of the α*(t) (Figure, n) in the range of 0.25 – 0.45,
as well as a time minimum of the Kf(t) (Figure, p) in the range of 0.0 to -1.5 were detected.
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But the most interesting thing, in our opinion, on the day of the earthquake in the behavior of the
multifractal characteristics was that about half an hour before the earthquake itself, "falls" in the function
fα(t) (Figure, q) appear in the registrations of both components. Such "falls" were not found anywhere
else on any of the analyzed days. For the D-component of the geomagnetic field, these "falls" were
accompanied by the formation of the αmin(t) maximum in the range from 0.05 to 0.25, minimums of the
αmax(t) from 0.3 to 0.6, Δα(t) from 0.2 to 0.55), Kf(t) from 0.0 to -1.3 and µα(t) from 0.5 to 1.6, a decrease
of the α*(t) from 0.5 to 0.25. For the H-component, the minimums of the αmax(t) (Figure, l) from 0.3 to
0.5, Δα(t) (Figure, m) from 0.2 to 0.5), α*(t) (Figure, n) from 0.2 to 0.4, Kf(t) (Figure, p) from -0.5 to -
1.5 and µα(t) (Figure, o) from 0.5 to 1.6 were found. In addition, as shown by the CWT SDF (Figure, r),
in the half hour before the earthquake, the activity in the period band T = 15…1000 s generally became
very small.
5. DISCUSSION
Both considered disturbances, detected on January 23, 2020, are quite similar in nature. In both cases, a
wave perturbation appeared in the form of the UWB process, which can be considered non-fractal. As
it was found during our investigations of the large model signal set, the appearance of a non-fractal
component on the background of a fractal signal leads to a significant increase of the αmax(t), Δα(t) and
α*(t). In addition, in many cases, these values may even go beyond the limits of fractality (0<α<1). This
was observed here for the first two functions. If the function αmin(t) also does not change, then this is a
normal reaction of the fractal signal to the appearance of an additive non-fractal component. But in both
cases, a slight increasing of the αmin(t) were appeared to be detected. That is, we can make an assumption
that the parameters of the fractal component of the signal have also changed somewhat, and this gives
grounds to say about the presence of not just the UWB process, but the fractal UWB (FUWB) process.
Now let’s return to the "falls" in the function fα(t). From a physical point of view, the obtained results
mean that half an hour before the earthquake, in the absence of actual disturbances, there was a
significant change in the fractal properties of the time variations of both components of the geomagnetic
field. The typical multi-fractal behavior (Δα=0.5, α*=0.4) changes sharply to almost monofractal
(Δα=0.2, α*=0.2) one, which is clearly shown by the drop in the multifractal support dimension fα(t)
relative to the traditional unit level. Therefore, before the earthquake itself, the multifractal nature of the
variations of both components of the geomagnetic field changed to a monofractal, moreover, strongly
anti-persistent (fractal dimension D=2- α* is equal to 1.8). suddenly, only future studies of geomagnetic
field time variations caused by the powerful earthquakes will be able to answer the question of whether
the obtained feature can be considered as a "marker" of a future earthquake and can be used for the
earthquake prediction.
It is worth emphasizing that the results of the multi-fractal analysis coincide very well with the results
of the monofractal analysis. A significant addition to the monofractal analysis result is the fact that the
growth of the DH(t) (and, accordingly, the decrease of the α*(t)) was accompanied by the transition of
the multi-fractal process to the monofractal regime. It is also important that this process was more
significant for the first maximum of the DH(t) than for the second one: although the narrowing of the
multi-fractal spectrum is well observed in both cases, the decrease of the function fα(t) in the second
case is less noticeable. The last means that the degree of "monofractalization" of the multi-fractal process
in the second case was appeared to be smaller.
6. CONCLUSIONS
Using fractal and multi-fractal analysis methods, fractal and multi-fractal properties of the Earth’s
magnetic field time variations caused by the earthquake took place on January 24, 2020 in Turkey were
investigated. The set of fractal and multi-fractal characteristics was estimated.
The UWB processes found in the complex time-period structure of disturbances were shown to be the
FUWB ones.
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Peculiarities of time dynamics of fractal and multi-fractal characteristics, which may be associated with
precursors of earthquakes, have been revealed. It was found that before the earthquake itself, the multi-
fractal nature of the variations of both components of the geomagnetic field changed to a monofractal,
moreover, strongly anti-persistent one, which is clearly shown by the drop in the of the multifractal
support dimension. It is possible that this transition can be used as a "marker" of a nearby earthquake,
but studies of other earthquakes are needed to confirm or disprove this.
In both components of the geomagnetic field, another, less pronounced transition to the monofractal
regime was detected. It occurred already after the beginning of the earthquake and was possibly
associated with the aftershock. The fact that the degree of "monofractalization" of the multi-fractal
process in the second case was smaller can be explained by the lower power of the aftershock compared
to the first shock.
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[7] Mallat S. A wavelet tour of signal processing. San Diego, London, Boston, N.Y., Sydney, Tokyo,
Toronto: Academic Press, 1998.
[8] Kantelhardt JW, Zschiegner SA, Konscienly-Bunde E, Havlin S, Bunde A, Stanley HE. Multifractal
detrended fluctuation analysis of nonstationary time series. Physica A, 2002, 316: 87-114.
[9] Astanin LY, Kostylev A A. Ultrawideband Radar Measurements: Analysis and Processing. London:
The Institute of Electrical Engineers, 1997.
61
2022, 1(1), 62-76., DOI: 10.5281/zenodo.7252851
APPLYING OF THE NEW GENERATION PLASTIC ADDITIVES TO THE

KITCHEN APPLIANCES: INVESTIGATION OF STRUCTURAL AND
THERMOSTATIC PROPERTIES OF ORGANOMETALLIC MN (II) AND CU (II)
STREAT- BORATE COMPLEXES
İlkan KAVLAK
Br Dizayn Mobilya İnşaat ve Isıtma ve Soğutma Sistemleri A.Ş., Industrial Design Centre, Eskişehir Industrial Area, Turkey.
ABSTRACT
In this study, two new organometallic stearate complexes are described in Mn(C18H35O2)2. (B4O7) (1) and Cu(C18H35O2)2.
(B4O7) (2) have been synthesized as plastic additive materials. Thermostatic behaviors of the complexes have been analyzed
with described methodology at the ISO 182-2 standard. Additionally, the structural properties of the synthesized complexes
were investigated by elemental analysis, powder XRD, and vibrational (FT-IR and Raman) spectroscopic techniques.
The Thermostatic analyses show that synthesized complexes act as a strong HCI scavenger during plastic decomposition. If
the plastic dough is composed of strong HCl scavenger agents. The heating resistance capacity will be increased. According to
the thermostatic analysis results, the synthesized complexes have been added to the PVC rough as plastic additives. Then,
Plasticized complexes were injected into the plastic mold. The obtained plastic materials have been used in domestic built-in
hobs as thermal insulator gaskets at the burner pools. The thermally insulated behaviors of the new generation plastic additives
have been observed via Elimko 32T channel probes digital thermometers and analyzed with described methodology at the TS
EN 30-1-1+A3:2014 standard.
The results are shown that both complexes behaved as thermal barriers between surface of built-in hobs and burners. The
thermal decay of the plastic doughs is following 1>2.
Keywords: PVC, plastic additives, heat-barrier, organometallic complex, EN ISI 182-2, Dehydrocholorination, HCl
scavengers, EN 30-1-1+A3:2014, built-in hobs.
1. INTRODUCTION
Plastic is an important raw material for products or product groups that make our daily life easier in a
wide area, from household appliances to the production of automotive spare parts, from the door and
window joinery systems to packaging materials. Since plastic is an easily produced and recyclable
material are needed for insulator, heat barrier, mold material, prototype material as a product group, or
the production of electronic device appliances and home appliances as products. It is also widely used
in the white goods industry as a plastic raw material. It is used as sound insulation materials on the
engine covers and engine walls for aspirators or hoods. Similarly, the heat barrier, thermal insulator,
liquid sealing gaskets, gas sealing gaskets, and gas control systems are used for built-in hobs and ovens.
The plastic additive materials which, are included in the plastic dough, contribute to applying plastic in
such a wide range as a raw material. In this study, polyvinylchloride (PVC) was used as plastic raw
material, and Mn(II) or Cu(II) metal complexes of stearate and borax molecules were synthesized with
an aim of thermal plastic additives applied as a heat barrier in built-in hobs production. The synthesized
plastic additives will trap the hydrochloric acid (HCl) gas ions released during the thermal degradation
of polyvinyl chloride (PVC) into their molecular structures, thus allowing the thermal degradation rate
of PVC to be delayed and prevented [1]. Many studies examining the effects of Stearic Acid, borax and
barbiturate molecules and their metal complexes on the thermal stability of PVC are available in the
literature [2, 3] [4]. [1, 5-9]. Within this context, the borax and stearate-based metal (II) complexes were
synthesized as powder. These complexes were investigated by elemental analysis, powder XRD
diffraction techniques, XRF spectroscopy, thermoanalytic analyses techniques (TG, DTG, DTA).
Additionally, the vibrational properties of the complexes were studied by FT-IR and Raman spectral
techniques. Furthermore, the new generation PVC dough were prepared with synthesized complexes in
order to reach out thermal stabilization effect on PVC degradation. The new generation PVC doughs
*Corresponding Author: ilkankavlak@brdizayn.com.tr

2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
were plasticized via gelation methods. Hence, the new plastic materials were manufactured.
Dehydrochlorination test was performed which is described methods in EN ISO 182-2 standards. The
plastic materials were shaped as gasket. Then the plastic materials have applied as surrounded burner
pools between built-in hobs surfaces. Thermal barrier properties have been controlled via 32 channel
thermometers with their thermocouple by Elimko 32T digital thermometer device. The test results were
shown that synthesized complexes were behaved as thermal stabilizer in the PVC dough and the plastic
materials behaves thermal barrier between built in hob surface and burners.
2. MATERIALS AND METHODS
The tests and analyses performed on the new generation plastic additives obtained from stearate and
borate-based Mn(II) and Cu(II) metal complexes, which are intended to be used as a heat barrier in built-
in hobs and ovens, are listed in Table 1.
Table 1. Test and Analyses for new generation plastic additives
Analyses Methods
The test of
The molecular formula of Thermal thermal barrier
New Generation Plastic Stability applying
Elemental FT- TG-DTG-
Additives XRD XRF Raman Test Surface
Analyses IR DTA
Ref: ISO Temperature
EN 182-2 (°C)
Ref: EN 30-2-2+1
Mn(C18H36O2)2.(B4O7)∙2H2O ■ ■ ■ ■ ■ ■ ■/ 65 ■/96-142
Cu(C18H35O2)2.(B4O7) H2O ■ ■ ■ ■ ■ ■ ■/ 57 ■/ 108-142
2.1. Materials
All materials, copper (II) chloride dihydrate (CuCl2·2H2O, 99%), Manganese(II) chloride tetrahydrate
(MnCl2·4H2O, 99%) Sodium stearate (CH3(CH2)16COONa, 97%) and sodium tetraborate anhydrous
(Na2B4O7, 99.5%) were used as received from commercial sources.
2.2. Syntheses of the complexes

2 mmol sodium stearate was solved in the ethanol and stirred for 2 hours. To provide the best solvent,
the solution is warmed to 50 °C and slightly added the ethanol due to evaporation. 1 mmol of metal salts
(CuCl2·2H2O)(aq) or (MnCl2·4H2O)(aq) was added dropwise to the solution. The solutions are stirred
for 1 hour. On the other hand, Sodium tetra borate is solved in warm water (100 °C). Sodium tetra borate
is added dropwise to the solution. The mixture was stirred for 14 hours. After stirring for 14 hours, the
complexes collapsed. Then, the solutions were filtered and dried at room temperatures. Finally, The
colors of the obtained complexes for Mn(II) and Cu(II) are brown and blue, respectively. The freshly
prepared complexes were analyzed for C, H and N and the results are given in Table 2. Elemental
analyses are in good agreement with the calculated values.
Table 2. Molecular formula for complexes
Complex Molecular Formula MA (g/mol) %C %H %N
Experimental 54,8 9,22 -

1 Mn(C18H36O2)2.(B4O7)∙2H2O 815,50
Theoretical 54,38 9,13 -
Experimental 55,73 9,35 -
2 Cu(C18H35O2)2.(B4O7) H2O 805,49
Theoretical 53,80 9,03 -
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
Similarly, determined closed formulas of the complexes by elemental analysis methods were supported
by thermogravimetric analysis. For 1 complex, according to the DT-DSC thermal degradation curve of
the complexes, it shows a stable structure up to 306 ºC (Figure 1).
105 3,5
100
95 TG
90 3
85
80 2,5
75
70
65 2
Mass (%)
60
55
∆T
50 1,5
45
40 1
35
30
25 0,5
20 DTA
15 0
10
5 DTG
0 -0,5
31
48
76
103
131
159
188
216
244
272
300
328
356
385
413
441
469
497
525
553
581
609
637
665
693
721
749
777
805
833
861
889
917
945
973
1001
1029
1057
Temperature (º C)
Figure 1. The TG, DTG, and DTA curves of the complex 1
The 1 complex decomposed in 3 stages in the temperature range of 30-1059 ºC as seen Table 3. It is
seen that 2 moles of H2O molecules, corresponding to 4.5% of the total mass, are separated from the
complex in the temperature range of 30-306 ℃. 2 moles of stearic acid were removed from the complex
in the temperature range of 306-411 °C. It is separated into two different forms as B2O4 and B2O3 in the
temperature range of 411-567 °C from the complex. B2O4 left the structure while B2O3 remained
unchanged. Finally, the curve stabilized in the temperature range of 567-1059 °C and MnO and B2O3
materials, corresponding to 21% of the total mass, remained.
Table 3. Thermoanalytical Data (TG, DTG, DTA) for the complex 1
Solid
Mass loan (%)
decomposition
Compounds Removed
Temperature
Compounds Removed Group Stage product Group Found Calculated
Range
(MA) (MA)
(%) (%)
30-306 ºC Mn(C18H36O2)2B407·2H2O 2H2O 815,5 36,02 4,50% 4,51%
306-411 ºC Mn(C18H36O2)2B407 (C18H36O2)2 779,13 568,54 66,54% 69,71%
411-567 ºC Mn·B407 B2O4 210,94 86 8% 10,54%
567-1059 ºC CdO+B2O3+CO2 199,5 - 21% 24,46%
For 2 Complex, the thermal degradation curve of the complex is given in Figure 2. Here, it has been
determined that the Complex degrades in 3 stages in the range of 30-1068 ºC. The thermoanalytic
decomposition steps of the complex and the percentage of separated material are listed in Table 4. It is
seen that the complex is stable up to a temperature value of 212 ºC. After this temperature value, 1 mol
of H2O molecule is separated from the complex which corresponds to 2.23% of the total mass.
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
120 -30
-25
100
-20
80
-15
60
∆T
-10
Mass %
40
-5
20
0
0 5
30
53
88
116
146
176
206
236
266
295
325
355
385
414
444
474
504
533
563
593
622
652
682
711
741
771
801
831
860
890
920
950
979
1009
1039
1068
Temperature (°C)
Figure 2. The TG, DTG, and DTA curves of the complex 2
In the temperature range of 212-419 °C, 2 moles of stearic acid were removed from the structure. Borate
was separated into two different forms B2O4 and B2O3 in the temperature range of 419-852°C, and B2O4
was separated from the structure in this temperature range. In the temperature range of 852-1068 °C, it
was determined that CuO and B2O3, which constitute 19% of the initial mass, remained.
Table 4. Thermoanalytical Data (TG, DTG, DTA) for the complex 2

Solid
Mass loan (%)
decomposition
Te Compounds Removed
mperature Compounds Removed Group Stage product Group Found Calculated
Range (MA) (MA)
(%) (%)
30-306 ºC Cu(C18H36O2)2B407·2H2O H2O 805,49 18,01 2% 2,23%
306-411 ºC Cu(C18H36O2)2B407 (C18H36O2)2 787,48 568,54 68% 70%
411-567 ºC Cu·B407 B2O4 218,79 86 9% 10,67%
567-1059 ºC - CuO+B2O3+CO2 199,5 - 19% 18,51%
2.3. Plasticizing
The plastic dough is blended with k=74 hardness PVC, 5% by mass, CaCO3 by mass, 5% by mass of
chlorinated polyethylene, and 5% by mass of plastic additive materials. Mass values in the plastic recipe
are not a rule, they are the values at which the best fluid plastic is obtained after blending. The best flow
rates were obtained with these values for the plastic blend prepared by the gelling method. After
preparing the plastic blend, the mixtures were stirred mechanical mixer. When the blend were mixed
with a mechanical mixer, acetone was added drop by drop. The obtained liquid mixtures are dropped
plastic mold and pressed after the molds are baked in the oven at 170°C for 15 minutes. After baking,
the plastic molds are dropped in the cold water. Finally, plastic materials are obtained.
2.4. Physical measurements

The complexes obtained were performed elemental analyses. Elemental analyses were carried out on
LECO, CHNS-932 analyzer for C, H, and N at the Middle East Technical University Central Laboratory.
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
FT-IR and Raman spectra of the complexes were recorded in the region of 4000–250 cm-1 via Perkin-
Elmer FT-IR 100 spectrometer at a resolution of 4 cm-1 and Bruker Senterra Dispersive Raman
Microscope using the 785 nm line of a 3B diode laser, respectively. Perkin Elmer Diamond TG/DTA
thermal analyzer was used to record simultaneous TG, DTG, and DTA curves in the static air atmosphere
at a heating rate of 10 K min-1 in the temperature range of 30–700 °C using platinum crucibles at the
Eskişehir Osmangazi University Central Laboratory (ARUM). The XRD patterns of the powder
products were obtained on a Rigaku Rint 2200 diffractometer using Cu-Kα radiation. Then, the
molecular structures were obtained by powder XRD diffractometers. Meanwhile, the PXRD data were
solved via the Rietveld analysis program as Match 3.0 [10]. XRF data of the complexes were obtained
in the Rikagu ZSX PRIMUS device in Eskişehir Technical University Physics Department. The
standards used; Na2O, SiO2, Fe2O3, NiO, MgO, Al2O3, K2O, CaO, MnO, BaO, CuO, P2O5, CdO, SnO2,
As2O3. The thermostatic analyses and dehydrochlorination test were performed in the DHC device at
the Eskişehir Osmangazi University Molecular Spectroscopy and FT-IR laboratory. Surface heating test
and thermal barrier tests were performed via Elimko 32 channel thermometer and with thermocouples
by BR Dizayn Industrial Design Center Laboratory.
2.5 Thermostatic Analysis (DHC Test)
The ISO 182-2 standard was established to determine the thermal stability of vinyl chloride
homopolymer and copolymer-based products and to determine the release tendencies of hydrogen
chloride and other acidic components resulting from the oxidation of PVC while heat treatment. The
stability time determined by the ISO 182-2 standard is measured by the time measured during the change
in the initial PH value (6.00) and the test termination PH value (3.20) of the HCl gas released from the
plastic at 200 °C. In this study, the plastic sheets obtained from the plasticization process are turned into
1 cm2 square pieces and placed in the sample cell. 0.1 mol/L NaCl (125 ml) solution is added to the
DHC test cell. High purity N2 gas is used as the conditioning gas to transmit the H+ and Cl- ions that
arise during the heating of the sample from the sample cup to the test cup. The gas flow rate is adjusted
by a flow meter (120 cm3/min). To adjust the DHC cell to the initial PH value (6.00), 0.1 mol/L NaOH
solution and 0.1 mol/L HCl solution are used as PH stabilizers. The Dehydrochlorization test system is
given in Figure 3.
2.6 Heat Barrier Test Unit
The plastic materials produced from plastic doughs containing new generation plastic additives were
shaped with the help of a knife to frame the built-in hobs burners, placed between the built-in hobs
surface and the burners. Then built-in hobs were mounted. Thermocouples connected to Elimko branded
32-channel T-type thermometer are placed on the surface, bottom plate, and inside of the built-in hob.
Hence, the surface temperatures were thus transmitted to the digital thermometer.
The experiment was carried out in 3 phases. In the first phase, commercial gaskets were used and the
furnace temperature values were obtained during heating and cooling. In the second phase, heating and
cooling tests were carried out on plastic materials obtained with plastic doughs containing Mn (II) or Cu
(II), respectively. Finally, the data obtained from the three tests were placed on top of each other and the
heat barrier results were compared.
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
(a) (b)
(c)
Figure 3. Thermostatic Analysis test unit: (a) Sample Cell, (b) U-type sample cell, (c) DHC test unit.
3. Results and Discussion

In this study, Mn(C18H36O2)2·(B4O7)∙2H2O (1), Cu(C18H35O2)2.(B4O7)∙H2O (2) were synthesized as a new
generation plastic additive and obtained as powder. The structural properties of the synthesized
complexes were investigated by FT-IR and Raman spectroscopy, XRD diffraction, XRF spectroscopy,
and gravimetric thermal analysis methods. Plastic blend was obtained by using synthesized new
generation plastic additives. The obtained plastic blends were turned into plastic by plasticization
method. The thermal stability of the plasticized materials was determined by thermostatic analysis. In
addition, the thermal barrier behavior of the obtained plastic materials was examined and compared with
the thermal barrier behavior of standard commercial gaskets.
3.1 Structural Analyses

Vibration spectroscopy (FT-IR, Raman) analysis of the complexes was investigated based on the
stearate and borate vibrational wavenumbers in the complexes. In addition, the metal oxide bond
vibration wavenumbers of the synthesized complexes were compared with the metal-oxide bond
vibration wavenumbers obtained from some studies in the literature [11, 12] . Infrared spectra of sodium
stearate, sodium borate as ligands in this study are given in Figures 4 and FT-IR and Raman spectra of
the complexes are given between Figures 5.
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
(a) (b)
Figure 4. The infrared spectra of sodium tetraborate (a), sodium stereate (b)
As seen in Table 5, ν(OH) stretching and ν(H-O-H) bending vibration bands are observed in wave
numbers of 3405 cm-1 and 1652 cm-1, respectively [11]. For this region, vibration bands with wave
numbers of 1432 cm-1, 1344 cm-1, and 1258 cm-1 were determined as asymmetric stretch vibration bands
of the B-O bond in BO3. In the complexes, the borate ligand is expected to coordinate through the oxygen
atoms. For this reason, a shift to the high-frequency region is expected for ν(B-O) stretching vibrations
and d(O-B-O) bending vibrations. For the sodium borate ligand, ν(B-O) stretching vibrations were
recorded at 1432 cm-1, 1344 cm-1, and 1258 cm-1, respectively, while d(O-B-O) were recorded at 500
cm-1 and 454 cm-1.
(a) (c)
(b) (d)
Figure 5. The FT-IR and Raman spectra of 1 (a,b), 2 (c,d).
The vibration bands at wave numbers 1130 cm-1 and 1076 cm-1 for sodium borax are due to the
asymmetric stretching of the B-O bond in BO4 [11]. While this vibration band was observed at 1159
cm-1 and 1087 cm-1 wave numbers for the Mn(B4O7)2∙2H2O complex, it was observed at 1176 cm-1 and
1109 cm-1 wave numbers for the 1 complex.
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
Table 5. Borate anions wavenumbers in the compexes (cm -1)
Sodium
Mn(B4O7)2∙2H2O (1) (2)
Assignments* a Borate
FT-IR*a FT-IR FT-IR Raman FT-IR Raman
ν(OH) 3405 br - - - - 3490 vw
d(HOH) 1652 m - 1686 br - 1698 br 1637 m
ν(B-O) from BO3 1432 s 1456 m 1435 s 1437 m 1438 br 1469 vs
ν(B-O) from BO3 1344 m 1405 m 1409 s - 1416 vw -

1320 w - 1322 br 1315 s
ν(B-O) from BO3’ 1258 w 1298 w
1299 w 1304 m 1302 vw
νas(B-O) from BO4 1130 w 1159 vw 1112 w 1132 m 1113 vw 1135 m
νas(B-O) from BO4 1076 m 1087 w 1068 w 1065 w 1097 vw 1069 m
ν(B-O) from BO4 944 m 979 w 1006 vw - - 1021 w
ν(B-O) from BO4 826 s 862 m 861 w - 861 m 873 sh

718 s 718 m
d(B-O) from BO3 710 w - 716 vw 716 sh
708 sh 703 sh
575 w
d(O-B-O) 500 w 529 w 510 vw - 532 vw
524 vw
d(O-B-O) 454 m 482 w 489 vw - 493 vw 485 m
*ν: stretching; d: bending, s: symmetric as: asymmetric, s: strong, m: medium; w: week; sh: shoulder [11]
a
It is seen that the B-O asymmetric stretching vibrations observed in the complexes are shifted to higher
frequencies than sodium borate. Similarly, symmetric stretching bands of B-O in BO3 and BO4 were
observed at wave numbers of 944 cm-1 and 826 cm-1. Planar bending of B-O in BO3 is observed at a
wave number of 710 cm-1 [11]. These vibration bands were observed in the 1 complex at wave numbers
of 979 cm-1 and 862 cm-1. The symmetrical stretching and out-of-plane bending vibrations of the B-O
bond were observed at higher frequencies in the complexes than in the sodium borate crystal. Finally,
the vibrational bands at 454 cm-1 and 500 cm-1 are due to dring(O-B-O) in the structure [11]. Wave
numbers of 482 cm-1 and 529 cm-1 were observed for the dring(O-B-O) for 2 complexes. It was
determined that the dring(O-B-O) deformation vibration shifted to higher frequency values from sodium
borate.
The characteristic vibrational bands for stearic acid are listed in Table 6. Characteristic vibration bands
are asymmetric and symmetrical carbonyl group vibrations ν(COO-), ν(CHx) stretching are asymmetric
and symmetric stretching vibrations from ethylene and methylene groups [13-17]. According to the
literature, for the stearate vibration bands, the vibration bands at 2963 cm-1 and 2877 cm-1 in the C-H
stretching region were observed as asymmetric and symmetric stretching vibration bands of the methyl
group, respectively. In addition, νas(CH3) and νs(CH3) vibrations of the methylene group were recorded
at wave numbers of 2917 cm-1 and 2849 cm-1, respectively [13-17].
The coordination point for the stearate anion is the carbonyl group via electronegative oxygen atoms.
For this reason, the study is focused on the stress and bending vibration wave numbers of the carbonyl
group. While the ν(C=O) strain vibration was observed at 1697 cm-1 in stearic acid, this vibrational band
is recorded at 1689 cm-1 for Complex 1 and 1676 cm-1 for Complex 2. It was observed that the C=O
stretching vibration mode shifted to the low-frequency region in the complexes. However, ν(COO-)
stretching vibrations were observed at 1518 cm-1 in stearic acid, while 1587 cm-1 for complex 1 and
complex 2 were observed. It was determined that the stress vibration frequency ν(COO-) shifted to the
high-frequency region. Thus, it is thought that coordination is provided through oxygen atoms.
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Table 6. Vibration wavenumbers of stearic acid in complexes (cm-1)

Assignments *,a,b,c,d,e,f,g Stearic Acid (1) (2)
FT-IR FT-IR Raman FT-IR Raman
νas(CH3) 2964 - 2933 sh 3171 vw 3157 vw
νas(CH3) 2954 2956 w - 2957m 2953 sh
νs(CH3) 2937 - - - 2926 m
νas(CH2) 2918 2915 vs - 2916 vs -
νs(CH3) 2870 2875 m 2882 w 2873 m 2894 s
νs(CH2) 2850 2849 vs 2848 w 2850 vs 2828 m
ν(C=O) 1697 1689 w - - 1676 m
νas(COO-) 1518 1587 vs - 1587 vw -
dsc(CH2) 1471 1544 vs - 1561 sh 1566 m
dsc(CH2) 1470 1467 m - - -
dsc(CH2) 1464 - - - -
dsc(CH2) 1458 - - - -
ν(C-O)+ ν(O-H) 1437 1440 sh - - -
ν(C-O)+ ν(O-H) 1431 - - - -
νs(COO-) 1419 1417 sh - 1410 m -
dsc(CH2) 1416 - - - -
dw(CH2) 1369 1384 sh - 1376 sh -
dw(CH2) 1357 1377 sh - - 1386 s
dw(CH2)+ dtw(CH2) 1350 - - - -
dw(CH2) 1348 1352 vw - 1353 vw -
dw(CH2)+ dtw(CH2)+ drock(CH2) 1333 1335 vw - 1335 vw -
dw(CH2)+ dtw(CH2)+ drock(CH2) 1318 1321 w - - 1315 s
dw(CH2)+ dtw(CH2)+ drock(CH2) 1300 1303 vw - - -
dw(CH2)+ dtw(CH2)+ drock(CH2) 1281 1289 sh - - 1292 sh
dw(CH2)+ dtw(CH2)+ drock(CH2) 1263 1277 vw - - 1272 sh
dw(CH2)+ dtw(CH2)+ drock(CH2) 1244 1257 vw - 1258 vw -
dw(CH2)+ dtw(CH2)+ drock(CH2) 1225 1233 vw - 1235 vw 1225 w
dw(CH2)+ dtw(CH2)+ drock(CH2) 1206 1213 w - 1210 br 1219 m
dw(CH2)+ dtw(CH2)+ drock(CH2) 1187 1191 vw - 1190 sh 1194 sh
dw(CH2)+ dtw(CH2)+ drock(CH2) 1150 1168 sh - - -
ν:stretching , d: bending , dw:wagging, dtw: twisting, dsc: scissoring, s: symmetric, as: asymmetric
a[17]
(Lee ve Kim 1998), b[18] (Hostetler, Stokes vd 1996), c[19](Snyder 1967), d[14](Snyder, Strauss vd 1982) , e[20](Allara ve Nuzzo
1985), f [15](Rabolt, Burns vd 1983), g[13](Snyder ve Schachtschneider 1963)
PXRD diffraction patterns as new generation plastic additives of the complexes are given in
Figure 6. The PXRD diffraction patterns of the complexes were clarified with the Match 3.0 Rietveld
program [21]. Structure studies by comparing the PXRD diffraction patterns of the complexes with the
matching structures from the literature. In addition, data from XRD diffraction patterns are listed in
Table 7 by comparison with metal-oxide vibrational wavenumbers observed by vibrational
spectroscopy.
(a) (b)
Figure 6. The XRD diffraction pattern for 1 (a) and (2) (b)
By Rietvielt analysis [26], the PXRD diffraction pattern of 1 was determined to match the powder
pattern of sodium tetraboratedecahydrate molecule [12] with monoclinic a= 11.8843 Å b= 10.6026 Å
c= 12.2111 Å β= 106,790 º unit cell parameters with 47.5% probability [12]. Additionally, the PXRD
diffraction pattern of the Complex was found to match with the monoclinic C10Mn2O10 structure with a
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
probability of 30.5%, with a unit cell a= 14.1257 Å, b= 6.8799 Å, c= 14.3121 Å, β= 105.07 [22].
Moreover, the PXRD diffraction pattern for 1.1 was found to be compatible with Mn2O3 with a 22%
probability orthorhombic cell a= 9.4118 Å b= 9.4177 Å c= 9.4233 Å [23].
Table 7. XRD powder diffraction pattern matching and vibrational wavenumbers corresponding to metal oxide bonds in
complexes (cm-1)
Complex Molecular Formula Matched structure of Vibrational Spectroscopy (Metal-Oxide wavenumbers)

PXRD diffraction pattern cm-1
for the complexes*
Wavenumbers (cm-1)
a
Na2B4O7 Assigments*
*d
b
IR IR Raman
1 Mn(C18H36O2)2.(B4O7)∙2H2O C10Mn2O10
c
β-Mn02 618 611 619
Mn2O3
β-Mn02 545 - 520
β-Mn02 387 - 383
Cu(CNB4O7)4 Wavenumbers (cm-1)

Assigments*
2 Cu(C18H35O2)2.(B4O7) H2O a
Na2B4O7 IR IR Raman
e
ν(Cu-O) 470 - 487
f
ν(Cu-O) 440 438 -
*a[12]
(Gainsford et all, 2008); b[22] (Louis et all, 1967) c[23] (Norrestam et al,1967); d[24](Julien et al. , 2004) e[25] (Hibble et all,
2002)
For Complex 2, The PXRD diffraction pattern of the complex was matched by Rietveld analyses via the
Match 3 program with copper tetracyano borate with a cubic a=5.4314 Å unit cell with a ratio of 58.2%.
According to this result, it is seen that the borate (B4O7)2- anion binds to the Cu(II) atom from the oxygen
end [27]. In addition, the PXRD diffraction pattern of the Complex was matched with a monoclinic a=
11.8900 Å b= 10.7400 Å c= 12.1900 Å β= 106,580 º unit cell with a ratio of 41.8% [27]. Thus, the
presence of borate anion in the formula proposed according to the results of the elemental analysis was
also supported by PXRD powder diffraction.
The XRF data of the complexes were analyzed based on the intensity, mass ratio and v/o ratio. XRF
data analysis results are given in Table 8 and Table 9, and the data are compared graphically in Figure
5 and Figure 6. The molecular formula of complex 1 was determined as Mn(C18H36O2)2∙(B4O7)∙2H2O
by elemental analysis method. It is found as 87.46% probability that the complex has Mn-Kα
characteristic layer in XRF data. It is thought that Na-Kα (4.47%) sodium oxides determined in the
structure come from Na2B4O7.10H2O or NaC18H36O2 during the complex formation. The trace amount
of determined Cl ion is thought to be caused by the conversion of MnCl2 metal salt into Mn+2 and 2Cl-
ions during the formation of the complex and forming as a salt solution according to the reaction with
the N+ ions from sodium borate and sodium stearate. Trace amounts of aluminum and silicon oxide were
observed in the structure. It can be said that the other metal oxides seen are due to the impurity of the
metal salt.
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
Table 8. XRF data analyses for Complex 1
Element Compound Ratio w/o normal % Mass Source Limit

Na-Kα Na2O 0,0668 0,5809 4,47% 1,06331
Mg-Kα MgO 0,0116 0,0332 0,00% 0,50853
Al-Kα Al2O3 0,7273 0,4938 3,40% 0,43233
Si-Kα SiO2 0,5893 0,3993 3,08% 0,15375
Cl-Kα Cl 0,3428 0,1167 0,90% 0,17878
K-Kα K2O 0,4255 0,397 0,31% 0,08122
Ca-Kα CaO 0,5628 0,0518 0,40% 0,11842
Mn-Kα MnO 164,2788 11,3664 87,46% 0,14380
Fe-Kα Fe2O3 1,6488 0 0,00% 0,15810
180 1
164,2788
160 87,46%
0,8
140
120 0,6
% Mass Ratio
100
Ratio
0,4
80
60 0,31% 0,2
4,47% 0,00% 3,40% 3,08%0,90% 0,40% 0,00%
40
0 0
20 11,3664
0 0,0668 0,0116 0,7273 0,5893 0,3428 0,4255 0,5628 1,6488
0 -0,2
…
g…
-…
-…
-…
n…
-…
e
Kα
Kα
Na
Fe
Al
Cl
Ca
M
El
w/o normal
Si-
K-
Figure 7. Graphical demonstration of obtained XRF data for Complex 1
Table 9. XRF data analyses for Complex 2
Element Compound Ratio w/o normal % Mass Source Limit

Na-Kα Na2O 0,1306 1,1371 6,85% 1,15612
Mg-Kα MgO 0,0215 0,067 0,00% 0,45415
Si-Kα SiO2 0,3641 0,2681 1,61% 0,08242
P-Kα P2O5 0,0966 0,0223 0,13% 0,05603
Cl-Kα Cl 0,5121 0,1915 1,15% 0,14900
Ca-Kα CaO 0,3963 0,0492 0,30% 0,09397
Fe-Kα Fe2O3 1,687 0,0679 0,41% 0,07434
Cu-Kα CuO 669,8581 14,391 86,64% 0,76100
Ba-Kα BaO 2,9356 0,4167 2,51% 0,92850
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
Similarly, The closed formula of complex 2 was determined as Cu(C18H35O2)2·(B4O7)·H2O by elemental

analysis methods. It is found as 86.64% probability that the complex has Cu-Kα characteristic layer in
XRF data. It is thought that Na-Kα (6.85%) sodium oxides determined in the structure come from
Na2B4O7·10H2O or NaC18H36O2 during the formation of the complex. The trace amount of Cl ion is
thought to be caused by the decomposition of the CuCl2 metal salt into Cu+2 and 2Cl- ions during the
formation of the complex, and the formation of a salt solution according to the reaction with the N+ ions
from sodium borate and sodium stearate. Trace amounts of iron, silicon, phosphate, and barium oxide
were observed in the structure. It can be said that the other metal oxides seen are due to the impurity of
the metal salt.
800 1
700 86,64%
669,8581 0,8
600
0,6
500
% Mass Ratio
Ratio
400 0,4
300
6,85%
0,30% 0,2
0,00% 2,51%
1,15%
200 1,61% 0,13% 0,41%
0 0
100
14,391
0 0,1306 0,0215 0,3641 0,0966 0,5121 0,3963 1,687 2,9356
0 -0,2
Element Na-Kα Mg-Kα Si-Kα P-Kα Cl-Kα Ca-Kα Fe-Kα Cu-Kα Ba-Kα
w/o normal
Figure 8. Graphical demonstration of obtained XRF data for Complex 2
3.2 Thermal stability and Thermal Barrier Analyses
The thermostatic analysis diagram of the new generation plastic additives obtained from the metal
complexes of stearate and borate ligands obtained with Mn(II) and Cu(II) atoms is given in Figure 9.
For the complexes, Mn(C18H36O2)2∙(B4O7)∙2H2O and Cu(C18H35O2)2.∙ (B4O7)∙H2O scavenged. It is seen
that the H+ and Cl- ions formed by the thermal decomposition of PVC were scavenged till 65 minutes
for 1 complex and 57 minutes for 2 complex. Sodium stearate and its derivatives have high thermal
stability and are used in industry as a fire extinguisher and acid absorber material. Therefore, sodium
stearate was preferred, considering both its resistance in acidic environments and its thermal stability.
for both complexes at the 200 C temperature, a sudden increase occurs in the pH value of the plastic
dough, which receives heat, and in this way, the acidic environment is quickly neutralized by the thermal
degradation of PVC. Considering these results, it is suggested that a plastic additive with high thermal
and UV resistance may be one of the basic building blocks. In addition, it was determined that complexes
containing Mn(II) were more thermally stable, while complexes containing Cu(II) acted as stronger HCl
scavenger material.
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
Figure 9. Thermostatic stability analysis of PVC dough containing New Generation Plastic additives
Obtained Plastic dough from new generation plastic additives is plasticized and made into gaskets. The
gaskets are mounted between burners and the bottom of the built-in cooker surface. In this context, 3
tests were carried out. The first test concerns the testing of commercially used gaskets. The second test
is about testing plastic materials containing complex 1, and the third test is about testing plastic materials
containing complex 2. The test start temperature was set to 24 °C. Thermocouples are connected on
three different hob surfaces containing three different gasket types and the data is connected to Elimko
32T digital thermometer with its probes. The tests were started simultaneously for three different built-
in hobs by boiling 2.5 liters of water in three different built-in hobs. Thermal barrier tests for three
different built-in cookers were carried out for 45 minutes. The tests were completed after 45 minutes.
The variation of surface temperatures during the test is given in Figure 10.
Figure 10. Thermal Barrier analysis of PVC dough containing New Generation Plastic additives
The most important reason for the surface heating of a built-in hob is the surface heating of the flame
reflected from the bottom of the pans and pots on the built-in hob grids. In particular, reasons such as
yellowing of the stainless steel surface and glass bursts are due to the heat dissipation not being correct.
During the test, it was determined that the surface temperature reached 140 °C for commercially used
gaskets, but the gaskets obtained with plastic doughs containing new generation plastic additives heated
the surface less.
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2022, 1(1), pp. x-x, DOI: 10.5281/zenodo.7248487
4. Conclusion
In this study, Mn(II) and Cu(II) metal complexes of borate and stearate ligands were synthesized. The
closed formulas of the synthesized metal complexes were determined by elemental analysis methods
and supported by thermogravimetric analysis methods (TG-DTA and DTG). Structural analyzes of the
obtained metal complexes were clarified by vibration spectroscopy (FT-IR and Raman), XRD
spectroscopy and XRF spectroscopy methods, respectively.
The data obtained from the FT-IR and Raman spectra of the complexes were compared with the Stearic
acid and Sodium borate vibrational wave numbers in the literature. The shifts in the vibrational
wavenumbers obtained that the complexes coordinate with the oxygen donor atoms and that these
components take place in the structures. The existence of metal oxide bonds in the complexes has been
explained by vibration spectroscopy and the presence of metal-oxide bonds has been supported by XRD
spectroscopy methods and XRF methods.
The obtained metal complexes were blended with the components of standard plastic dough according
to their mass percent composition, and they were turned into plastic by gelling.
The thermal stability of the plasticized materials was investigated by the thermostatic analysis method
described in the ISO 182-2 standard. It has been determined that the plastic materials obtained with the
synthesized complexes are HCl scavenger materials. According to the test results, it was determined that
the complex containing Mn(II) was more stable than the complex containing Cu(II).
Plastic materials obtained with metal complexes were located between the surface of the built-in hob
and the burners, and the temperature changes of the built-in hob surface were examined according to the
EN 30-1-1+A3:2014 standard. It has been determined that gaskets obtained from plastic dough
containing new generation plastic additives have higher thermal barrier capacity than commercial
gaskets.
This study can be considered as an initial study. In particular, while obtaining plastic material in this
study, thermal barrier capacities of plastic additives can be improved by changing the type of plastic
raw material, its hardness or ratio, filler type or ratio, or the type or ratio of other plastic additives. Thus,
the usage areas of plastic will be extended.
ACKNOWLEDGEMENTS
The author highly thankful to the Eskişehir Osmangazi University, Scientific research Unit (Project No.
2017-1588). Additionally, thank you to Prof.Dr. Güneş Süheyla Kürkçüoğlu due to provide laboratory
facilities for synthesis and obtaining spectroscopic data.
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FLEXIBLE PRINTED STRUCTURES QUALITY MODELS

FOR MOBILE ROBOT PLATFORM
Iryna ZHARIKOVA1, Viktoriia NEVLIUDOVA1, Olena CHALA1

1
Department of Computer-Integrated Technologies, Automation and Mechatronics, Faculty of Automatics and
Computerized Technologies, Kharkiv National University of Radioelectronics, Kharkiv, Ukraine
ABSTRACT
The main factors influencing on quality of the flexible printed structures for mobile robot platform are analyzed.
Requirements for the bases materials characteristics of such structures are considered. Models of mechanical, electrical and
electromagnetic processes in electronic devices based on flexible printed structures are proposed. The developed models
allow to predicate flexible printed structures quality level for use in the mobile robot platform design.
To automate the flexible printed structures design based on the proposed models, the software "Flexible PCB Designer" was
developed, with the use of which it is possible to determine many design, technological and electrical flexible printed
structures parameters.
Keywords: mobile robot platform, flexible printed structures; quality model, design, production technology.
1. INTRODUCTION
The flexible printed structures (FPS) using is an actual trend for the development of highly reliable
electronic devices with a high density of printed circuit elements layout. Such structures include
elements of flexible electronics, flexible electronic components, printed circuits and interconnection
elements [1-3].
Particularly useful is the use of FPS for portable telecommunication devices, for terrestrial and
satellite communication systems, military, household, and medical equipment, as well as for MEMS
devices design.
The replacement of rigid hardware components of mobile robot platform (MRP) with flexible ones to
improve their quality, functionality, reliability and reduce weight-size parameters, manufacturing labor
intensity, cost, as well as the development of tooling based on flexible structures, are currently relevant.
Requirements for such products are constantly increasing due to the toughening of their operating
conditions. At the same time, there is a serious problem of providing quality indicators of flexible
components, since they can be exposed to a lot of destabilizing factors at all stages of the life cycle. For
example, modules installed on mobile objects such as cars, airplanes, missiles, etc., during operation can be
exposed to intensive mechanical influences such as impacts, vibrations, linear overloads [4-5].
One of the important directions in this area is the automation design of the main FPS elements and
determining the technological process parameters for such structures manufacturing, as well as
analyzing and predicting the state of FPS during their operation [6]. Therefore, the goal of the work
was the development of a complex models of FPS parameters, as well as its software implementation.
*Corresponding Author: xxxxxx@xxxxxxxx.xxx.xx

Receiving Date: ... Publishing Date: ...
2. MATERIALS AND METHODS
2.1. Analysis of the FPS Requirements and Parameters
The important task for manufacturing is development of methods of quality technological support for
electronic products based on FPS. One of such methods is forecasting of devices failures at the design,
manufacturing and operation phases based on the analysis of the product operating conditions and
modes, the parameters of technological process of its fabrication, and its output parameters.
FPS are widely used for a long time for intra- and interblock commutation of electronic devices (ED).
Compared with traditional rigid printed circuit boards they have several advantages:
– compact dimensions achieved due to the thinner dielectric base,
– ergonomics, depending on the degree of FPS rigidity, flexible components can take various shape
without loss of functional parameters,
– weight reduction that achievement also due to a thinner base, on average FPS are lighter than rigid
boards by 75%,
– reduction of time and cost of assembly, due to the group methods of assembly and components
mount.
Requirements for the FPS bases materials characteristics are the following.
a) Stability of dimensions: A flexible foiled dielectric must have exceptional dimensional stability.
Shrinkage or expansion of the FPS base material during its processing can cause problem for
electronic products fabrication and assembly and during it using.
b) Heat resistance: Since most high-temperature group heating processes, such as reflow soldering, are
used at most electronic equipment manufacturers for components mount, it is extremely important that
the material chosen for FPS fabrication also be able to withstand the soldering temperature without
deforming.
c) Mechanical reliability: Many FPS designs are based on thin and not reinforced films, so they tend to
break. So, the base material for FPS fabrication must have a high breaking resistance.
d) Electrical characteristics: As the signal transmission rate increases, the requirements to dielectric
properties of FPS base increase. At high signal transmission rates (more than 100 MHz), the insulating
material must have a small dielectric constant and a low loss tangent. In addition, for various high-
energy problems it is desirable to have an average insulation resistance.
e) Flexibility: Depending on the application, FPS can be exposed to extreme temperatures. Therefore,
flexibility over a wide range of temperatures is extremely important. Of particular importance is
flexibility at low temperatures when most materials tend to be fragile.
f) Moisture absorption: Moisture absorption is not desirable for any flexible substrate. Moisture can
adversely affect both the production process, causing stratification during processing or assembly, and
on the characteristics of the finished product, changing the value of the dielectric constant and
increasing the signal loss.
g) Resistance to chemical effects: The material of the FPS must withstand the effects of a number of
reagents that accompany it during the manufacture and operation. The substrate must be compatible
with various chemical reagents and typical solvents used in assembly and cleaning processes.
h) Repeatability of characteristics from batch to batch: The variability of the material parameters has
an extremely negative effect on the FPS production, so the repeatability of the characteristics is
78
important for good fabrication process control. Although the requirements for quality indicators may
not be achieved in real production, the high repeatability of all material characteristics, including
physical, mechanical, and electrical, is a key factor during technological processes. This property
ensures that flexible structure will be processed well at manufacturing stages and will operate well
during it using.
i) Cost: Standing for inexpensive solutions is a common practice in the field of electronics. As a rule,
in the calculation of the product cost price, the base material price is the main parameter.
One of the important tasks of ensuring the necessary quality indicators of technical products, in
particular, ED with the use of flexible components, is task of predicting their parameters and
automation of this process.
It is possible to use the following description types of flexible structures in the ED structure:
– functional – represents the basic principles of operation and the physical and information processes
taking place in ED based on FPS,
– design – represents the physical implementation of ED based on FPS, its geometric shapes, location
in space, as well as used materials and components,
– technological – refers to the methods and means of manufacturing FPS and ED on their base.
There is a concept of stability of ED based on FPS, that can be characterized by normal functioning of
the equipment under mechanical influences. The reasons for the disturbance of the electronic device
stability are following:
– resistance value changing in the contact groups of connectors,
– changing the parameters of ED passive elements,
– changing the parameters of ED active elements,
– appearance of noise voltages in conductors, that are oscillating in magnetic fields,
– noise voltages appearance in oscillations due to the arising electric charges during mechanical
actions in high-quality dielectrics.
The output parameters of the ED based on FPS can be influenced by mechanical, electrical, and
technological parameters (or, according to the systemological terminology, input variables) [6].
The mechanical characteristics are stiffness, natural oscillations frequency, dynamic flexibility of the
FPS base, wear out.
The electrical characteristics are parasitic parameters of the conductor system, electromagnetic
compatibility, etc. [7-31].
The technological parameters include materials of the printed substrate (most often used type is
polyimide) and conductive layers (aluminum, copper), number of FPS layers, width of the conductors
and the gap between them, interlayer connection type (ultrasonic welding, gluing, etc.).
2.2. FPS Quality Models Development
The experiment implementation plan for FPS quality analysis includes:

– study of mechanical processes in the FPS,
– study of electrical processes in flexible structures,
– modeling of FPS reliability and quality,
– analysis of simulation results.
Applying the system analysis apparatus, the interaction of dissimilar physical processes in the FPS can
be represented by a system of equations:
W {X (y ), Y (y ), B (Z )} = 0, (1)
79
where W are the model operators connecting the input actions X (y ) , the output characteristics Y (y )
and the internal model parameters B (Z ) ; Z is set of external influences; y is an independent
argument (time, frequency, spatial coordinate).
Write down expression (1) for the model of mechanical processes in FPS (2), model of electrical
processes (3), model of electromagnetic processes (4):
Wmech {[ain (y )] , [a e (y ), t d ] , [Be (y ), Bk ]} = 0, (2)
Wel {[Lin (y ), Rin (y )], [Qout (y ), K out (y )], [Bk ]} = 0, (3)
Wem {[Ye (y ), I n (y ), U n (y ), En (y )], [I i (y ), U i (y ), Ee (y )], [Bеm ( Bn (y )), Bk ]} = 0. (4)
Here: a in (y ) are sets of vibrations (harmonic and random) acting on the object under study, impacts,
linear accelerations; a e (y ) are sets of electronic components accelerations; t d are sets of time values
before the electronic components pins destruction; Be (y ) are sets of internal electrical parameters
characterizing a definite physical process; Bk is the set of FPS geometric parameters; Lin (y ) are sets
of input inductances; Rin (y ) is set of input resistances for the model of electrical processes in the FPS;
Qout (y ) is set of output Q-factors of the circuit; K out (y ) are sets of output coefficients characterizing
the filter capacity; Ye (y ) are sets of electrical characteristics of electronic components;
I n (y ), U n (y ), En (y ) are sets of currents, voltages and intensities of electromagnetic interferences;
I i (y ), U i (y ) are sets of currents and voltages induced by noises in electrical circuits; Ee (y ) are sets
of electromagnetic field intensities emitted by the ED; Bеm is a set of internal model electromagnetic
radiations; Bn is the set of internal model interferences caused by electromagnetic radiation.
Also, in the complex model structure developed for the ED on the FPS basis we introduce the sub
model of reliability and quality
{[ ]}
WRQ X RQ (y ), YRQ (y ), BRQ ((Yеl (y ), YT (y ), a a (y ), FTP , Ft ) = 0, (5)
where X RQ (y ) are input indicators of reliability and quality; YRQ (y ) are output values of reliability
and quality; BRQ are internal model parameters, depending on: Yеl (y ) – the set of electrical
characteristics of electronic components; YT (y ) – sets of thermal characteristics of electronic
components; a a (y ) – sets of electronic components accelerations; technological factors FTP and time
factors Ft .
Internal model characteristics depend on the ED operation modes, obtained because of modeling
various physical processes, technological factors (dispersion of parameters during FPS manufacture)
FTP , time factor (gradual change of parameters due to FPS aging and wear out) Ft .
Thus, the output parameter Y (y ) , considering the destabilizing factors, will have the form (10):
{
Y (y ) = Yе (y ), Yеm (y ), Ym (y ), YRQ (y ) , } (6)
where Yе (y ) is the output parameter of the electrical processes model; Yеm (y ) is the output parameter
of the electromagnetic processes model; Ym (y ) is the output parameter of the mechanical process
model; YRQ (y ) is the output parameter of the reliability and quality model.
Thus set of FPS parameters includes design D , electrical E , mechanical M , operational O and
technological T parameters [6]
F = {D, E , M , O , T }. (7)
80
In turn, the set of FPS design parameters includes the design parameters of the insulating and
conducting layers:
{ }
D = w, l , tb , t f , a, p, b, l p , Dm , N . (8)
where w is the FPS width; l is the FPS length; tb is the thickness of the FPS base; t f is the thickness
of the foil; a is the height of the adhesive layer, p is the length of the conductor, and b is its width;
l p is the distance between two conductors; Dm is the diameter of the metallized hole; N is the
number of layers.
The electrical parameters are determined by the properties of the base and the conducting layer
materials, as well as by the FPS operating conditions:
{ }
E = e , r , tgd , E p , L, C , C p ,U ,U p , I , R, f , Pp , Q, Rx . (9)
Here e is the permittivity of the FPS base; r is the electrical resistivity of the conductor material;
tgd is the loss tangent and E p is the breakdown strength of the insulating material; L is inductance;
C is FPS self-capacitance; C p is stray capacitance between two adjacent printed conductors located
on one FPS side; U is working voltage; U p is allowable voltage drop on the conductor; I is current
in the conductor; R is resistance of the printed conductor; f is the frequency of the current; Pp is
the loss power; Q is the quality factor; Rx is the reactance.
Mechanical parameters characterize the properties of FPS materials and their resistance to mechanical
effects, to which FPS can be exposed during their operation:
{ }
M = s y ,s B , d ,j , H , Em , G , P, µ , r, nl , (10)
where s y is the yield strength; s B is ultimate tensile strength; d is breakdown elongation; j is
relative breakdown necking; H is hardness; Em is the modulus of elasticity; G is the shear modulus;
P is plasticity; µ is the Poisson ratio; r is the permissible bend radius, nl is the value of the neutral
line of the FPS.
3. RESULTS
To automate the FPS design based on the proposed models, the software "Flexible PCB Designer" was
developed. The software interface is shown on the Figure 1.
With the use of "Flexible PCB Designer" it is possible to determine many design, technological and
electrical FPS parameters, in particular, the minimum allowable FPS bending radius, position of the
FPS neutral line, allowable voltage drop in the printed conductor, parasitic capacitance of two parallel
conductors, FPS self-capacitance and loss power, FPS interlayer capacitance, resistance of the printed
conductor and others.
81
Figure 1. The main software window
In addition to the listed functions, the program includes the implementation of the possibility of filling
design documentation (technological manufacturing parameters, recommended testing methods), and
allows to build and visualize the FPS structure
4. CONCLUSİONS
Thus, the quality models of FPS in the ED design for MRP are developed based on analysis of
mechanical, electrical, and electromagnetic processes in such structures. The software "Flexible PCB
Designer" was developed to automate the FPS design, their mechanical and electrical parameters
calculation.
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дзеркальних поверхонь МОЕМС-перемикачів / О. І. Филипенко, О. О. Чала, М. І. Відешин //
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І. Ш. Невлюдов, І. В. Боцман, В. В. Невлюдова, Є. А. Разумов-Фризюк. – Кривий ріг: КК
НАУ, 2018. – 256 с.
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Operations Parameters on Moems Components Formation," 2019 IEEE 8th International
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Components of Microoptoelectromechanical Sensors Manufacturing & Mechatronic Systems 2021:
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2022, 1(1), pp. 85-92, DOI: 10.5281/zenodo.7253629
ROBOT GROUP INTERACTION TECHNOLOGY USING A CLOUD SERVER

Igor NEVLIUDOV1, Shakhin OMAROV1, Serhii TESLIUK1,
Serhii NOVOSELOV1, Oksana SYCHOVA1
1
Department of Computer-Integrated Technologies, Automation and Mechatronics, Faculty of Automatics and
Computerized Technologies, Kharkiv National University of Radio Electronics, Kharkiv, Ukraine
ABSTRACT
This paper presents the technology of interaction of a group of robots using a cloud server. The cloud server is designed to
collect information from sensors of robotic equipment and use it to build a map of the workspace for the movement of mobile
robots and paving the way. The proposed technology can be combined with the robot control system. The paper gives an
example of a constructed map using the sensors of a mobile robot. The method of constructing a map of the space based on
the data of odometry and methods for updating previously obtained information is considered. The development of a
structural diagram of the cloud storage for the construction of the map of the area was carried out. The structure of the data
collection server and the algorithm of the mobile platform in the interaction with the cloud server is proposed.
Keywords: Lidar, ROS, odometry, cloud server.
1. INTRODUCTION
The basic idea behind cloud robotics is that, as a rule, the robot interacts with its environment using its
sensors and actuators. In fact, this means that the data received from the sensors must be processed
and used to make decisions (as feedback) about the next action of the robot. For tasks requiring real-
time operation, processing can be moved to the cloud. This reduces the required processing power of
the robot, which can improve the duration of its mobile operation (without recharging) and reduces the
cost of the robot. To work in this mode, it is necessary to build a map of the area where the navigation
is supposed to be performed in advance.
2. DEVELOPMENT OF A NAVIGATION SYSTEM FOR MAP BUILDING
Autonomous navigation on a predetermined map is one of the possible scenarios for robotic
applications, which is of great interest to researchers in the field of robotics. To operate in this mode, it
is necessary to build a map of the terrain where navigation is supposed to be performed in advance. In
the case where the robot moves only on a flat surface, for example, when moving indoors, the
representation of the map can be greatly simplified by considering only the plan of the area.
In this case, the map is represented as a raster 8-bit image, each point (0 – free, 100 – interesting,
1 – unknown) of which encodes the presence of interference in the corresponding area on the
map (Figure1).
A map of the entire area is referred to as a global map. To save and load a global map in ROS, there is
a map server package which is part of the ROS navigation stack.
The global map is used for localization – determining the position of a job on it. The global map is
also used to build a global trajectory for autonomous navigation.
Usually, the requirements for the work to solve the problem of building a map of the terrain are a
minimum set of sensors and an automated system for controlling the movement of the work on a given
trajectory. The minimum set of sensors required to build a map: wheel encoders (odometers) to
estimate the distance covered, necessary to prompt the SLAM algorithm to increase coordinates;
sensor distance to obstacles – leaders; IMU (or BINS) optionally may be used as an additional source
of information to clarify the data odometry and tilt compensation when driving on an uneven surface.
An example of a possible mobile operation design is shown in Figure2.
*Corresponding Author:xxxxxx@xxxxxxxx.xxx.xx
ReceivingDate: ... Publishing Date: ...
2022, 1(1), pp. 85-92, DOI: 10.5281/zenodo.7253629
Figure 1. Example of a constructed room map Figure2. Example of a possible mobile robot design
The motion control tasks in this case are three of them: determining the current coordinates of the
robot (relative, for example, to its initial position); plotting trajectories (for both well known and
unknown map); and specifying the map itself. To construct a flat map of the surrounding space, we
have in mind a set of points on the plane bounding insurmountable obstacles.
We use odometers (wheel speed sensors) and a laser scanning rangefinder, which measures the range
to obstacles in a plane parallel to the plane of motion of the robot, as our main sensors. As
insurmountable obstacles, we understand only the protruding obstacles that fall within the
rangefinder's field of view (i.e., they have a height not less than the height of the rangefinder
installation).
Therefore, mapping is carried out in three stages: binding the current rangefinder measurements to the
map given the current position of the robot; locating the current points on the current map;
constructing the map given the new points.
The first task is quite simple. Let the current coordinates of the robot on the plane be expressed by the
coordinate transformation of a 3x3 matrix:
æ cos(a ) - sin(a ) x ö
ç ÷
ç sin(a ) cos(a ) y ÷ (1)
ç 0 0 1 ÷ø
è
here αis an angle of rotation of the robot at zero – initial position; x and y – shift of the robot at
zero – initial position.
Then the current coordinates of the point measured by the rangefinder will be as follows:
æ x cuy cos(a ) - y cuy sin(a ) + x ö
ç cuy ÷
ç x sin(a ) + y cuy cos(a ) + y ÷ (2)
ç 1 ÷
è ø
where ! !"# and " !"# are the local coordinates of the point measured by the rangefinder.
The second task is to arrange the current points on a known map. It is known that changes may have
occurred since the known map was created. It is necessary not only to make these changes to the map,
but also not to miss old known obstacles that can be re-measured.
The map is a set of segments in which there are three known points, two end-points and a middle
point. The middle point is taken for the stability of the approximation method. To improve accuracy,
all points should be memorized, but this will quickly enough cause the control program to require
resources beyond the capabilities of any computing system, since the number of points to be handled
simultaneously can exceed any reasonable number.
Next, a grid is built on the map, the size of the cells of which should exceed the allowable error. For
example, for the case when it is not necessary to solve the problem of passing through a narrowness in
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2022, 1(1), pp. 85-92, DOI: 10.5281/zenodo.7253629
advance, the cell size is reasonable to choose half of the width of the robot, possibly extended by the
size of the safety zone. A cell is considered occupied if at least one rangefinder measurement falls into
it. If the cells are large, enough, these dimensions compensate the inaccuracy of interference
coordinates.
A cloud server designed to collect information from sensors of robotic equipment and use it to build a
map of the workspace of mobile work. The main requirements to the server are collection of data from
sensors; accumulation of the received information in the built-in database management system, display
of actual data in graphic or text form, automatic updating of information; organization of access to the
server through a dedicated interface, display of graphic information of the workspace map on any
device that has network access and a graphic display.
Figure 3 shows the architecture of interaction between the server and the developed sensors of the
mobile robot.
Figure 3. Architecture of interaction between the server and sensors of the mobile robot
To solve the problem, the data collection server must have the following software modules: – database
management system; REST-server; service for preparation of graphic information; service for
interaction with the network using REST-technology. Service for interaction with the network receives
requests using REST-technology. Software controllers process the requests and distribute the received
information to the required directions. REST is an architectural style of interaction between
components of a distributed application in a network. REST is a consistent set of rules considered
when designing a distributed system. A single interaction interface allows different devices to
communicate with the data collection server. The received data are distributed in the database tables
according to the mobile equipment from whose sensors they were received.
At the customer's request, the service of preparing the graphical information finds the necessary
information in the database and prepares for display the necessary content to build a map of the area.
The control system of the mobile robot performs the orientation of the device depending on its current
position and data about the map downloaded from the cloud server terrain.
Figure 4 shows the algorithm of the mobile robot path finding module using the disturbance location
data obtained from the cloud server.
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2022, 1(1), pp. 85-92, DOI: 10.5281/zenodo.7253629
Figure 4. Control algorithm for a mobile robot using LiDAR technology
The data coming from the cloud server allows the navigation system to optimize the robot's trajectory
and correct it if obstacles prevent it from moving. The motion control process ends when the robot
reaches the target point.
As it moves, this robot, like any other robot, transmits the coordinates of obstacles found, as well as
the coordinates of its location, to a cloud server so that other mobile platforms can quickly rearrange
their trajectory.
The data to be stored on the cloud server comes from various sensors placed on the mobile work. Such
sensors can be: a scanning laser device for measuring distance to interference in a wide field of view
(LiDAR); wheel rotation sensor; acceleration sensor; magnetic sensor (digital compass).
Each of the above sensors has a specific set of data that makes up a packet of information to the
server. Let's look at an example of a data packet that is generated from Lidar and transmitted to the
server.
Figure 5 shows the contents of the data packet transfer from LiDAR to the data acquisition unit.
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2022, 1(1), pp. 85-92, DOI: 10.5281/zenodo.7253629
Figure 5. Format for transmitting information from LiDAR to the data collection unit
The Lidar data acquisition unit receives information about the objects surrounding the mobile work
with a laser scanner. Based on the received data a terrain map is created by the corresponding unit.
The decision-making block analyzes the received information and based on this information forms
commands for execution by the control unit. After that, the control unit exerts control action on the
propulsion mechanisms for further movement of the work in space.
In each field of the frame, the following information is transmitted: the current measured distance
between the rotating sensor and the interference point; the current angle of rotation of the distance
measurement sensor; the measurement accuracy; the sign of the beginning of a new scanning. After
receiving the above information from the laser scanner, the data acquisition unit transmits the data to
the terrain mapping unit. This unit is based on the SLAM development.
Simultaneous navigation and mapping method (SLAM) is a concept that links two independent
processes in a continuous cycle of consecutive calculations, in which the results of one process are
involved in the calculations of the other process.
To verify the proposed algorithm for working with cloud storage, a program was developed that
performs the following functions: displaying the list of mobile devices registered on the server;
displaying the room plan; generating a terrain map based on data from the cloud storage; accumulating
information about the environment of the mobile platform to build a terrain map.
The main window of the program is shown in Figure 6. The interface consists of the list of mobile
robots registered on the server (left area of the program), and the work area, which allows the operator
to perform research related to the construction of the room map based on data from sensors (right area
of the program). In the workspace there is a TabPage component with three tabs. The first tab shows a
test layout of the room. There are various objects in the room, which must be considered when moving
the robot. For a mobile robot entering an unfamiliar room, its plan will be completely undefined. The
first step is to explore the cordoned-off area using the built-in sensors.
The program implements a simulation of the space scanning process. In this mode, consecutive waves
of searching and determining the coordinates of the interference location in the sensor area are
run (Figure 7).
Figure 6. Main window program interface Figure 7.Determining the distance to an

obstacle
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2022, 1(1), pp. 85-92, DOI: 10.5281/zenodo.7253629
From the example, you can see that the scanning distance increases sequentially from the minimum to
the maximum value. In the process of scanning, the angle of rotation of the sensor changes
sequentially from zero to 360 degrees. If for the given angle an obstacle is found, the distance to it and
the angle of rotation are memorized. At the next scanning radius, this angle is no longer used to reduce
the time of this procedure.
The result of the scanning is a set of points in the format:
50-{X=815,Y=84};270-{X=816,Y=87};320-{X=815,Y=76};100-{X=815,Y=72};150-
{X=815,Y=56};30-{X=788,Y=32};80-{X=773,Y=32};250-{X=793,Y=33};300-{X=778,Y=32};350-
{X=761,Y=32};130-{X=755,Y=32};200-{X=813,Y=32};180-{X=734,Y=33};230-{X=702,Y=33};
Figure 8 shows an example of visualization of the obtained data. The described scanning principle is
completely identical to the real work of a mobile robot. All data obtained after each interference
search cycle is stored in the cloud storage database. After completing the phase of room exploration
and collecting all the interference data in the sensor coverage area, we get a cloud of points described
by the workspace. Figure 9 shows an example of visualization of the point cloud.
Figure 8. Example of space scanning by a robot Figure 9. Example of room map visualization
The developed program allows to view the point clouds for each mobile device registered on the cloud
server. Appropriate models are used to access the data.
Data model for the Profile entity:
publicclass Profile Model

{
publicstringID_Device { get; set; }
publicstringName { get; set; }
publicstringStatus { get; set; }
}
Data model for the Measureentity:
publicclassMeasureModel
{
publicintID_Measure { get; set; }
publicstringDateMeasure { get; set; }
publicstringTimeMeasure { get; set; }
publiclongDateTimeMeasure { get; set; }
publicstringDataLidar { get; set; }
publicintID_Device { get; set; }
publicintDevice_X { get; set; }
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2022, 1(1), pp. 85-92, DOI: 10.5281/zenodo.7253629
publicintDevice_Y { get; set; }

}
Data model for the Place entity:
publicclassPlaceModel
{
publicintID_Place { get; set; }
publicintID_Device { get; set; }
publicintDevice_X { get; set; }
publicintDevice_Y { get; set; }
publiclongDateTimePlace { get; set; }
}
The developed program also provides the ability to store all points of the trajectory of the mobile
robot. Further, in the course of the study it is possible to see the dynamics of the work along the room,
taking into account all points where the scanning took place.
3. CONCLUSION
Thus, this paper presents the results of research in the field of navigation of mobile robots, the
proposed technology of navigation of a group of robots using a cloud service with the use of a single
server designed to collect information from sensors of robotic equipment and use it to build a map of
the working space. An example of a constructed map of a room using sensors of a mobile robot is
given. An example of a possible design of a mobile workplace used to build a map of the area is given.
The structural diagram of the cloud data storage for the construction of the terrain map is developed.
The structure of the data collection server is developed and the algorithm of the mobile platform in
interaction with the cloud server is proposed. The developed application performs the following
functions: displaying the list of mobile devices registered on the server; displaying the room plan;
generating the ground map based on the data from the cloud storage; accumulating information about
the environment of the mobile platform to build a ground map.
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2022, 1(1), pp. 93-99, DOI: 10.5281/zenodo.7267708
A STUDY ON AIR QUALITY NEAR SOLID WASTE TREATMENT PLANTS

AMONG UNIVERSITY POPULATION: ADANA CASE
Tugce PEKDOGAN
Department of Architecture, Faculty of Architecture, Adana Alparslan Türkeş Science and Technology
University, Turkey.
ABSTRACT
In the city of Adana, which constitutes the field of this study, rapid urbanization with rapid population growth causes increasing
waste consumption. This uneven increase has brought along the problem of urban waste collection and disposal. The fact that
the Sofulu solid waste disposal facility in Adana is located within the residential areas causes the health and social life of the
city to be negatively affected. Even if measures are taken for sanitary landfills, it is likely to adversely affect public health as
they create various sources of air pollutants such as chemicals, odor, and volatile organic compounds. The aim of this study;
Alparslan Türkeş Science and Technology University, located near the Adana Sofulu solid waste disposal facility and host
many individuals daily, to investigate the impact of a solid waste disposal facility on the user with a user-oriented survey.
Statistical techniques were used to examine the relationships between residents' responses to the layout of the landfill. The
research was carried out among 100 participants, 50 were university students, and another 50 were academic and administrative
staff working at the university. The difference between these two groups was observed statistically with the cross-classification
analysis. In addition, research on environmental awareness towards solid waste disposal facilities.
Keywords: Solid waste landfill, air quality, environmental awareness, survey.
1. INTRODUCTION
The changing socio-economic structure in the process of getting difficult living conditions and
urbanization requires re-questioning and rearranging the life we live. Cities today are rated primarily for
the quality of life. Quality of life, on the other hand, is a phenomenon that contains many concepts
together. In this context, increasing air pollution because of technological developments and changing
lifestyles is one of the factors that make up the whole of this concept. While creating the concept
framework, boundaries are determined by today's living conditions and technology. Today, this
framework has surrounded almost every area of our lives with its different shapes and appearances.
Along with the increase in population, the production volume of municipal solid waste facilities
increases because of urbanization, industrialization, and technological developments.
The National Waste Management and Action Plan have been prepared within the sustainability principal
framework in the past years. However, new sanitary landfills are also in need with the increase in waste.
The selection of these alternative landfills is very important [1].
Rapid population growth and rapid urbanization in the city of Adana, which constitutes the field of this
study, have led to increasing waste consumption, and this irregular increase has brought along the
problem of urban waste collection and disposal. The fact that the existing solid waste disposal facility
in Adana is located within the residential areas causes the health and social life of the city to be
negatively affected [1].
In general, the amount of solid waste is directly proportional to the economic development and
urbanization rate. Globally, the amount of waste is increasing rapidly all over the world. Solid waste
*Corresponding Author: tpekdogan@atu.edu.tr
Recieving Date: ... Publishing Date: ...
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growth rates appear to be rapidly increasing in China, other parts of East Asia and parts of Eastern
Europe, and the Middle East and Pacific Region, as are urbanization rates and GDP [2]. There is a strong
relationship between urban solid waste generation rates and greenhouse gas emissions. The increase in
solid waste, greenhouse gas emissions and ozone-depleting substances is due to pollution and
urbanization. Most landfills are open dumps and pose serious environmental and social threats [3].
Figure 1 shows the global municipal solid waste generation percentages in selected countries in 2018.
While production is mostly seen in China and India, Turkey is in the top ten with 1.5% [4].
Figure 1. Global municipal solid waste generation [4].
According to statistical data between 1990 and 2017 about the global distribution of deaths from outdoor
air pollution, most of the deaths due to outdoor air pollution occur in India, and Turkey ranked 2. with
36%, China is 3rd, with a 30% increase [5].
Also, indoor air quality is affected by the presence of various microorganisms and allergens such as
particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO2), temperature, relative humidity,
and formaldehyde (HCHO) etc. Several studies have documented the relationship between indoor air
quality and students' school performance [3]. These studies show that classroom ventilation rates are
directly related to student's academic achievement.
To control the IAQ related to COVID-19, [6] analyzed the design strategies in post-pandemic
architecture. By offering methods to understand the health and environmental problems of COVID-19,
this research aims to show architects the increased risk of disease transmission. To improve IAQ, this
paper offers a conceptual model based on this problem and explores the integration of engineering
controls, design strategies, and air sanitization approaches. Buildings contain a comprehensive IAQ
management approach for human-centered designs requiring sufficient ventilation systems, air filtration,
humidity regulation, and temperature control [7], [8].
In Çanakkale, Turkey, [9] surveyed 121 households and gathered data over 12 months. Air
contaminants, including CO2, VOCs, temperature, and humidity, were observed. Additionally, several
infections were common, and the SBS symptoms changed seasonally. There is a correlation between
the frequency of SBS symptoms, the calculated IAQ parameters, and personal factors (p 0.05).
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[10] proposed an analytical model and its variables of IAQ related to thermal comfort and health.
According to this research, factors such as outdoor/indoor temperature, wind velocity, outdoor/indoor
relative humidity, physical features of the room, natural/mechanical ventilation, the number of
occupants, and air exchange rate were determined to define health, IAQ, and thermal comfort [7].
This research covers the surveys and evaluations about the indoor environmental quality that will be
made with the user population within the boundaries of the Adana Alparslan Türkeş Science and
Technology University campus, which is located near the Sofulu solid waste disposal facility. This study
is planned to investigate the effect of air pollutant emissions from landfills on indoor air quality and
thermal comfort on users at ATU near Adana Sofulu solid waste disposal facility. For this purpose,
conducting a user-oriented survey at the university, which hosts many individuals daily, is part of the
study. A separate survey was conducted between 08:00 and 17:00 in the morning for a year between the
administrative and academic staff working at the university and the students in the university education
period. Thus, this study includes research on air pollutant emissions from landfills, including quality of
life.
2. METHODOLOGY
The methodology followed in the study includes designing survey questions to determine the study's
objectives, conducting surveys across campus, processing the survey data, and ultimately evaluating the
results of the surveys, along with a series of research that includes a review of the relevant literature.
The surveys were made to the Adana Alparslan Türkeş Science and Technology University campus staff
and students working there. First, ethics committee approval was obtained for the study, the participants
were informed about the subject and answers were received.
In this study, Sarıçam district, where ATU and Sofulu landfill, located on a total area of 1,431,673.82
m² in Balcalı District, 202 blocks, 52 parcels, is located, is the region that hosts approximately 10% of
the total population with rapid development transformation and urbanization will be discussed (Figure
1). The university campus, which is approximately 1.00 km from the Sofulu municipal solid waste
landfill, has been determined as the study area.
Figure 1. Location of the university campus and municipal solid waste landfill
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A simple and understandable questionnaire was designed, and criteria related to the thermal comfort of
offices/classrooms, indoor air quality and the impact of storage space were evaluated to collect data on
the campus public. Using a Likert-type scale, it was expected to be evaluated with multiple options
between the two extremes. Likert-type questions contain a statement that includes an attitude or opinion
about the subject under investigation and options that indicate the level of agreement with this statement.
These options are ranked "highest to lowest" or "best to worst." The questionnaire, which consists of 10
questions in total, includes four questions about indoor air quality and thermal comfort, five about solid
waste treatment plant and its effect, and one about indoor air pollutants. Table 1 shows the criteria used
in the survey.
Table 1. Landfill site survey questions
Survey Questions
1 Rate of fresh air in classroom/office
2 Feel about the air quality in classroom/office
3 Satisfaction of indoor temperature of classroom/office
4 Feel about the indoor temperature in the classroom/office
5 Principle of municipal solid waste landfill
6 Impact of the municipal solid waste landfill on the university campus
7 Odor period from municipal solid waste landfill
8 Impact of the municipal solid waste landfill on classroom/office air quality
9 Health impact of municipal solid waste landfill
10 Indoor air pollutants
2. ANALYSIS OF SURVEY DATA
100 completed questionnaires were processed to analyze the air quality impact of the landfill's proximity
to the campus. The analysis includes responses to questions about indoor air quality to campus users
near a landfill. Responses were analyzed with 10 questions describing participants' knowledge of the
impacts of landfills and their concerns about office/classroom air quality and health concerns. These
answers were taken within the questions of the rate of fresh air, the satisfaction of indoor temperature
and fresh air, the principle of municipal solid waste and information about indoor air pollutants. In the
analysis phase, these options were coded by assigning a numerical value according to their degree, and
the qualitative data were converted into quantitative data and analyzed. The data obtained from the
questionnaires were coded and analyzed with the SPSS statistical program. Table 2 includes the analysis
of the answers given by the staff and students as mean.
Table 2. Mean of the statistical analysis of survey for student and staff
Student Personal
1 Rate of fresh air in classroom/office 2.4 2.5
2 Feel about the air quality in classroom/office 2.4 2.5
3 Satisfaction of indoor temperature of classroom/office 2.7 3.7
4 Feel about the indoor temperature in the classroom/office 3.5 3.0
5 Principle of municipal solid waste landfill 1.6 1.6
6 Impact of the municipal solid waste landfill on the university campus 4.1 3.8
7 Odor period from municipal solid waste landfill 1.3 1.3
8 Impact of the municipal solid waste landfill on classroom/office air quality 4 3.5
9 Health impact of municipal solid waste landfill 1 1.1
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A box whisker plot is a diagram showing the data's minimum, maximum, and three quartiles, with a
vertical box and two lines coming out of that box [11]. The length of the box section of the graph is the
quartile difference Q3-Q1. The line in the middle of the box shows us the median value of Q2. It is
possible to see the smallest value in the data set, the first, second and third quartiles of the data and the
largest value in the data set with the box-whisker plot [12]. The fact that it is located right in the middle
shows that the data are normally distributed [13]. Figure 2 shows the box whisker diagrams for all
questions. In this figure, "S" represents the students and "P" represents the personnel/staff. If the median
line of one boxplot is outside the box of another boxplot, a difference is likely between the two groups.
The longer the box, the more scattered the data. The smaller the box, the less dispersed the data will be.
Figure 2. Boxplot diagrams for some questions
It is necessary to use different analysis tools to understand whether there is a statistical difference
between them. Therefore, a t-test analysis was performed in this study after the box plot. Whether there
is a mean difference between the two sample groups was examined with this analysis.
When the answers given by the students and staff were examined, it was found that the results were
different from each other after the t-test (Table 3) for satisfaction with the office/class indoors. And the
8th question about the impact of the municipal solid waste landfill on classroom/office air quality results
differs. Accordingly, it has been observed that the satisfaction of the staff with the indoor air quality and
ambient temperature in the office is higher than the satisfaction of the students with their classrooms.
Also, according to the survey, a significant difference is observed in the answers between the students
and the staff for odor annoyance. It has been concluded that the odor emitted from the solid waste
treatment plant is more effective in classrooms.
Table 3. t-test table
Q1 Q2 Q3 Q4 Q5 Q6 Q7 Q8 Q9
Sig. (2-tailed) 0.780 0.588 0.002 0.136 0.909 0.226 0.949 0.054 2.000
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The last question of the survey was asked to measure information in general, and the analysis result for
the question, which is all indoor air pollutants, and some options include toxic gases, is given in Table
4. As can be seen in the table, the question of which options are indoor air pollutants from particulate
matter (PM), carbon dioxide (CO2), methane (CH4), hydrogen sulfide (H2S), and carbon monoxide (CO)
and formaldehyde (HCHO) were asked. While 60% of the students said that CO2 is not an indoor air
pollutant, 17.1% of the staff did not. In addition, 68% of the participants said they did not know whether
formaldehyde is an indoor air pollutant. While 64% of the participants do not know about hydrogen
sulfide, 53% do not know about particulate matter.
Table 4. Multiple response analysis
PM CO2 CH4 H2S CO HCHO

Student 54.0% 40.0% 80.0% 44.0% 60.0% 8.0%
Staff 35.5% 83.9% 71.0% 22.6% 58.1% 6.5%
Total 46.9% 75.3% 76.5% 35.8% 59.3% 32.1%
3. RESULTS
This study, in which the opinions of campus users are determined, includes questions about
classroom/office use and indoor air quality of indoor areas. This study shows the importance of raising
awareness and choosing the right land. In addition, this situation, which affects the quality of life of
those residing around the landfill, is expected to raise awareness among managers.
A summary of the research findings is as follows;
• 44.4% of users say that solid waste integrated facility impacts indoor air quality. Also, 90 out of 100
samples think it's affecting their health.
• Decentralized heating and cooling systems are used in offices and classrooms where ventilation can
only be done naturally. While 25% of users were unsatisfied, 42% gave an average rating. There were
only 2 examples that claimed to have a clean air indoor environment.
• 60% stated that they do not know the system's working principle. For this reason, it is important to
increase the general knowledge and awareness of those living near this landfill area.
In addition, managers must involve the public and institutions in their immediate vicinity when
implementing waste management programs and making landfill site decisions. Public support is
essential for the success of such decisions.
ACKNOWLEDGEMENTS
The present study was sponsored by the Adana Alparslan Türkeş Science and Technology University
Scientific Research Projects Fund (BAP Project No. 2212001).
REFERENCES
[1] M. Unal, A. Cilek, and E. D. Guner, "Implementation of fuzzy, Simos and strengths, weaknesses,
opportunities and threats analysis for municipal solid waste landfill site selection: Adana City
case study," Waste Manag. Res., 2020, doi: 10.1177/0734242X19893111.
[2] A. Al-Fakih, B. S. Mohammed, M. S. Liew, and E. Nikbakht, "Incorporation of waste materials
in the manufacture of masonry bricks: An update review," Journal of Building Engineering.
2019, doi: 10.1016/j.jobe.2018.09.023.
[3] M. Pulimeno, P. Piscitelli, S. Colazzo, A. Colao, and A. Miani, "Indoor air quality at school and
students' performance: Recommendations of the UNESCO Chair on Health Education and
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Sustainable Development & the Italian Society of Environmental Medicine (SIMA)," Health
Promotion Perspectives. 2020, doi: 10.34172/hpp.2020.29.
[4] Statista, "Statista - The Statistics Portal for Market Data, Market Research and Market Studies,"
Statista. 2019.
[5] OurWorldInData, “{CO}₂ emissions per capita vs {GDP} per capita,” Our World in Data. 2016.
[6] N. A. Megahed and E. M. Ghoneim, "Antivirus-built environment: Lessons learned from Covid-
19 pandemic," Sustain. Cities Soc., 2020, doi: 10.1016/j.scs.2020.102350.
[7] T. Pekdogan, A. Tokuç, M. A. Ezan, and T. Başaran, "Experimental investigation of a
decentralized heat recovery ventilation system," J. Build. Eng., 2021, doi:
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[8] T. Pekdogan, A. Tokuç, M. A. Ezan, and T. Başaran, "Experimental investigation on heat transfer
and air flow behavior of latent heat storage unit in a facade integrated ventilation system," J.
Energy Storage, 2021, doi: 10.1016/j.est.2021.103367.
[9] S. Mentese et al., "A long-term multi-parametric monitoring study: Indoor air quality (IAQ) and
the sources of the pollutants, prevalence of sick building syndrome (SBS) symptoms, and
respiratory health indicators," Atmos. Pollut. Res., vol. 11, no. 12, pp. 2270–2281, 2020.
[10] N. Ma, D. Aviv, H. Guo, and W. W. Braham, "Measuring the right factors: A review of variables
and models for thermal comfort and indoor air quality," Renew. Sustain. Energy Rev., vol. 135,
no. March 2020, p. 110436, 2021, doi: 10.1016/j.rser.2020.110436.
[11] M. E. Gündoğmuş, V. R. Kalfa, and H. Başkaya, “Real Estate Valuation and Statistical
Analysis,” J. Süleyman Demirel Univ. Inst. Soc. Sci. Year, vol. 1, no. 42, pp. 173–197, 2022.
[12] N. Gürsakal, Descriptive statistics: Statistics I. 2012.
[13] Ş. Kalaycı, SPSS applied multivariate statistical techniques, vol. 5. 2010.
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COMPARISON OF ENERGY EFFICIENCY STUDIES OF TURKEY AND

GERMANY
Fatih Burak ÖZKANLI1, Zafer DEMİR2
1
Department of Advanced Technologies, Graduate School of Science, Eskişehir Technical University, Eskişehir, Turkey
2 Department of Electricity and Energy, Porsuk Vocational School, Eskişehir Technical University, Eskişehir, Turkey
ABSTRACT
Where energy is used is as important as obtaining it from a source. It has been demonstrated by the studies that significant
savings will be achieved with the regulations to be made in the use of energy. With the concept of energy efficiency, countries
attach importance to efficiency studies and adopt various policies to reduce energy waste. Turkey’s energy efficiency studies,
which started with Turkey's Regulation on Energy Efficiency in Industry, which started in 1995, became more frequent with
the 2000s, and with the Energy Efficiency Law enacted in 2007, some obligations and sanctions were introduced to ensure
energy efficiency. Especially in the European Union harmonization process, legal arrangements have been made for the
directives published by the European Union (EU). With the Energy Conservation Law (EnEG) enacted in 1976, Germany took
the first step in this sense by giving the government the authority to enact laws in the field of energy efficiency. Then with the
EnEV regulation, standards in the field of energy efficiency were determined and legal regulations were made that would
directly affect the citizens. Germany has published new updates over the years in order to comply with the directives and
programs published by the European Union. In this study, an overview of the energy efficiency policies determined by Turkey
and Germany from the past to the present will be made, and the progress made by the two countries on energy efficiency will
be compared. The significant impact of EU Directives on energy efficiency laws will be examined. A comparison will be made
about the differences in the laws enacted within the framework of the policies determined by Turkey and Germany. Different
reference values in laws and regulations published for the same purpose will be compared. The effects of the renewable and
emission-free energy target determined by Germany against the domestic energy target determined by Turkey on energy
efficiency studies will be examined.
Keywords: Energy efficiency, Energy efficiency law, Building energy certificate, Energy efficiency policy
1. INTRODUCTION
Energy efficiency is now a concept that has an important place in the energy policies of most countries.
The importance of energy efficiency as a policy objective is linked to benefits such as reducing CO2
emissions and creating a clean environment, as well as creating economic, industrial competitiveness
and energy security. Efficient use of energy is aimed with energy saving and energy efficiency.
Obtaining energy from different energy sources has caused different legal regulations in the policies of
the countries. Telli et al. (2021) compared Turkey's transition from fossil energy to renewable energy,
energy policy, strengths and weaknesses, and targets with Germany, considering its own conditions.
Thanks to the “Energiewende” policy, which entered the literature in the 1980s, Germany gained
important experience in the energy transformation process. For this reason, the transformation model of
Germany, which has technological superiority, has come to the view that it is a sample for Turkey, which
has an important potential in renewable energy as well as other countries. It is shared that one of the
differences between Germany and Turkey is that Germany aims to shut down nuclear energy in 2022,
while Turkey will have nuclear power for the first time in 2023. [1] Turkey and Germany aim to achieve
energy efficiency by adopting various energy policies. At the point where the adopted energy efficiency
policies are not sufficient, new policies have been adopted or old legislation has been updated. In the
study, it is aimed to determine the deficiencies and differences on the laws by comparing the energy
policies of Turkey and Germany. Making this comparison contributes to the determination of more
effective energy policies for countries.
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2. COMPARISONS OF ENERGY EFFICIENCY STUDIES
2.1 Policies in Energy Resources

The main differences in the energy transition between Germany and Turkey can be said to be related to
coal power plants and nuclear energy. Turkey has aimed to make energy domestic and renewable.
Turkey has determined policies to achieve the goals. On the other hand, Germany has set the goal of
gradually removing the use of coal and ending the use of nuclear energy and developing in renewable
energy sources. Germany has placed the concept of "Energiewende" on its energy policy. In this concept,
which emerged by combining the words "energy" and "conversion", the aim is to replace nuclear energy
with renewable energy. Nuclear disasters in the world have an important role in taking this decision.
Germany planned to fill the energy gap that will occur with the deactivation of nuclear power plants,
with renewable energy sources, natural gas turbines, energy efficiency and savings, demand
management, and existing conventional power plants.[2] Another target that Germany has set in line
with its energy transformation strategy is to reduce coal power plants with 41 GW installed capacity to
17 GW by 2030. The German Coal Commission's forecast for 2030 is that renewable energy sources
will increase to 65% and current coal production will decrease by two-thirds.[3]
Turkey does not consider to reduce the amount of coal use as a priority target. Domestic coal is preferred
in power stations. Various studies are carried out to encourage the use of domestic coal to reduce foreign
dependency in energy. Turkey’s target is to have electricity by using nuclear power and reduce foreign
dependency. Nuclear energy is an important element in Turkey's policy to diversify its energy resources.
Although Germany will close its last nuclear power plant in 2022, Turkey has a target of gradually
producing electricity from nuclear energy in 2023.
There are three similar goals about the energy transition of Germany and Turkey: reducing greenhouse
gas emissions, expanding the use of renewable energy, and increasing energy efficiency. It is very
important for every country that the energy has economic and continuous supply security. The
cooperation between two countries in the energy field, especially the information and technology
transfer from Germany to Turkey is constantly developing. Both countries arrange their national energy
policies in line with the EU’s goal, which is to make zero GHG emissions by the year 2050. [1]
2.2 Energy Efficiency Studies in Transportation

The use of clean and environmentally friendly fuels in the transportation sector, the reduction of fuel
consumption and the efficient and effective use of energy by using efficient transportation systems are
energy efficiency. In this purpose, it is aimed to restrict private cars in traffic and to reduce single
driving. At the same time, various support policies are established to encourage the use of public
transport. Increasing the number of clean and energy efficient vehicles in traffic is possible by applying
different strategies that support each other. There are legal regulations and incentives behind these
strategies. [4] Intelligent transportation systems, developed by using information and communication
technologies, will contribute to the improvement of environment and air quality as well as energy
efficiency. In 2018, the transportation sector has a 26.2% share in final energy consumption in Turkey.
Therefore, ensuring energy efficiency in transportation will reduce energy consumption and reduce
foreign dependence on energy. In this context, the "Regulation on Procedures and Principles for
Increasing Energy Efficiency in Transport" was published by the Ministry of Transport and
Infrastructure in 2019. With this regulation, the principles and procedures of reducing the fuel
consumption of motor vehicles, increasing efficiency in vehicles, encouraging the use of
environmentally friendly fuel, reducing air pollutants and greenhouse gas emissions, expanding public
transportation, establishing smart transportation systems, improving transportation infrastructures and
preparing city transportation plans have been determined.
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Table 2.1.1. Turkey and Germany energy efficiency targets
Turkey Germany
• Reducing energy costs, ensuring energy • Three targets have been set: energy
supply security, transition to a low- security, efficient and economical
carbon economy and protecting the energy, and environmentally
environment compatible energy supply.
Energy Policies
• It is aimed to reduce the risks arising • There is a target to phase out coal-fired
from foreign dependency by producing power plants by 2030 and to switch to
energy from domestic energy sources. renewable energy by closing nuclear
power plants by the end of 2022.
• In 2023, it is aimed to reduce Turkey's • Germany aims to achieve Net Zero
primary energy consumption by 14%. Emissions by 2045. It has set
• Turkey has set a net-zero emission preliminary targets to reduce emissions
target until 2053. by at least 65 percent by 2030 and 88
• Annual energy consumption in percent by 2040, compared to 1990
Energy Efficiency buildings and facilities of public levels.
and Greenhouse institutions will be reduced by 10% • Projected photovoltaic solar power
Gas Emission until 2015 and 20% until 2023. capacity will be increased from 1.9
• Within the scope of Turkey's 2023 GW to 6 GW in 2022.
energy strategy, it is aimed to increase • The target of having a share of at least
the share of renewable energy in 32% for renewable energy has been
electricity generation to 30%. adopted.
The above chart shows the amount of energy consumed in the transportation sector in Turkey between
the years 2008-2018. In 2018, 28.0 MTOE was consumed, corresponding to 28% of the total final
consumption. 28 MTOE is equivalent to approximately 300 TWh of electricity. Total transportation
energy demand has grown rapidly, increasing by 88% since 2011. It can be said that the main reason for
the remarkable increase in energy consumption in transportation is the growth in automobile use.
Between 2006 and 2016, vehicle kilometers traveled per capita for cars and light trucks nearly doubled.
[5] Road transport accounted for 92% of the total transport energy demand in 2018, the remaining 5%
of local aviation and pipeline transport, rail transport shares.
Figure 2.2.1. Final energy consumed in the transportation sector in Turkey between 2008-2018 [5]
It is important for the Ministry to prepare calculation, modeling and reporting practices for reducing fuel
consumption and emission values by improving transportation infrastructures. At this point, urban
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transportation planning should be done properly. In transportation plans, priority is given to surrounding
highways and rail system studies. To encourage public transportation, the share of the rail system is
increased in corridors where passenger demand is sufficient. In this way, applications are developed to
reduce vehicle use, especially in city centers. With the reduction of vehicle use, areas where bicycles
can be left safely are created in public parking lots to support bicycle transportation. Apart from these
measures and practices, training and awareness raising activities are also an important factor in ensuring
energy efficiency in transportation. Along with the educations, the awareness of the citizens is ensured
by including economic driving technique and environmental pollution.
In addition to these, it is an important factor to remove the vehicles with high energy consumption from
the traffic to ensure efficiency. Turkey enacted a scrap vehicle law and encouraged users not to use old
vehicles. Thus, it provided a reduction in CO2 emissions with the old cars removed from the traffic. For
example, without the scrap law in 2010 and 2011, approximately 16.11 and 16.75 million tons/year of
CO2 emissions will occur, respectively, from automobiles. It has been calculated that if an effective
scrap law for 20-year-old vehicles is enacted in 2010, these CO2 emissions could decrease by 0.3% in
2010 and 1.9% in 2011. [6]
Another way to reduce CO2 emissions is to reduce the number of internal combustion engine vehicles
in traffic and to expand the use of electric vehicles. The electric vehicle trend in the world has also been
effective in Turkey. There has been an increase of electric vehicles in Turkey in recent years. When
compared to the increase in the world, it is seen that the increase is not enough. The main reason for this
is the lack of incentives for electric vehicles. It is important to attract investors to this area with incentives
and to reduce fossil fuel dependence, since the number of vehicles is still low and the cost of investment
takes many years. In addition, Turkey is preparing to start mass production of its own domestic electric
car in 2023.
When we look at the transportation sector of Germany, it constitutes approximately 28% of the total
final energy consumption in Germany as of 2015. One of the aims of German energy efficiency is to
reduce carbon emissions by 80 to 95% by 2050, with contributions from the electricity and heating
sectors as well as transport. In the field of transport, Germany has set a target of reducing final energy
consumption by 10% by 2020 and 40% by 2050, with reductions compared to 2005 levels. [7]
Effect of crisis
Figure 2.2.2. Final energy consumed in the transportation sector in Germany between 2005-2014 [7]
The chart above shows the final energy consumption in transportation in Germany between 2005 and
2014. While it decreased to its lowest level in 2009 with the effect of the economic crisis, it increased
to 727 TWh in 2013 again.
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Figure 2.2.3 Final energy consumed in the transport sector in Germany in 2020
(https://www.umweltbundesamt.de)
The chart above shows the final energy consumption values in transportation for 2020. Looking at the
2020 data, the final energy consumption in transportation has been measured as 635 TWh. Fossil fuels
(petroleum products) accounted for 91.8% of this consumption. It can be said that the lower energy
consumption level compared to previous years is due to the pandemic. The closure decisions taken
within the scope of Covid measures caused a significant decrease in energy consumption in the
transportation sector. Experiencing the pandemic process has resulted in lower levels of final energy
consumption than the crisis in 2009.
Measures such as the Energy Concept, the German Government's roadmap for the transition to
renewable energy, and the 2014 Energy Efficiency National Action Plan (NAPE) outlined the promotion
of a wide range of renewable energy technologies and policy tools, including the promotion of electric
vehicles. At this point, electric vehicles have an important place in the climate-friendly transformation
of transportation. All-electric cars produce no exhaust emissions while driving. It also produces no CO2
emissions when charged with electricity from renewable sources. Also, batteries in electric cars can take
on a storage function for the power system if they are charged when large amounts of electricity are
available from wind and solar power plants. In this way, the batteries also support the system integration
of renewable energy. As part of its goals to reduce CO2 emissions, Germany put into use the world's
first hydrogen-powered trains as of 2018. However, the use of hydrogen-powered buses in German cities
is becoming more common day by day. Considering all these, the widespread use of electric and
hydrogen-powered vehicles increases efficiency in transportation and has an important role in reducing
carbon emissions. To achieve this, the German government provides a maximum subsidy of 9000 Euros
for users who want to buy electric cars. As a matter of fact, with the determination of these incentives,
the share of electric vehicles, which was 13.5% in 2020, increased to 26% in 2021.
There are big differences between the energy used in transportation in Turkey and the energy used in
transportation in Germany. Looking at the final consumption, consumption in Germany is almost twice
that of Turkey. When these policies are compared, it can be said that there is not enough incentive for
electric vehicles in Turkey compared to Germany. Since the initial investment cost is higher than the
current internal combustion engine vehicles, these vehicles were not preferred in Turkey. On the other
hand, there are not enough vehicle charging stations and infrastructures for electric vehicles in Turkey.
As of 2021, while there are 3457 electric vehicle charging stations in Turkey, it has been announced as
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50,901 in Germany. It can be said that the big difference is due to the low number of electric vehicles
in Turkey and the lack of adequate charging infrastructure when compared to Germany.
There are no significant differences at this point, as automobile manufacturers use European similar
vehicle models in terms of low fuel consumption and reduction of vehicles. However, due to high oil
prices, high volume engine options of some vehicles are not offered in Turkey. As engine volumes
increase, the increase in tax brackets has directed users to vehicles with smaller engine volumes.
2.3 Energy Efficiency in Buildings

The concept of energy efficiency has gained importance for Turkey and Germany over the years, and
both countries have increased their studies in this field and supported these studies with laws and
regulations. Along with these determined policies, energy efficiency has also been achieved. Turkey and
Germany, together with their efforts to ensure energy efficiency, have made laws mandatory for the
implementation of the requirements. Sanctions were imposed in case of non-implementation of these
laws. Considering the concepts of energy efficiency, the concept of energy efficiency in Germany
emerged earlier than in Turkey.
It has been concluded that technically possible and economically necessary savings in the field of energy
efficiency in Germany cannot be implemented without legal regulations. For this reason, with the EnEG
law in 1976, it was aimed to ensure economical and rational energy use. Not only energy efficiency, but
also reducing dependence on imported energy sources is one of the energy policies that Germany has
determined in the first place. The first legal energy efficiency study in Turkey emerged with the
Industrial Energy Efficiency Regulation in 1995. With the first laws enacted, it is possible to say that
Germany has issued a more general regulation in the first place, while Turkey has only issued a
regulation to reduce energy expenditures in the industrial sector and to save energy. With this law, some
obligations have been brought to the enterprises operating in the industrial sector to ensure energy
efficiency. However, in the EnEG Law enacted by Germany, the law has no direct effect on the citizens
and the government has been given the authority to regulate. With this authority, the government can
issue regulations based on EnEG. Requirements for energy efficient thermal insulation and operation of
heating and ventilation systems for buildings to be built are mentioned. In fact, EnEG provided a legal
basis for other laws enacted by Germany in the field of energy efficiency.
Energy efficiency has become increasingly important globally in the 2000s. With the depletion of fossil
fuel resources and the increase in energy demand, the number of studies and legal regulations on this
concept has increased. With the Energy Efficiency Law enacted in 2007 in Turkey, it can be said that a
policy that includes efficiency in every sector has been adopted to use energy effectively and to prevent
waste. Within the framework of similar policies, in the other version of EnEG issued by Germany in
2005, it was decided to determine an efficiency certificate for existing buildings and new buildings, just
like electrical appliances. This decision was determined under the same title in the Energy Efficiency
Law in 2007.
It can be said that the "Energy Performance in Buildings Directive (2002/91/EC)" of the European
Parliament and the Council, which entered into force on January 4, 2003, was effective in determining
the energy efficiency certification policy for both countries. In line with this directive, when
constructing, selling or renting a building, a certificate is required to be submitted with details of its
energy performance. The validity period of this certificate is determined as 10 years. To comply with
the European Union Laws for Germany and to follow the policies in accordance with the European
Union harmonization process for Turkey, energy certificate requirements have been introduced in
buildings. When the energy certificates of the two countries are compared, the “energy consumption”
values are taken as a basis while obtaining the building energy certificate in Turkey. However, Germany
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offers two different building energy certificate options according to consumption and demand. The
usage areas of these two certificates were determined according to the construction date of the building
in Germany and the scope of the 1977 WSWO Thermal Insulation Regulation. In some cases (for
example, if it meets the 1977 Thermal Insulation Regulation), the right to choose between the energy
requirement certificate and the energy consumption certificate is granted. The table below contains
general comparison information about the contents of the building energy certificates of Turkey and
Germany.
Table 2.3.1. Comparison of Energy Performance Certificates of Turkey and Germany
Turkey Germany
• Energy Performance Certificate is • Energy Performance Certificate is valid for

valid for 10 years from the date of 10 years from the date of issue.
Energy issue. • Classified from A+ to H. (GEG 2020)
Performance • Classified from A to G. • The reference value is placed in the C
Certificate • The reference value is placed in the class.
C class.
• New buildings require energy • Energy certification is required for new

certification. Newly constructed or buildings. If a new building is built, the client
under construction buildings with a must ensure that the owner of the building is
level lower than Class C cannot obtain provided with a proof of need for the
occupancy permits by law. completed building.
• Energy Performance Certificate (EKB) • Structures exempt from Energy Certificate are
will be used in all buildings except for as follows.
the buildings mentioned below. -Residential buildings intended for less
- Buildings where production than 4 months of use per year,
activities are carried out in industrial -Places of Worship
areas, buildings with a planned - Buildings with a total usage area of less
Places Where usage period of less than two years, than 50 m2,
Energy - Buildings with a total usage area -Holiday apartments
Performance of less than 50 m2, • An energy certificate should be issued and
Certificate is -Greenhouses, Workshops, exhibited in officially used buildings with
Required Buildings such as warehouses, heavy public traffic and more than 250 m² of
warehouses, barns, barns that are usage area. Private owners of buildings with
built individually and do not need to high public traffic must show identification
be heated or cooled. for 500 m² or more of usable space.
• When the building or detached section • Landlords are obliged to present the energy
is sold or rented, the building's Energy certificate to the buyer or tenant if they rent or
Performance Certificate is also given sell their house. After the purchase or rental
to the buyer or tenant by the owner. agreement is signed, the landlord must deliver
• A copy of the energy identity the energy performance certificate to the
document must be given to the other buyer.
party in the purchase, sale and rental
transactions.
Places • Consultancy companies authorized by • Energy Efficiency Consulting companies
authorized to the Ministry to issue EKB
issue Energy
Performance
Certificate
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In the table above, there are energy efficiency classes in the energy identity certificates of Turkey and
Germany, as in electrical appliances. While Germany determined 9 different efficiency classes, Turkey
determined 7 different energy classes. This difference is because the Energy Performance/Reference
Indicator (EP/RI) ratio is specified in the German energy certificate for A+ and for H level.
Table 2.3.2. Classification table showing the building energy performance class of Germany
Building Energy Efficiency Class Energy Class Index (EP) by Primary Energy Consumption
A+ 0 ≤ EP ≤ 30
A 30 ≤ EP ≤ 50
B 50 ≤ EP ≤ 75
C 75 ≤ EP ≤ 100
D 100 ≤ EP ≤ 130
E 130 ≤ EP ≤ 160
F 160 ≤ EP ≤ 200
G 200 ≤ EP ≤ 250
H 250 ≤ EP
The table above shows the values of the building energy efficiency class determined in Germany. In the
table below, building energy efficiency class values for Turkey are determined according to the EP
Index.
Table 2.3.3. Classification table showing the building energy performance class of Turkey
Building Energy Efficiency Class Energy Class Index (EP) by Primary Energy Consumption
A 0 ≤ EP < 40
B 40 ≤ EP < 80
C 80 ≤ EP < 100
D 100 ≤ EP < 120
E 120 ≤ EP < 140
F 140 ≤ EP < 175
G 175 ≤ EP
While the EP/RI ratio is between 0-40 in Turkey, it is classified as A+ class for 0-30 and A-class for 30-
50 in Germany. While the lowest efficiency class is G in Turkey, this class is determined as H in
Germany.
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Figure 2.3.1. Greenhouse Gas Emission Value fields in the Energy efficiency certificate of Turkey and
Germany (Left side: Turkey, right side: Germany)
As seen in the image above, it is mandatory for each country to specify the Greenhouse Gas Emission
values in addition to the energy efficiency class. In the certificates in Turkey, classes have been
determined for the greenhouse gas emission value, just like the energy need. In the energy certificate of
Germany, only the Greenhouse gas emission value must be entered in the relevant part, there is no other
classification system. These information and parameters constitute the energy identity class of the
building. The lowest class of the energy certificate for newly constructed buildings has been determined
as class C for Turkey and Germany. It is obligatory for buildings not to be lower than this energy class.
Building permits are not issued for buildings with a level lower than C class. These certificates are issued
by energy efficiency consultancy companies authorized by the state in both countries. Companies
analyze the buildings and create the building energy certificate in line with the data they obtain.
When the energy efficiency policies of the two countries are examined, the laws and regulations created
include decisions to ensure the energy efficiency of the buildings. It can be said that a significant part
of the energy produced is due to its use in buildings and housing sector. The share of the building sector
in final energy consumption worldwide has exceeded 30%, and its share in global electricity
consumption has exceeded 50%, and the building sector is responsible for one third of global carbon
emissions. [8] Therefore, saving on energy consumption in buildings is of great importance in terms of
ensuring energy efficiency and reducing consumption.
To ensure energy efficiency, Germany and Turkey have determined reference limit values to be used in
technical designs for existing and newly constructed buildings. When these design values and
parameters are examined, one of the important differences is the situations determined by the countries
depending on the climatic conditions. For example, the heat transfer coefficients vary according to 4
different degree-day regions for Turkey. It expresses the severity of weather conditions (cold and hot)
in a specific period, considering the degree day zones, outdoor temperature and room temperature.
Different reference values have been determined for regions with colder/warmer climates.
Heating/Cooling Degree Days measures the amount of heating or cooling required in your property.
Degree days are measured on a base of 18 degrees. Above 18 degrees it is assumed that property will
need cooling, and below 18 degrees it is assumed that property will need heating. For each degree greater
or less than the reference value, the degree-day concept is used. However, reference limit values for the
heat transfer coefficient in Germany are same and constant for each region. Although 4 seasons are seen
prominently in Turkey, Germany has a temperate climate. Due to the geographical and climatic
characteristics, there are large temperature differences in most regions of Turkey in summer and winter.
Therefore, countries have determined different reference values in line with their climates. There are
differences when the heat transfer coefficient values are compared.
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Table 2.3.4. Comparison of thermal conductivity coefficients of Turkey and Germany
Turkey Germany
1st 2nd 3rd 4th Residential Non-residential

Component Unit Zone Zone Zone Zone Building Building (a
building with a
temperature of
more than 19°C)
Outer Wall (UD) W/m2K 0.70 0.60 0.50 0.40 0.28 0.35
Window UP) W/m2K 2.4 2.4 2.4 2.4 1.3 1.3
Ceiling (Ut) W/m2K 0.70 0.60 0.50 0.40 0.35 0.35
The table above shows the heat transfer coefficients determined by Turkey and Germany. In Turkey,
these values are determined as common for all building types, but in Germany, reference limit values
are determined differently for residential buildings and non-residential buildings. For non-residential
buildings, Germany has determined different values for buildings that are heated between 12-19 degrees
and have temperatures higher than 19 degrees. For example, in the TS 825 standard, the heat
permeability coefficient of the exterior wall in residential buildings in Turkey is 0.70 W/m2K for the 1st
zone, 0.60 W/m2K for the 2nd zone, 0.50 W/m2K for the 3rd zone and 0.40 W/m2K for the 4th zone [9].
In Germany, this value was determined as 0.28 W/m2K in GEG 2020. For non-residential buildings, it
is determined as 0.28 W/m2K for buildings with heating temperatures higher than 19 degrees, and 0.40
W/m2K heated between 12-19 degrees. [10]
While the heat transfer coefficients for windows were determined as 2.4 W/m2K in all heat zones in
Turkey, this value was determined as 1.3 W/m2K in Germany. Therefore, it can be said that reference
values in building design are determined at more stringent levels in Germany. According to statistical
information: The heating energy need of an existing house in Turkey, which has the same climate
conditions and the same usage area as countries where energy is used efficiently, such as France,
Germany, England, Sweden, is 2-5 times more than a house in these countries. [11]
2.4 Comparison of Standards

The standards set by the countries are the set of instructions used when answering the question of how
to do a job better. Standards consist of technical information and have prescriptive features by being
used with laws.
To ensure energy efficiency, Turkey and Germany have set various standards. Among these standards,
there are TS 825 Thermal Insulation Rules determined in Turkey and similar DIN4108 standards
determined in Germany. The purpose of these standards is to limit the amount of energy used for heating
buildings, to increase energy efficiency and to determine the calculation methods and references to be
used for calculating energy needs. Looking at the TS 825 Standard, it was created after the DIN 4108
determined by Germany. While creating the TS 825 standard, the German DIN 4108 standard was taken
as reference. Therefore, these standards show many similarities. So much so that when TS 825 was first
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published, idiomatic errors were made and the heat transfer concept could not be studied well because
the German DIN 4108 standard was translated without a good understanding. [13] In general, the aim
of adapting these standards to EU standards has been adopted.
In part of the TS 825 standard, the data of the DIN 4108 German standard has been accepted. For
example, DIN 4108 and TS 825 accept a limit of 1440 hours for condensation times on walls and roofs,
and 2160 hours for evaporation time. However, considering factors such as the difference in climatic
conditions and material quality, it is seen that the usability of these values is a matter of discussion for
Turkey. The use of a single value in the standards for these two countries, which are located in different
geographical regions from each other, is not a correct standard setting method. It can be said that the
outside temperatures vary greatly depending on the climate of the countries, especially in terms of
providing insulation in buildings. [13]
Table 2.4.1. Comparison of the building's annual energy need calculation of DIN 4108 and
TS 825 Standards [13]
Germany’s DIN 4108 Turkey’s TS 825
(QAnnual) (QAnnual)
A/Vgross ≤ 0.2 54.0 kWh/m2 27 - 104 kWh/m2
0.5 70.2 kWh/m2 41 - 129 kWh/m2
1.0 97.3 kWh/m2 64 - 171 kWh/m2
A/Vgross ≥ 1.05 100.0 kWh/m2 66 - 175 kWh/m2
Qannual : The total annual heating energy requirement of a building.
In the table above, it is seen that the German DIN 4108 Standard and the Turkish TS 825 standard are
compared based on the annual total heating energy needs of a building. Comparative values in this table
are selected values for the same A/Vgross ratios. [14] A/Vgross ratio is the value obtained by the ratio of
the total heat-losing surface area (A) to the heated gross volume (Vgross)of the building. While calculating
the annual heating energy of the building, the calculation is made using this ratio. While different
A/Vgross constants are used for 4 different degree day regions in Turkey, this ratio is constant for each
region in Germany. Looking at the average of the values in the table, it can be said that the annual
heating energy need of the building in Germany is less than that of a building in Turkey. The reason for
this may be that the reference values determined by Germany are lower than those of Turkey.
3. CONCLUSIONS AND SUGGESTIONS

Energy is an important issue on which all countries work intensively. How the energy will be used is an
important factor as well as from which source it is produced. At this point, both countries have
determined various energy targets and policies. It has put these policies into practice with both laws and
regulations and strategic action plans.
Energy efficiency studies have gained importance in both countries in the 2000s. With the concept of
energy efficiency, which emerged earlier in Germany than in Turkey, the aim is to save in areas where
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energy is used intensively. Laws enacted to ensure savings in these areas have imposed obligations on
the sectors and, if not implemented, sanctions have been imposed along with strict controls. On the other
hand, together with the objectives and processes determined by the European Union, the legal
regulations of the countries have also been shaped over time. At this point, due to the harmonization
process initiated by Germany to meet the requirements the European Union has been effective in
updating the legal regulations and taking it as a reference. European Union Directives are effective in
updating legal regulations and taking references for Turkey to become a member of the European Union.
The energy efficiency study appeared earlier in Germany compared to Turkey. It is obvious that the
adoption of these policies and the provision of energy efficiency will benefit countries both
economically and environmentally. To achieve these efficiencies, these policies have been made
mandatory in various sectors and sanctions have been applied if they are not implemented. In this way,
compliance with the standards was ensured. The directives published by the European Union have an
impact when determining these standards. These directives have been put into practice by both countries.
Germany, which is a member of the European Union, has the aim of fulfilling the requirements and
Turkey has the aim of fulfilling the requirements in the harmonization process. Therefore, laws and
regulations issued by countries have been subject to various updates in line with these directives.
Releasing these updates is a requirement for both countries. Changes in technologies, energy usage
habits and climates of countries over the years require changes in legal regulations.
Countries are working in the field of energy efficiency with the thought that the use of energy is as
important as its production. By comparing these studies between countries, information about the
accuracy of the determined targets and policies can be obtained. Although it seems like a common goal
for the two countries to give importance to energy efficiency, the need for energy efficiency is to reduce
foreign dependence on energy in Turkey. In Germany, the aim is to increase the use of renewable
resources, reduce carbon emissions and increase energy efficiency.
When we look at the studies carried out by Turkey in the field of energy efficiency, it is obvious that
there are standards and studies that take Germany as a reference. Providing a comparative assessment
of the energy efficiency of the two countries may be beneficial in identifying weak and open points in
current energy policies. The establishment of joint energy efficiency commissions by the two countries
may be effective at this point. In addition, the applied examination of the studies of the two countries
together with the energy efficiency joint programs at undergraduate, graduate and doctoral levels will
pave the way for the creation of a more beneficial and development-based system for young engineers
and politicians.
REFERENCES
[1] Telli, A., Erat, S., & Demir, B. Comparison of energy transition of Turkey and Germany: energy
policy, strengths/weaknesses and targets. Clean Technologies and Environmental Policy, 2021;
2(23), 1-15.
[2] Morris, C., & Pehnt, M. Energy Transtion: The German Energiewinde. Berlin: Heinrich Böll
Fundation, 2015.
[3] A Roadmap for a Just Transition from Coal to Renewables. Agora energiewende, 2019. Retrieved
March 15, 2022, from www.agora-energiewende.de: https://www.agora-
energiewende.de/en/publications/the-german-coal-commission
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[4] Kessler, J., & Schroeer, W. Meeting mobility and air quality goals: Strategies that woek.
Transportation, 1995; (22), 241-272.
[5] Turkey - Energy policy review report. International Energy Agency (IEA). 2021 Retrieved January
2022 from https://iea.blob.core.windows.net/assets/cc499a7b-b72a-466c-88de
d792a9daff44/Turkey_2021_Energy_Policy_Review.pdf
[6] Şahin, Ü., Onat, B., Sivri, N., & Yalçın, E. Hurda yasasının otomobil kaynaklı sera gazı emisyonunda
oluşturacağı muhtemel etki. Journal of the Faculty of Engineering and Architecture of Gazi
University, 2013; 3(26).
[7] Energiewende outlook: transportation sector - executive summary. PWC. 2015 Retrieved April
2022, from https://www.pwc.de/de/energiewende/assets/energiewende-outlook-transportation-
2015.pdf
[8] Kabakçı, O. K. Binalarda Enerji Verimliliği.Wordl Energy Council, 2019. Retrieved April 2022,
from https://www.dunyaenerji.org.tr/wp-content/uploads/2019/11/21112019Sunum.pdf
[9] TS 825 - Binalarda Isı Yalıtım Kuralları. Turkish Standards Instution, Turkey, 2013.
[10] Gebäudeenergiegesetz. German federal ministry for economic affairs and climate action, Germany,
2020.
[11] Açıklamalı ve Örneklerle TS 825 Standardı Binalarda Isı Yalıtım Kuralları. İzocam. 2013.
[12] Dağsöz, A. K., Bayraktar, K. G., & Ünveren, H. H.. Isı yalıtımı ve kalorifer tesisatı standartları
üzerine görüşler. Tesisat Mühendisliği 2001; 50-54.
[13] Pehlevan, A. Binalarda isı yalıtım kuralları standardının yoğuşma ve buharlaşma süreleri açısından
değerlendirilmesi. V. Ulusal Tesisat Mühendisliği Kongresi, 3-6 October 2001; İzmir, Turkey,
441-458.
[14] Özenç, A. Edirne’deki Isı Yalıtım Uygulamaları, Trakya Üniversitesi Fen Bilimleri Enstitüsü,
Yüksek Lisans Tezi, Edirne, Turkey, 2007.
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MOLECULAR STRUCTURE, NBO AND TD-DFT ANALYSIS OF

4-METHYL-3-FURALDEHYDE BASED ON DFT CALCULATIONS
Nihal KUŞ
Department of Physics, Science Faculty, Eskisehir Technical University, 26470, Eskisehir, Turkey
ABSTRACT
In this study, molecular structure of 4-methyl-3-furaldehyde (4M3F) was analyzed using density functional theory (DFT) with
level of B3LYP/6-311G++(d,p). As a result of the scanning of the CCC=O dihedral angle, two conformers (trans and cis) were
found at minimum energy and the trans was more stable than the cis at ca. 6.4 kJ mol-1.
Time dependent DFT (TD-DFT) calculations have been used to calculate the low-energy excited states energies and oscillator
strengths. As a result of calculations, it was found that the highest transition probability and most effective oscillator strength
were in the S0→S3 singlet state for both conformers. This excitation energy corresponds to 5.9 eV for the trans conformer,
while it is around 5.6 eV for the cis conformer.
The change in electron density in bonding-antibonding orbitals and their interactions as well as stabilization energies E(2) and
natural atomic charges were calculated by Natural Bond Orbital (NBO) analysis. Electronic properties were analyzed using
HOMO and LUMO energies.
Keywords: Keywords: 4-methyl-3-furaldehyde, Time dependent DFT, Natural Bond Orbital (NBO) analysis
1. INTRODUCTION
Aldehydes are organic compounds with a carbonyl group in their structure and hydrogens attached to
this group. They are called aldehydes because they can usually be obtained from the dehydrogenation
of alcohols at high temperatures. Furans are an aromatic heterocyclic ring of five atoms and the Ring
has one oxygen and four carbon atoms. Furan and its derivatives play an important role in the
pharmaceutical and chemical industry. Furan and its derivatives, which are also widely used in medicine
and chemistry, are also atmospheric pollutants and are produced as a result of burning forests (1, 2).
Furans, known as one of the most toxic volatile substances (3-5), contain polychlorine, which is
dangerous for all living things, and are found in a wide variety of furan derivatives. Investigation of the
presence of toxic compounds such as reactive aldehydes in foods is very common and has been an
important research topic. With the increasing importance of consumer protection and quality control, it
has started to be investigated more. Spano et al. reported that there are furanic aldehydes in honey (6).
It has also been found in popcorn (7).
Theoretical studies of 5-nitro-2-furaldehyde oxime molecule, which is a derivative of furaldehyde, were

studied by Arivazhagan et al. Vibration spectra of the molecule were examined, HOMO-LUMO and
NBO analyzes were made (8). In our previous study, the structure of the 3-Furaldehyde (3FA) molecule,
which is one of the furan pollutants in the atmosphere, was investigated using matrix isolation
experiments (9). The interest in the furan molecule has increased day by day and theoretical studies on
its derivatives have continued. In our previous study, the structure of the 3-Furaldehyde (3FA) molecule,
which is one of the furan pollutants in the atmosphere, was investigated using matrix isolation
experiments. Photochemical reactions were observed for matrix-isolated 3FA upon irradiation with λ >
234 nm and λ > 200 nm.
In this study, the two conformers of 4M3F (shown in Figure 1) differ by the orientation of the aldehyde
group were studied theoretically by density functional theory (DFT) and Natural bond orbital (NBO)
methods. Low-energy excited states were calculated using the time-dependent DFT (TD-DFT) theory
(TD-DFT).
2. THEORETICAL CALCULATIONS
4M3F calculations were performed using the DFT program in Gaussian 09 (10) and analysis at minimum
energy was performed. All calculations were done using the 6-311++G(d,p) basis set. The three-
parameter hybrid density function, designated B3LYP, includes Becke's gradient change correction (11)
and Lee, Yang, and Parr (12). DFT scans of the potential energy surface (PES) were used to define the
minimum energy geometries of the molecule (trans and cis forms). These scans were carried out by
2022, 1(1), 113-123, DOI: 10.5281/zenodo.7319331
incrementally increasing the dihedral angles (15 degree steps) that determine the rotations of the
aldehyde groups and optimizing (with energy minimization) the values of all other parameters.
NBO analysis was performed using NBO 3.1 by applying the Gaussian 09 program (13). Using the
second-order Fock matrix, trans and cis-4M3F dominant donor-acceptor orbital interactions were
investigated and analyzed.
The TD Schrödinger equation results of low-energy singlet and triplet states were calculated at
B3LYP/6-311++G(d,p) theory level as functions of internal rotation of the aldehyde group of cis and
trans forms (14,15).

The two different conformational energies in the minimum energy state were calculated using B3LYP
level and 6-311++G(d,p) basis set. The geometries of the two conformers found, together with their
adopted atomic numbers, are shown in Figure 1.
Figure 1. Conformers of 4M3F and Adopted Atom Numbering.
Calculations made for both trans and cis conformers were found to have a planar geometry and a Cs
point group. Electronic energy difference (6.19 kJ mol-1 with DE+ZPV) was calculated 6.38 kJ mol-1
between the two conformers obtained due to the rotation of the aldehyde group. With this energy
difference, the trans form is more stable than the cis form. The energy differences are given in Table 1.
As a result of the calculations made about the 3FA molecule in the previous study, the trans form was
found to be more stable than the cis form by 4.4 kJ mol-1. Considering the zero point vibration energy
correction, this value was calculated as 4.03 kJ mol-1 (9). Microwave spectrum study by Marstokk and
Møllendal showed that the trans conformer of 3FA is at least 5 kJ mol-1 more stable than any other
rotameric form of this molecule (16). Lunazzi et al. published that the minor conformer ratio should be
approximately 11% at RT by studying 3FA conformations with dynamic NMR (17).
Table 1. Calculated electronic energies difference (with and without zero-point vibrational energy), Gibbs energy difference
and dipole for trans and cis of 4M3F using B3LYP/6-311++g(d,p) level.
Energy Trans cis
DE (kJ mol-1) 0 6.38

DE(ZPV) (kJ
0 6.19
mol-1)
DG (kJ mol-1) 0 5.94
dipole (debye) 2.52 3.57
By scanning the dihedral angles C−C−C=O (or C−C−O=H) in 15-degree steps, two conformers with the
same energy value in both scans, called trans and cis, were obtained and presented in Figure 2. In the
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figure, barrier energies and reverse energies are given. The calculated energy barrier for 4M3F-trans to
4M3F-cis was calculated as 39.8 kJ mol-1. The reverse process is 33.4 kJ mol-1.
Figure 2. Potential energy profiles calculated by B3LYP/6-311++g(d,p) level for conformational interconversion in 4M3F
(atom numbers are given in Fig. 1).
According to the value taken from the bottom of the potential well, the barrier energy calculated between
the trans and cis form was 33.4 kJ mol-1. (Fig. 2).
Figure 3. Natural atomic charges for trans and cis forms of 4M3F calculated by DFT/B3LYP/6-311++g(d,p) level of theory.
The NBO charges calculated for the two conformers were given in Figure 3. It is seen that the bond with
the highest polarization for both the trans and cis forms of the charges indicated on the Figure 6 is the
C3−H10 bond. For the trans form, the C3 charge is −0.288 e, the H10 charge is +0.408 e, while for the
cis form, the corresponding charges for these atoms are calculated as -0.252 and +0.412 e. For both
conformers, we can note that the C2−H9 bond is non-polarized. In this case, the charges for the trans
form are +0.200 and +0.201 e, respectively, while for the cis form this value is +0.223 and +0.210 e.
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Table 2. Orbitals, occupancy, coefficients, and hybridization for trans form of 4M3F, calculated using B3LYP/6-311++g(d,p)
level.
Occupancy Coeficients (%)a

trans NBO Hybridizationb
Ratio A B
p (C2−C3) 1.79070 45.64 54.36 0.6755p + 0.7373p
p (C4−C5) 1.86963 48.48 51.52 0.69635p + 0.6893p
Donor L2(O1) 1.69387 p
L1(O7) 1.98499 sp0.69
L2(O7) 1.88395 spd2.75
p*(C4−C5) 0.23474 51.52 48.48 0.7178p - 0.6963p
p*(C6=O7) 0.13253 66.94 33.06 0.8182p - 0.5749p
p*(C2−C3) 0.30104 54.36 45.64 p
Acceptor
RY1*(C6) 0.01152 sp4.48
s*(C3−C6) 0.05428 46.78 53.22 0.6840sp1.93 - 0.7295sp1.64
s*(C6−H8) 0.06659 42.82 57.18 sp2.34 - s
a
Percent contribution of each atom.
b
Definition of hybrid orbitals.
The dipole interactions for both conformers were found to be related to the C=O bond with strong
polarization (+0.408 and -0.589 e for trans form, and +0.412 and -0.586 e for cis form, respectively).
Under these explanations, we can say that it is a proof that the bond that affects the lower energy of trans
is the C4−H10 bond.
Table 3. Orbitals, occupancy, coefficients, and hybridization for cis form of 4M3F, calculated using B3LYP/6-311++g(d,p)
level.
Coeficients (%)a
cis NBO Occupancy Ratio Hybridizationb
A B
p (C2−C3) 1.78787 44.26 55.74 0.6653p + 0.7466p
p (C4−C5) 1.87172 44.26 55.74 0.69635p + 0.6893p
Donor L2(O1) 1.69387 p
L1(O7) 1.68785 sp 0.68
L2(O7) 1.88467 p
p*(C4−C5) 0.24962 51.17 48.83 0.7153p - 0.6988p
p*(C6=O7) 0.12315 66.85 33.15 0.8176p - 0.5757p
p*(C2−C3) 0.29488 55.74 44.26 p
Acceptor RY1*(C6) 0.01153 49.63 sp 4.48
s*(C3−C6) 0.05428 46.78 53.22 0.6841sp 1.93 - 0.7294sp1.65
s*(C6−H8) 0.06509 42.82 57.18 sp 2.32 – s
a
Percent contribution of each atom.
b
Definition of hybrid orbitals.
Calculated NBOs with significant orbital interactions are given in Tables 2 and 3 for the trans and cis
forms, respectively. These tables also show the percentage of atomic orbitals on each atom obtained
from the NBO polarization coefficients and 1-center lone pair (LP-nonbonding) NBOs consists of a
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single normalized natural hybrid orbital (NHO). 2-centered NBOs (BD-bonded atoms) consist of
normalized linear combinations and can form p and s bonds. NBOs corresponding to each phase of the
valence hybrids form anti-bonds and indicate with BD* (p* or s*). Valence non-Lewis NBOs are a
series of "Rydberg type" 1-centered NBOs and are identified by the label RY*.
Regarding the occupancy rates in the two conformers, it was found that the occupancy rate of the L2(O7)
atom was highest in trans and cis forms. We have also proved here that there is a strong polarization on
this atom. It was found that the O1 atom of the furan ring has the p character in both conformers.
However, the polarization of the O1−C2 bond is greater in the cis form than in the trans form. In the
O1−C5 bond, the polarization is greater in the trans form. Two hybrid orbitals have strong polarization
that these gives the same result as explained above in natural atomic charges. The orbital interactions
with the highest stabilization energies for both forms are given in Table 4 and plotted in Figure 3. The
table also shows the percentage of bond-forming atomic orbitals in each atom, deduced from the NBO
polarization coefficients for NBO orbitals.
Table 4. Donor and acceptor interactions and stabilization energies for NBO pairs results from calculated by the Fock matrix
equation (Eq.1) for trans and cis forms of 4M3Fa.
Donor Acceptor
E(2) ej- ei Fij
4M3F Pair NBO NBO
kJ mol-1 au au
(i) (j)
A1 p (C2−C3) p*(C4−C5) 16.81 0.31 0.065
B1 p (C2−C3) p*(C6=O7) 22.21 0.30 0.074
C1 p (C4−C5) p*(C2−C3) 14.72 0.29 0.061
D1 L2(O1) p*(C2−C3) 31.22 0.36 0.094
trans
E1 L2(O1) p*(C4−C5) 21.63 0.38 0.082
F1 L1(O7) RY1*(C6) 13.71 1.82 0.141
G1 L2(O7) s*(C3−C6) 17.00 0.73 0.101
H1 L2(O7) s*(C6−H8) 22.92 0.62 0.108
A2 p (C2−C3) p*(C4−C5) 18.09 0.30 0.067
B2 p (C2−C3) p*(C6=O7) 20.70 0.29 0.071
C2 p (C4−C5) p*(C2−C3) 14.21 0.30 0.060
D2 L2(O1) p*(C2−C3) 31.64 0.36 0.096
cis
E2 L2(O1) p*(C4−C5) 22.42 0.37 0.083
F2 L1(O7) RY1*(C6) 13.97 1.80 0.142
G2 L2(O7) s*(C3−C6) 17.28 0.73 0.102
H2 L2(O7) s*(C6−H8) 22.54 0.62 0.107
a
See atom numbering in Figure 1. LP, lone electron pair orbital, Ry, Rydberg orbital.
As can be seen from the G and H pairs in Table 4, these bonds belong to the aldehyde group and form
strong sigma bonds for both trans and cis forms. The calculated total stabilization energy associated
with the main orbital interactions was found to be almost the same for both conformations (160.22 kJ
mol-1 and 160.85 kJ mol-1 for trans and cis forms, respectively). It was found that the most important
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contribution to the stabilization was due to the LP2(O1) → p*(C2−C3) NBO pairs. While this value
was 31.22 kJ mol-1 for the trans form, it was calculated as 31.64 kJ mol-1 for the cis form.
The electron densities between the donor and acceptor orbitals depend on the Lewis and non-Lewis
NBO orbitals. Non-Lewis extra valence Rydberg orbitals are also included in the calculations of the
stabilization energies obtained from the NBO results. The Fock matrix equation given in Eq.1 is used
for calculate stabilization energy, which is obtained from the 2nd order delocalization energies (13).
#
#!"
!(2) = ∆!!" = '! $ (Eq.1)
" %$!
In the eq.1, the term given with Fij represents the matrix elements between the i and j NBO orbitals. The
energies of donors and acceptors are given as !! and !" , respectively, and #! indicates the occupancy rate
of the donor orbital.
A1 B1
C1 D1
E1 F1
G1 H1
Fig. 4. NBOs electron density surfaces for trans of 4M3F calculated at the B3LYP/6-311++G(d,p) level of theory (see Table
2 for dominant interactions). The electron densities iso-values were chosen as 0.02 e. Negative and positive wave functions
are shown with yellow and violet colors. Atom colors; red, O; gray, C; white, H.
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The σ-type NBO interactions (G and H in Table 4), which contribute to the stabilization, are calculated
with energies E(2), a sum of 39.92 kJ mol-1 for the trans form, a sum of 39.82 kJ mol-1 for the cis form,
and they are found to be almost the same value. These interactions correlate with the electronic charge
back-donation from the aldehyde oxygen lone electron pairs (specifically the p-type lone pair; LP2) to
the C3-C6 bond and, in particular, to the C6-H8 aldehyde bond. This well-known back donation effect
has been identified as the most significant effect leading to the observed elongation of the C-H bond
attached to the carbonyl group and its reduced C-H stretching frequency as with aldehydes (18-20).
The same type of NBO interactions were observed in both forms of 4M3F, and the interaction with the
highest energy was given with D1 and D2 pairs in Table 4. These interactions are of the trans and cis
forms, respectively, and include the p-system of the molecule. The contribution of the D1 pair to the
stabilization is the highest, and the total stabilization energy of the trans form (greater than 10% is taken
into account) was calculated as 160.22 kJ mol-1and the cis form as 160.85 kJ mol-1. In this case, the E(2)
energy of the cis is only 0.63 kJ mol-1 higher than trans.
Figure 4 and 5 show the pi orbital interactions in pairs A, B, C, and D. E and F lone electron pairs are
oxygen and furan ring orbital interactions, while G and H pairs are sigma orbital interactions.
A2 B2
C1 D2
E2 F2
G2 H2
Fig.5. NBOs electron density surfaces for cis of 4M3F calculated at the B3LYP/6-311++G(d,p) level of theory (see Table 2
for dominant interactions). The electron densities iso-values were chosen as 0.02 e. Negative and positive wave functions are
shown with yellow and violet colors. Atom colors; red, O; gray, C; white, H.
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In the table 5, the percentage of electron density calculated by NBO method is given. The quality of the
natural Lewis and non-Lewis structure is almost the same in both forms. Lewis and non-Lewis were
calculated 56.93307 and 1.06693 for trans, 56.93715 and 1.06285 for cis forms of 4M3F. The NBO
results also indicated the relatively important role of 170 Rydberg orbitals (NBOs 31-201) to valance
non-Lewis orbitals (6 anti-bonds NBOs between 202-218) in the Lewis structure model for 4M3F.
Table 5. Total Lewis and non-Lewis occupancies (valence, core, and Rydberg shells) for trans and cis forms of 4M3F
(e=1.60217646×10-19 C).
trans cis
Core 15.99392 ( 99.962% of 16) 15.99396 ( 99.962% of 16)
Valence Lewis 40.93915 ( 97.474% of 42) 40.94319 ( 97.484% of 42)
Total Lewis 56.93307 ( 98.160% of 58) 56.93715 ( 98.168% of 58)
Valance non-Lewis 0.96330 ( 1.661% of 58) 0.96103 ( 1.657% of 58)
Rydberg non-Lewis 0.10363 ( 0.179% of 58) 0.10182 ( 0.176% of 58)
Total non-Lewis 1.06693 ( 1.840% of 58) 1.06285 ( 1.832% of 58)
Table 6. Energy of Vertical Absorption (ΔE) and Oscillator Strength (f) of Trans and Cis Conformers of 3FA Calculated for
their Ground State Equilibrium Geometries Using the TD-DFT Method at theB3LYP/6-311++G(d,p) Level.
trans – 4M3F cis – 4M3F

state type E/ eV E/ nm f state type E/ eV E/ nm f
S0 0 S0 0.07
S1 n-p* 3.91 317.24 0.0002 S1 n-p* 3.75 330.61 0.0001
S2 p-p* 4.66 266.19 0.0373 S2 p-p* 4.48 276.89 0.0372
S3 p-p* 5.87 211.32 0.1542 S3 p-p* 5.61 221.02 0.1465
S4 p-p* 5.98 207.25 0.0000 S4 p-p* 5.82 213.18 0.0002
S5 p-p* 5.99 206.89 0.0007 S5 p-p* 6.13 6.1263 0.0005
S6 p-p* 6.05 204.78 0.0089 S6 p-p* 6.19 200.22 0.1060
Table 6 summarizes the six calculated lowest excited singlet states of trans and cis forms of 4M3F
resulting from TD-DFT calculations. It was observed that while the excitation energy was 5.98 eV (l =
207.25 nm) in the S4 state in the trans form, there was no oscillator power. A very low oscillator power
indicates that the S0 → S1 excitation is ineffective. The highest oscillator power is observed in the S3
state in both trans (0.1542) and cis (0.1465) forms of 4M3F. In this case, we can say that S0→S4
excitation can be at the most effective level and changes in the molecular structure can be observed as
a result of the excitation (l >211). The potential energy graph of excited singlet states formed as a result
of aldehyde group rotation is given in figure 6. As can be seen from the graph, the energies of the S2 and
S3 states have increased in parallel with each other. According to the TD-DFT results obtained with the
105o rotation of the aldehyde group, it was found that the S0+S4 and S0+S5 singlet states were at the same
energy. Likewise, S0+S5 and S0+S6 singlet barrier energies were found to be equal to each other as a
result of rotation with an angle of 120o (Fig.6).
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Fig. 6. Potential energy curves of the lowest excited singlets of 4M3F calculated using the theory level B3LYP/6-
311++G(d,p) as a result of rotation of aldehyde group.
While the S1 singlet state exhibits minimum energy at two points (0 and 180o) in trans and cis form, as
in the ground state, the first minimum observed in the S2 singlet state was determined when the aldehyde
group was 90o. In the S3 singlet state, the first minimum was obtained by rotation of the aldehyde group
by 75 degrees, while in the S4, S5 and S6 singlet states the trans form was still in the 0o state of the
aldehyde group when ground state energies are added.
LUMO LUMO
5.24 eV 5.02 eV
HOMO HOMO
Fig. 7. Orbital schemes of HOMO-LUMO energy differences for trans and cis forms.
The electrons of covalently bonded molecules are assumed to reside in molecular orbitals formed by
orbitals of atoms. Each of these orbitals has different steady-state energies. Filled orbitals are donors,
vacant orbitals are acceptors. Shorter HOMO-LUMO gap indicate that the molecule has high reactivity
(color: yellow is a positive value and purple is a negative value). The HOMO tends to donate the
outermost orbital containing electrons, and these electrons act as an electron donor. On the other hand,
LUMO refers to the orbital containing free sites to accept an innermost electron. The HOMO-LUMO
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energy difference was found to be 5.24 and 5.02 eV for trans and cis forms, respectively. The negative
and positive density distributions of the HOMO and LUMO orbitals are given in Figure 7.
Electron density calculated for trans and cis are given with color codes and surface maps of molecular
electrostatic potential (MEP) are shown in Fig. 8. The MEP map shows the Van der Waals surface for
the trans and cis forms, and the approximate maximum distance that electron densities can reach is
calculated on this surface.
Fig. 8. MEP surface for trans and cis forms of 4M3F.
GaussView5 visualization program was used while drawing MEP surfaces of trans and cis conformers.
MEP can be defined as the interaction energy between the unit positive charge and the charge
distribution of the molecular system. Color coding system is used to define MEP. On the MEP map, the
most negative potential (the region where the electron density is higher than the nucleus over the entire
molecule) is shown in red, while blue is used to show the most positive potential (the region of partial
positive charges) (21). These values are +5.065e-2 (max. red region) to -5.065e-2 (max. blue region) for
the transform and +5.196e-2 (max. red region) to -5.196e-2 (max. blue region) for the cis form. The map
showed that for the trans and cis forms, (red region, electrophilic attack) concentrated around the OH
aldehyde group, while the maximum positive electrostatic potential (blue region, nucleophilic attack)
increased around the hydrogen atoms of the furan ring.
4. CONCLUSIONS
The conformers of 4M3F were calculated in the ground electronic state using DFT/B3LYP/6-
311++g(d,p) level of theory. Trans form was more stable than the cis ca. 6.19 kJ mol-1 taking account
zero point vibration energy. The dipole interactions for the trans and cis forms were found to be with
strong polarization of the C=O bond. Orbital interaction energies, electron density surfaces and
hybridizations of 4M3F were determined using B3LYP/6-311++g(d,p) level using NBO method. The
NBO pair that contributed the most to the stabilization energy was found to originate from the LP2(O1)
→ p*(C2−C3) orbital interaction. The quality of the natural Lewis and non-Lewis structure is almost
the same in both forms. The calculated six lowest excited singlet states of the trans and cis forms of
4M3F were obtained from TD-DFT calculations. The HOMO-LUMO energy gap was calculated for
trans and cis forms. From the energy gap, it can be estimated that the mobility of the π electrons of the
trans form is slightly greater than that of the cis form. According to the natural charge distribution on
the atoms and the MEP map, the negative electrostatic potential region was observed around the oxygen
atom attached to the aldehyde, while the positive potential region was observed around the hydrogen
atoms for two conformers.
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ACKNOWLEDGMENT
This work was supported by the Eskisehir Technical University Commission of Research Project under
grant no: 22ADP074.
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ELECTROMAGNETIC ENERGY CONSERVATION BY BIQUATERNIONS
Nur ULUHAN1, Abidin KILIÇ2

1
Physics, Graduate Education Institute, Eskisehir Technical University, Eskisehir, TURKIYE
2
Physics,Department, Eskisehir Technical University, Eskisehir, TURKIYE
ABSTRACT
In this document, after defining biquaternions algebra, Poynting Theorem is derived in this algebra.
Because of 8-component biquaternions containing 3-dimensional vector space and 4-dimensional quaternion
space, we can examine many physical quantities in biquaternion algebra. Based on this information, the
generalized field Maxwell Equations and Gauge Transformations is showed in non-comutative but associative
biquaternion algebra in homogenous media. Then, Noether and Poynting Theorems are introduced in terms of
biquaternionic differential operator equation and used for deriving equations in electromagnetic energy
conservation. In conclusion, it is seen that these biquaternionic equations can be derived from generalized 3-
dimensional vector space in literature before.
Keywords: Quaternions, Biquaternions, Maxwell Equations, Poynting Theorem
INTRODUCTION
With the discovery of quaternions by William Hamilton in 1843, studies on complex numbers
began to increase. Quaternions are a hyper-complex number system for studying 4-dimensional
spacetime. [1] In the years when the quaternion algebra was discovered, British mathematicians such as
A. Carley, K. Clifford and J. J. Slyvester used quaternions as well as physicists such as J. C. Maxwell
and P. G. Tait, who built the electromagnetic theory continued their studies on electromagnetic issues
by using quaternions. [2] Physicists adopted the use of vector and tensor algebra in the early 20th
century. Until the middle of the 20th century, the practical use of quaternions was minimal compared to
other methods. However, this situation has changed rapidly as progress has been made in these areas
with the increasing use of quaternions in robotics, animation and computer technology. [3]
On the other hand biquaternions are the 8-dimensional form of quaternions. Its applications in
physics are also taking place at an increasing rate in recent years. Gürlebeck and Wolfgang applied
biquaternions to special theory of relativity, particle mechanics and electromagnetism and showed that
biquaternions have a wide range of applications. [4]
Poynting's theorem includes an expression of energy density representing the dissipation of

energy for time-varying electric and magnetic fields. It also says that the reduction in energy stored in
the fields due to the work done on the charges by the electromagnetic force, minus the energy flowing
out from the surface. Poynting's theorem is also identified in the literature as the work-energy theorem.
[5]
In this paper, the history and algebra of quaternions and biquaternions are included. Then,
Maxwell's equations, which are also valid for biquaternions, are obtained, and Poynting's theorem is
defined for biquaternions.
QUATERNION ALGEBRA
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A quaternion α is defined as a complex number:
α = !! + !" i + !# j + !$ k (2.1)
formed from 4 different units (1, i, j, k) by means of the real parameters !% (i =0, 1, 2, 3), where i, j, k
are 3-orthogonal unit elements. With ideas from both vector and matrix algebra, the quaternion α may
be viewed as a linear combination of scalar and base element !! and a vector !⃗:
α = !! + !⃗. (2.2)
$⃗ is a purely imaginary number

If !! = 0 is a real number and is called a scalar quaternion; when !⃗ = 0
and is called a vector quaternion. As we can observe, quaternions includes scalars and unit elements,
and they are in the subspace of quaternions.
The conjugate of a quaternion α, denoted by %∗ , is defined by negating its vector part (or
imaginary part); that is
%∗ = !! - !⃗. (2.3)
It is convenient to represent, quaternions and their algebra in matrix form to simplfy equation
manipulations. The matrix (column vector) representation of an arbitrary quaternion α with respect to
the basis (1, i, j, k) is merely the collection of its parameters:
α = [!! , !" , !# , !$ ] ' = [!! , %' ] ' (2.4)
where superscript T indicates the transpose of a matrix.
Since scalars and spatial vectors are in the subspace of quaternions, the rules in scalar and vector
algebra alsa apply to quaternions. Let us consider the following three quaternions:
α = !! + !⃗, β = *! + *$⃗, γ = +! + +⃗.
Addition and subtraction, ±, of two quaternions α and β are defined as
α ± β = (!! + *! ) + (!⃗ ± *$⃗). (2.5)
The quaternion addition and subtraction obey associative and commutative laws.
Quaternion multiplication, designated by ×, is defined as
α × β = (!! + !⃗) × (*! + *$⃗)
= !! × *! + !! × *$⃗ + *! × !⃗ + !⃗ × *$⃗ (2.6)
Where the scalar-scalar and scalar-vector quaternion products are defined, respectively, the same way
as scalars and spatial vectors; thus !! ×× *! = !! *! , !! × *$⃗ = !! *$⃗. The vector-vector quaternion
product is defined as:
!⃗ × *$⃗ = - !⃗ . *$⃗ + !⃗ × *$⃗ (2.7)
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Where the operations “.” and “×” define the dot product and the cross product in the space of unit
elements.
The norm of a quaternion α, denoted by N(α), is a scalar quaternion and is defined as N(α) =
% × α = α × % ∗ = !!# + !"# + !## + !$# .
∗
Unlike unit elements, the set of quaternions form a division algebra, since for each non-zero
quaternion α there is an inverse %(" such that α × %(" = %(" × α = 1. Consider two non-zero quaternions
)∗ ) × )∗
α and β = * ()) Since α × β = = 1, we find the inverse of α to be [6]
* ())
)∗
%(" = * ()) (2.8)
BIQUATERNIONS (COMPLEX QUATERNIONS)
Everything that can be measured in physics must be real. For this reason, real numbers have found
a field of application in every field since the early of science. On the other hand, it is also known that
complex numbers are used in mechanical and electrical applications, especially in circuit analysis.
Unfortunately this number system only adds 2 dimensions to applications. In 3D applications, vectors
are used, but vectors seem to be insufficient in some applications.
Firstly, we can think of real numbers as hyper-complex numbers that are 1-dimensional under any
sum, product or any complex number in 2D. We can treat the real numbers as a subset of the complex
numbers whose imaginary part is zero. Hamilton discovered the new number system, quaternions, by
using complex numbers in 4-dimensional space. In the algebra of quaternions, the combination of two
complex numbers is considered, thus a number system is obtained which is expanded in one real and 3
imaginary dimensions. [7]
Based on this result, he focused on the triple number system. Quaternion subsumes vector and a
real component so we can see that a quaternion has 4-dimension. As in vector space, addition and
multiplication operations can be defined in quaternions, but a different method has been developed for
division. Quaternions is an algebra that can be expressed in different dimensions, which are complex,
divisional and dual. [8]
Biquaternions are complex quaternions, so they have 8-dimensions. [9] We can extend the
applications in Physics such as quantum mechanics, robotics, electromagnetism, etc. by using
Biquaternions.
A - Biquaternion Algebra
A biquaternion Q is defined as a complex number and -/ = !/ + i */ (m = 0, 1, 2, 3) and . #

= -1, so
Q = -! /̂! + -" /̂" + -# /̂# + -$ /̂$ (3.1)
formed from four different units (/̂! , /̂" , /̂# , /̂$ ) by means of the real parameters /̂! = 1 and /̂% (i = 1,
2, 3), where /̂" , /̂# , /̂$ are three orthogonal unit elements and /̂%# = -1. Here the orthogonal units obey
the product of /̂% /̂0 = - δ %0 /̂! + ε%01 /̂1 rule. With ideas from both vector and matrix algebra, the
biquaternion Q may be viewed as a linear combination of a scalar -! and a spatial vector - $⃗ because of
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Q = (!! + i*! ) /̂! + (!" + i*" ) /̂" + (!# + i*# ) /̂# + (!$ + i*$ ) /̂$ = (!! + i*! , !" + i*" , !# + i*# , !$ +
i*$ ) = (!! + i*! , !⃗ + i*$⃗). Thus,
$⃗
Q = -! + - (3.2)
$⃗ = 0
If -! = 0, Q is a purely imaginary number and is called vector biquaternion; when - $⃗, Q is a real
number and is called a scalar biquaternion.
Scalar unit element according to the multiplication in biquaternıon algebra is:
1Q = Q1 = Q (3.3)
Because of /̂! = 1.
For two biquaternions such as P and Q, to be equal, their opposite elements must be equal. If P
and Q are equal biquaternions, then it must be as:
P = 3! /̂! + 3" /̂" + 3# /̂# + 3$ /̂$
Q = -! /̂! + -" /̂" + -# /̂# + -$ /̂$
3! = -! , 3" = -" , 3# = -# , 3$ = -$ (3.4)
The sum or subtraction of two biquaternions is a biquaternion consisting of the sum or

subtraction of the opposite elements of these two biquaternions:
P + Q = (3! ± -! ) /̂! + (3" ± -" ) /̂" + (3# ± -# ) /̂# + (3$ ± -$ ) /̂$ (3.5)
The multiplication of two biquaternions is:
PQ = (3! /̂! + 3" /̂" + 3# /̂# + 3$ /̂$ )( -! /̂! + -" /̂" + -# /̂# + -$ /̂$ )
= 3! /̂! -! /̂! + 3! /̂! -" /̂" + 3! /̂! -# /̂# + 3! /̂! -$ /̂$
+ 3" /̂" -! /̂! + 3" /̂" -" /̂" + 3" /̂" -# /̂# + 3" /̂" -$ /̂$
+ 3# /̂# -! /̂! + 3# /̂# -" /̂" + 3# /̂# -# /̂# + 3# /̂# -$ /̂$
+ 3$ /̂$ -! /̂! + 3$ /̂$ -" /̂" + 3$ /̂$ -# /̂# + 3$ /̂$ -$ /̂$
= 3! -! + 3! -" /̂" + 3! -# /̂# + 3! -$ /̂$
+ 3" -! /̂" + (− 3" -" ) + 3" -# /̂$ + (− 3" -$ /̂# )
+ 3# -! /̂# + (− 3# -" /̂$ ) + ( − 3# -# ) + 3# -$ /̂"
+ 3$ -! /̂$ + 3$ -" /̂# + ( − 3$ -# /̂" ) + ( − 3$ -$ )
= (3! -! − 3" -" − 3# -# − 3$ -$ )
+ (3! -" + 3" -! + 3# -$ − 3$ -# ) /̂"
+ (3! -# − 3" -$ + 3# -! + 3$ -" ) /̂#
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+ (3! -$ + 3" -# − 3# -" + 3$ -! ) /̂$
and this shows us that this equation is also equals to:
$$⃗ · 9
= 3! -! − 7 $$⃗ + 3! 9
$$⃗ + $7
$⃗-! + i7
$$⃗ × 9
$$⃗ (3.6)
Because
PQ = (3! /̂! + 3" /̂" + 3# /̂# + 3$ /̂$ )( -! /̂! + -" /̂" + -# /̂# + -$ /̂$ )
= (3! /̂! -! /̂! + 3! /̂! -" /̂" + 3! /̂! -# /̂# + 3! /̂! -$ /̂$ )
+ (3" /̂" -! /̂! + 3" /̂" -" /̂" + 3" /̂" -# /̂# + 3" /̂" -$ /̂$ )
+ (3# /̂# -! /̂! + 3# /̂# -" /̂" + 3# /̂# -# /̂# + 3# /̂# -$ /̂$ )
+ (3$ /̂$ -! /̂! + 3$ /̂$ -" /̂" + 3$ /̂$ -# /̂# + 3$ /̂$ -$ /̂$ )
= (3! -! + 3! -" /̂" + 3! -# /̂# + 3! -$ /̂$ )
+ (3" -! /̂" - 3" -" + 3" -# - 3" -$ )
+ (3# -! /̂# - 3# -" - 3# -# + 3# -$ )
+ (3$ -! /̂$ + 3$ -" - 3$ -# - 3$ -$ )
= 3! -! - $7
$⃗.9
$$⃗ + 3! $9
$⃗ + 7
$$⃗-! + i $7
$⃗ × 9
$$⃗
We can define conjugate of a biquaternion in two ways. The first one is:
-: = -! /̂! - -" /̂" - -# /̂# - -$ /̂$ = [-! , - 9

$$⃗] (3.7)
If we show the biquaternion Q as:
Q = (!! + i*! ) /̂! + (!" + i*" ) /̂" + (!# + i*# ) /̂# + (!$ + i*$ ) /̂$
so the conjugate of Q is:
-: = (!! + i*! ) /̂! - (!" + i*" ) /̂" - (!# + i*# ) /̂# - (!$ + i*$ ) /̂$ .
The second conjugation of a biquaternion is getting congugating of all complex coefficient of

biquaternion, like:
-∗ = -!∗ /̂! - -"∗ /̂" - -#∗ /̂# - -$∗ /̂$ (3.8)
So all the parts are:
-!∗ = !! - i*!
-"∗ = !" - i*"
-#∗ = !# - i*#
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-$∗ = !$ - i*$
If P and Q are two biquaternions, their multiplication is:
::::) = -3
(3- :::: (3.9)
And their multiplication’s conjugation is:
(3-)∗ = -∗ 3∗ (3.10)
If Q is a biquatenion, its norm is the multiplication of itself and its conjugate, like:
N(Q) = Q-: = -:Q = -!# + -"# + -## + -$# (3.11)
If the norm of a biquaternion Q doesn’t equal to zero, N(Q) ≠ 0, Q can have its inverse, like:
N(Q) = Q-: = -:Q

*(2)
Q= 23
So the inverse of Q is:
23
-(" = *(2) (3.12)
The multiplication of biquaternion and its intervers equal to one.
Q-(" = -(" Q = 1 (3.13)
The division of two biquaternions P and Q means multiplication of P and -(" . However
multiplication of two biquaternions has no interchange speciality, so therte are two kinds of division of
biquaternions [10] :
23
4
-(" 3 = *(2) 3
=; 23
= (3.14)
2
3-(" = 3 *(2)
ELECTROMAGNETIC ENERGY CONSERVATION BY BIQUATERNIONS IN

HOMOGENOUS MEDIA
In physics, magnetic charges are generally referred to as particles with zero electrical charges
and one magnetic pole, so magnetic monopoles can be expressed in accordance with Maxwell's
equations for magnetic charges in an isolated medium for quantized electric charges. In homogenous
media Maxwell equations are:
>. @ = A5
>. B = 0
8⃗
67
> × C = -
6:
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8⃗
6;
> × D = - - $$$⃗
E5
6:
Considering the existence of magnetic monopoles, the symmetrical generalized Maxwell-Dirac

differential equations in space with the SI unit system can be expressed in biquaternions as:
33333
∇.>?∇.>
>. @ = -
#
Here, we accepted c = ħ = 1. Now, we will find >. @ for biquaternions:

6 6 6
∇. D = (6@ /̂" + 6@ /̂# + 6@ /̂$ )(H! /̂! + H" /̂" + H# /̂# + H$ /̂$ )
6;" 6;# 6;$ 6;% 6;" 6;# 6;$ 6;% 6;" 6;# 6;$
= 6@
/̂" - 6@
+ 6@
/̂$ - 6@
/̂# + 6A
/̂# - 6A
/̂$ - 6A
+ 6A
/̂" + 6B
/̂$ + 6B
/̂# - 6B
/̂" -
6;%
6B
6; 6; 6; 6; 6; 6; 6; 6; 6; 6; 6;
::::::
∇. D = - 6@" /̂" - 6@# - 6@$ /̂$ + 6@% /̂# - 6A" /̂# + 6A# /̂$ - 6A$ - 6A% /̂" - 6B" /̂$ - 6B# /̂# + 6B$ /̂" -
6;%
6B
6;# 6; 6;
::::::
∇. D + ∇. D = -2 -2 6A$ -2 6B%
6@
&'# &' &'

(# (# $ (# % 6;# 6; 6;%
&( &) &*
>. @ = - #
= 6@
+ 6A$ + 6B
= A5 (4.1)
And we know
>. B = 0 (4.2)
It is also same for E:

33333
∇.C?∇.C 8⃗
67
>×C =- #%
=- 6:
. (4.3)
8⃗
6;
> × D = - 6:
. - $$$⃗
E5 . (4.4)
Here, A5 is electric charge density, E$$$⃗5 is current density, @ electric induction, C electric field, B is
magnetic induction and D is magnetic field.
Moreover, electric and magnetic fields are in gauge theory:

EF
E = -∇φD - EG
- ∇ × AH (4.5)
" EF+
B = -∇φI - +∇×A (4.6)
J$ EG
Here, φD and φI are electric and magnetic scaler potentials, A and AH are electric and magnetic vector
"
potentials and L = is electromagnetic waves speed. Vector potentials for biquaternions are [11] [12]
√LM
:
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$⃗) = φD /̂! + (A" eN" + A# eN# + A$ eN$ ) L

A = (φD , LA
$$$⃗H ) = LφI /̂! + (AH" eN" + AH # eN# + AH $ eN$ )

AH = (LφI , A
We can show a biquaternion Ψ as:
Ψ = E - i LB = (O" /̂" + O# /̂# + O$ /̂$ ) - i L(P" /̂" + P# /̂# + P$ /̂$ )
EF " EF+
= -∇φD - - ∇ × AH - i L (-∇φI - J$ + ∇ × A)
EG EG
POYNTING TEOREM
In this part of this presentation, we took up Poynting Teorem on electrical current form. In Gauss
or CGS, Maxwell equations are:
>. @ = 4QA5 (5.1)
>. B = 0 (5.2)
8⃗
" 67
> × C = - N 6:
(5.3)
8⃗
" 6; OP
> × D = N - $$$⃗
E5 (5.5)
6: N
If it is accepted that c=1, then these equations become:
>. C = 4QA5 (5.6)
>. B = 0 (5.7)
8⃗
67
> × C = - 6:
(5.8)
8⃗
6;
> × D = 6:
- 4QE$$$⃗5 (5.9)
If there is no electric charge density and current density, we can show them as:
>. C = 0 (5.10)
>. B = 0 (5.11)
8⃗
67
> × C = - 6:
(5.12)
8⃗
6;
> × B = 6:
(5.13)
If we multiply (5.10) and (5.12) by B and (5.11) and (5.13) by E:
$⃗ .( > × C) + O$⃗ . 6Q8⃗ + P

O$⃗ .( > × B) + P $⃗. 678⃗ = 0 (5.14)
6: 6:
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The directions of the electric and magnetic fields vectors perpendicular to each others are also
perpendicular to the direction of the electromagnetic field waves. The direction of electromagnetic
waves has also the direction of energy flux S⃗’s direction.
S⃗ = O$⃗ × P
$⃗ (5.15)
If energy flux S⃗ is also poynting vector and u is electromagnetic energy density:
6R " 6
=# $⃗ ) = "
(O$⃗ + P
6
(O$⃗ . O$⃗ + P
$⃗ . P
$⃗) = >. T (5.16)
6: 6: # 6:
We can show >.( U⃗ × P

$⃗) = P
$⃗.( > × V) + U⃗.( > × B) for two biquaternions so (5.15) and (5.16) are
rearranged:
>. T = >.( O$⃗ × P

$⃗ ) = P
$⃗.( > × C) + O$⃗.( > × B) = 0
6R
= >. T = 0 (5.17)
6:
This equation is named as “energy conservation equation” and also “Poynting Theorem”. [13]
CONCLUSION
In this study the Poynting Theorem and Electromagnetic Conservation are tried to be represented with
biquaternion algebra. It was shown that the biquaternionic expressions are nearly same with vector
algebra. Biquaternion algebra used in this study have extended to complex number system.
Biquaternions are useful and effective mathematical structure for energy conservation.
REFERENCES
1- J. C. K. Chou, “Quaternion Kinematic and Dynamic Differantial Equations”, IEEE Transactions

on Robotics and Automation, Vol. 8, No: 1, February 1992
2- I. K. Hong and C. S. Kim, “Quaternion Electromagnetism and Relation with 2- Spinor Formalism”,
arXiv:1902.09773v2, June 2019
3- J. Funda, P.P. Richard, IEEE Trans. Robot. Autom. 6, 348–356 (1990)
4- K. Gürlebeck, W. Sprössig, “Quaternionic and Clifford Calculus for Physicists and
Engineers”, Wiley, Chichester, 1997
5- https://en.wikipedia.org/wiki/Poynting%27s_theorem
6- J. C. K. Chou, “Quaternion Kinematic and Dynamic Differantial Equations”, IEEE Transactions
on Robotics and Automation, Vol. 8, No: 1, February 1992
7- V. Majernik, Adv. Appl. Clifford Alg. 9, 119 (1999)
8- T. Y. Lam, D. B. Leep, J. Tıgrol, “Biquaternion algebra and quaretic extensions”, Publication
Mathematiquaes De L’I.H.E.S, volume 77, 1993
9- P. R. Girard, P. Clarysse, R. Pujol, R. Goutte, P. Delachartre, “Hyperquaternions: A new Tool for
Physics”, Advances in Applied Clifford Algebeas, June 2018
10- W. R. Hamilton, “Elements of Quaternions Vol I, II, III”, Chelsea, New York, USA, 1899
11- B. Jancewicz, “Multivectors and Clifford Algebra in Electrodynamics”, World Scientific,
Singapore, 1989
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12- K.V. Khmelnytskaya, V. V. Kravchenko, “Biquaternions for analytic and numerical solution of
equations of electrodynamics”, https://arxiv.org/abs/0902.3490
13- A. Waser, “Applications of Bi-Quaternions in Physics”, Researchgate, July 2000
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2022, 1(1), pp. 135-142, DOI: 10.5281/zenodo.7380122
PREPERATION OF MCM-48 LOADED WITH LAVENDER OIL AND VITAMIN E UNDER

SUPERCRITICAL CARBONDIOXIDE CONDITIONS AND ITS USE IN PEEL
FORMULATION
Derya KILIÇ1*, Emine KUTLU1, Muhammad Asım ALİ1, Fatih Mehmet EMEN1, Ruken Esra DEMİRDÖĞEN2
1
Department of Chemistry, Faculty of Arts and Science, Burdur Mehmet Akif Ersoy University, TR 15030, Burdur, Turkey
2
Department of Chemistry, Faculty of Science, Çankırı Karatekin University, TR 18100, Çankırı, Turkey
ABSTRACT
This study aimed to prepare a new peeling formulation in which mesoporous MCM-48 loaded with lavender oil and vitamin E
in a supercritical carbon dioxide (sC-CO2) environment is used as a peeling agent. This study targeted at preparing a new
peeling formulation which consists of a mesoporous MCM-48 onto which an essential oil such as lavender oil was loaded via
a green method that utilized supercritical carbon dioxide (sC-CO2). This study aimed to prepare a new peel formulation
consisting of a mesoporous MCM-48 loaded with lavender oil using supercritical carbon dioxide (sC-CO2). Structural
characterization of MCM-48 and MCM-48-Lavender oil (MCM-48-L) were made via XRD and FT-IR techniques. The XRD
powder diffraction pattern shows the amorphous SiO2 structure at 2q=20o. Their particle sizes and morphologies were
investigated by FE-SEM. The average particle diameter was determined as 590 nm. Pore volumes were determined by
N2 adsorption/desorption analysis. The BET surface area for the prepared MCM-48 was calculated as 2641 m2/g and
the pore diameter of MCM-48 was found to be 3.60 nm. All the results obtained show that MCM-48 loaded with
lavender oil and vitamin e can be used as an exfoliating agent.
Keywords: MCM-48, Lavender oil, Chemoexfoliation, Chemical Peeling, Cosmetics.
1. INTRODUCTION
The technique that involves peeling the skin tissue to reach the desired skin depth using chemicals is called
chemoexfoliation-peeling. The peeling process helps the skin look cleaner and healthier. This technique is used
to evenly remove damaged dermal skin and rejuvenate the skin, as well as minimizing complications such as
scarring and unwanted pigment changes [1]. Chemical peels are among the most commonly used cosmetic
procedures. Controlled destruction of epidermis and dermis occurs by applying chemical agents on the skin. The
skin is induced and exfoliated. Later, dermal and epidermal regeneration observed in the adjacent epithelium and
skin appendages causes the surface texture and appearance of the skin to improve [2]. Lavender essential oils have
been used in cosmetic and medicinal preparations since Greek and Roman times. Studies have mainly focused on
linalool and linalyl acetate, which are found in lavender essential oils, but less common essential oil components
(eg, camphor, 1,8-cineol, carvacrol, etc.) are also considered. Among the lavender species, the most cultivated and
researched species are L. angustifolia Mill., L. latifolia Medik. and L. x intermedia Emeric ex Loisel, L. stoechas
L. and L.luisieri Rozeira [3, 4]. Many cultivars have been produced by standard breeding experiments [3]. By
using metabolic engineering and other techniques, regionally resistant and higher oil yield species are tried to be
produced [3-7]. Vitamin E, which has important antioxidant functions especially in cell membranes and
lipoproteins, is an important fat-soluble antioxidant. It is frequently used in the cosmetic industry because it
nourishes the skin and adds shine. Due to its high antioxidant and protective activity, vitamin E is applied in skin
cream formulations, various photo-aging cosmetics and to improve the skin barrier [8]. In 1992, the researchers of
Mobil Company developed a series of porous materials and named it as the Mobile Composition of Matter (MCM).
MCM-48 (Mobile Compound of Matter No. 48), one of the two most popular mesoporous molecular sieve
structures, still attracts the attention of researchers. Composed of amorphous silica walls, the MCM-48 has a long-
range regular frame with uniform pores. In addition, MCM-48 has a large surface area, which can be more than
1000 m2g-1. Moreover, the pore diameter of these materials can be adjusted from 1.5 to 20 nm in a controlled
manner by adjusting the synthesis conditions. There are many studies in which mesoporous materials are used as
catalysts for various chemical reactions, as a support for a drug delivery system, and as an adsorbent in wastewater
treatment [9]. No peeling formulation was found using MCM-48 loaded with lavender oil.
In this study, it was aimed to prepare MCM-48 loaded with lavender oil as the material of the new peel and use it
in cream peeling. First, MCM-48 was synthesized and its structural characterization was carried out by XRD and
FT-IR techniques. Lavender oil (Lavandula angustifolia) loading into the MCM-48 was carried out in a
supercritical carbon dioxide environment. Their particle sizes and morphologies were investigated by FE-SEM.
Pore volumes were determined by N2 adsorption/desorption analysis.
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2. MATERIAL AND METHOD

FT-IR spectra were recorded in the 4000-400 cm-1 range by Perkin Elmer Fronter FT-IR spectrometer using KBr
pellets. X-ray powder diffraction (XRD) using a Bruker AXSD 8 Advance Powder Diffractometer with CuKα =
1.54 Å radiation was used for structural phase identification of MCM-48. Rigaku SMARTLAB instrument was
used in low angle XRD measurements. Surface morphologies of MCM-48 was examined via a Jeol Sem-7100-
EDX Computer Controlled Digital Scanning Electron Microscope. Nitrogen absorption desorption studies were
performed using the Quantachrome Quadrasorb SI system.
2.1. Synthesis of MCM-48

MCM-48 synthesis was carried out according to the method given in the literature [10]. 30 g of CTAB (surfactant)
was dissolved in 147 mL of water. Then, about 2.72 g of sodium hydroxide was added to the mixture and stirred
for 15 minutes. 30 mL of TEOS was added. The mixture was then stirred for another 3 hours after the temperature
was adjusted to about 40 °C. This mixture poured onto a Teflon reactor and heated at 110 °C for 24 hours. Finally,
the prepared composites were separated by filtration, washed, and calcined at approximately 550 °C for 6 hours to
confirm successful removal of the used CTAB template [10].
2.2. Preparation of the Lavender Oil and Vitamin E Loaded MCM-48

0.5 g of MCM-48 was dissolved in 5 mL of ethanol. 0.5 g lavender oil and 0.5 mL vitamin E were taken into the
scCO2 reaction unit heated to 40 oC. Then it was kept under 200 bar CO2 pressure for 2 hours. The pressure was
reduced by opening the valve of the reaction unit. The lavender oil and vitamin E loaded MCM-48 (MCM-48/L)
nanostructure was removed from the unit in a dry state [11].
2.3. Preperation of cream peeling

Cream peeling was prepared using Ceteareth 20, Lanette O, Olea Europaea Fruit Oil, Caprıylyl methicone, PEG-
12 Dimethycone, PPG-20 crosspolymer, Unilactamin L7, Panthenol, sodium polyacrylate, EDTA,
Phenoxyethanol and lavender oil-vitamin E loaded MCM-48.
2.4. Microbiological Activity Studies

“Total mesophilic aerobic bacteria count” and “Total Yeast-Mold count” analyzes were performed on the peeling
sample. The peeling sample was diluted 1/10 in suspension containing 0.09% NaCl. For total mesophilic aerobic
bacteria count, PCA (Plate Count Agar) and for Yeast-Mold count PDA (Patato Dextrose Agar) agar medium, the
peeling sample, which was diluted with 3 repetitions, was inoculated with 1 ml drop and inoculated in the form of
smear sowing. Incubation was carried out at 35 oC for 48 hours for total mesophilic aerobic bacteria count, and for
72 hours at 25 oC for Yeast-Mold Counting. Colony count was performed after incubation.

3.1. Structural characterization
The structural characterization studies of the MCM-48 were carried out by XRD and low angle XRD dust pattern
measurements (given in the XRD graph), and the powder diffraction patterns are given in Figure 1. The XRD
powder diffraction pattern shows the amorphous SiO2 structure at 2q=20o. The (2 1 1) reflection observed at 3o in
the low angle powder diffraction pattern shows the regular mesoporous MCM-48 structure [10].
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Figure 1. The XRD powder patterns of mesoporous MCM-48
3.2. FT-IR studies

The FT-IR spectra of MCM-48 and MCM-48/L is given in Figure 2. Stretching and bending vibrations of Si-O in
MCM-48 were observed at 1050 cm-1 and 808 cm-1, respectively. Stretching and bending bands of Si-O in MCM-
48/L were observed at 1040 cm-1 and 807 cm-1, respectively. The expected C–H stretching bands of 1480, 2854,
and 2925 cm-1 of CTAB cannot observed in MCM-48 due to removal of surfactants by calcination. The symmetric
and asymmetric aliphatic C-H stretching bands are observed at 2861 cm-1 and 2932 cm-1 in MCM-48/L. This bands
can be attributed to the alkyl groups of lavender oil and vitamin E. FT-IR results show successful loading of
lavender oil and vitamin E into MCM-48.
Figure 2. FT-IR Spectrum of the MCM-48
3.3. SEM-EDX Studies

SEM micrographs of MCM-48 are given in Figure 3 and EDX spectrum is given in Figure 4. For SEM
measurements, MCM-48 powders, which were turned into pallets, were coated with Pt (containing traces of Pd)
and images were taken. It is observed that MCM-48 is obtained in a spherical structure and the particle sizes are
homogeneously distributed. The average particle diameter was determined as 590 nm. Elemental analysis of
MCM-48 was done via EDX. Si and O atoms were detected as 32% in the EDX spectrum.
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Figure 3. SEM images of the MCM-48
Figure 4. EDX spectrum of MCM-48
3.4. Nitrogen Adsorption/Desorption Studies (BET, BJH)

The pore sizes, pore volumes and surface areas of mesoporous materials are determined using the nitrogen
adsorption/desorption technique. According to the IUPAC classification. IV. Type isotherm is associated with
mesoporous materials. MCM-48 nitrogen adsorption (blue) desorption (red) isotherms are given in Figure 5.
Isotherms IUPAC’s IV. It is similar to the type of isotherm. The BET surface area for the prepared MCM-48 was
calculated as 2641 m2/g, which is considerably higher than the 1600 m2/g value given in the literature. In addition,
the pore diameter of MCM-48 was found to be 3.60 nm, in accordance with the literature. These data show that
mesoporous MCM-48 with its extremely high area can be prepared. The symmetry of the adsorption/desorption
graphs is intact in MCM-48. BET surface areas decreased as expected. An increase was observed in pore volumes
and diameters.
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2022, 1(1), pp. 135-142, DOI: 10.5281/zenodo.7380122
Figure 5. Nitrogen adsorption and desorption isotherms of MCM-48.
3.5. Microbiological Activity Studies

Count analysis of Staphylococcus aureus, Escherichia coli and Yeast-Mold microorganisms were performed in
the peeling sample. The Biomeriux TEMPO® instrument was studied at 1/40 dilution by applying instrument
procedures. Microbiological analysis results are given in Table 1. Microbial activity was not observed in the
microbiological analysis which was performed with the “total mesophilic aerobic bacteria count” and “total yeast
mold count”.
Table 1. Microbiological Analysis Results

Analysis Kit used Result
Staphylococcus aureus TEMPO® STA < 10 COB/g
Escherichia coli TEMPO® EC < 10 COB/g
Yeast-Mold TEMPO® YM < 10 COB/g
3.6. Applied of the peeling to the skin

The peeling sample was applied to the hands of two different people, and even in the first application, a visible
improvement and brightness was achieved on the skin (Figure 6).
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2022, 1(1), pp. 135-142, DOI: 10.5281/zenodo.7380122
Figure 6. Applied of the peeling to the skin.
4. CONCLUSION
In this study prepared a new peeling formulation which consists of a mesoporous MCM-48 loaded with lavender
oil and vitamin via supercritical carbon dioxide (sC-CO2). Structural characterization of MCM-48 was done by
XRD and FT-IR techniques and structural characterization of MCM-48/L nanocomposite was done by FT-IR
spectroscopy. The bands observed at 2861 cm-1 and 2932 cm-1 are aliphatic C-H bands, indicating successful
loading of lavender oil and vitamin E into MCM-48. The XRD powder diffraction pattern shows the amorphous
SiO2 structure at 2q=20o. The (2 1 1) reflection observed at 3o in the low angle powder diffraction pattern shows
the regular mesoporous MCM-48 structure. The pore diameter of MCM-48 was found to be 3.60 nm, in accordance
with the literature. PCA (Plate Count Agar) for total mesophilic aerobic bacteria count and PDA (Patato Dextrose
Agar) methods were used for Yeast-Mold count in the peeling sample. Microbial activity was not observed in the
microbiological analysis which was performed with the “total mesophilic aerobic bacteria count” and “total yeast
mold count”. Microbiological analysis results show that there is no reproduction and that the product can be used
safely. All the results obtained show that MCM-48 loaded with lavender oil and vitamin e can be used as an
exfoliating agent. Thus, lavender oil and vitamin e will be released slowly, and while the shelf life of the product
will increase, it will not lose its effectiveness.
REFERENCES
[1] Soleymani T. Lanoue J. Rahman Z. A practical approach to chemical peels: A review of fundamentals and
stepby-step algorithmic protocol for treatment. Journal of Clinical and Aesthetic Dermatology. 2018;11(8). pp.
21-28.
[2] Castillo D. E. Keri J. E. Chemical peels in the treatment of acne: patient selection and perspectives. Clinical,
cosmetic and investigational dermatology. 2018. 11. pp. 365.
[3] Lis-Balchin, M. (Ed.). Lavender: the genus Lavandula. CRC press. 2002.
[4] Upson T. Andrews S. The genus Lavandula. (1st ed.). Timber Press. USA. 2004.
[5] Mendoza-Poudereux I. Muñoz-Bertomeu J. Navarro A. Arrillaga I. Segura J. Enhanced levels of S-linalool by

metabolic engineering of theterpenoid pathway in spike lavender leaves. Metabolic Engineering. 2014;(23).
pp. 136–144.
[6] Muñoz-Bertomeu J. Arrillaga I. Ros R. Segura J. Up-regulation of 1-deoxy-D-xylulose-5-phosphate synthase

enhances production of essential oils in transgenic spike lavender. Plant Physiology. 2006. 142. pp. 890–900.
140
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[7] Muñoz-Bertomeu J. Sales E. Ros R. Arrillaga I. Segura J. Up-regulation of an N-terminal truncated 3-hydroxy-
3-methylglutaryl CoA reductase enhances production of essential oils and sterols in transgenic Lavandula
latifolia. Plant Biotechnology Journal. 2007. 5. pp. 746–775.
[8] Eiras F. Amaral M.H. Silva R. Martins E. Lobo J.S. Silva A. C. Characterization and biocompatibility
evaluation of cutaneous formulations containing lipid nanoparticles. International Journal of Pharmaceutics.
2017.519(1-2). pp. 373-380.
[9] Beck J. S. Vartuli J. C. Roth W. J. Leonowicz M. E. Kresge C. T. Schmitt, K. D. Schlenker, J. A new family
of mesoporous molecular sieves prepared with liquid crystal templates. Journal of the American Chemical
Society. 1992. 114(27). pp. 10834-10843.
[10] Yu. Q. Zhuang. R. Yi. H. Gao. W. Zhang. Y. Tang. X. Application of MCM-48 with large specific surface
area for VOCs elimination: synthesis and hydrophobic functionalization for highly efficient adsorption.
Environmental Science and Pollution Research. 2022. 29(22). pp. 33595-33608.
[11] Demirdogen. R. E. Emen. F. M. Karaçolak. A. I. Kılıç. D. Kutlu. E. Meral. O. Preparation of novel CaMoO4:
Eu3+-MCM-41 nanocomposites and their applications and monitoring as drug release systems. Journal of Drug
Delivery Science and Technology. 2021. 66. pp. 102792.
[12] Everett D. H. Manual of symbols and terminology for physicochemical quantities and units, appendix II:
Definitions, terminology and symbols in colloid and surface chemistry. Pure and Applied Chemistry. 1972.
31(4). pp. 577-638.
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2022, 1(1), pp. 143-150, DOI: 10.5281/zenodo.7384181
SYNTHESIS OF PYRIDINE DERIVATIVE POLYMERIC COPPER COMPLEX WITH

METAL-AZID BONDS
Fatih Mehmet EMEN*1, Ruken Esra DEMİRDÖĞEN2

1
Department of Chemistry, Faculty of Arts and Science, Burdur Mehmet Akif Ersoy University, TR 15030,
Burdur, Turkey
2
Department of Chemistry, Faculty of Science, Çankırı Karatekin University, TR 18100, Çankırı, Turkey
ABSTRACT
In this study, pyridine-derived polymeric copper (II) complexes containing metal azide bonds were prepared. The
characterization of the complexes given with the general formula, [Cu(L)2(N3)2Cl2]n (L1: 3,5-dimethyl pyridine, L2: 3,4-
dimethyl pyridine, L3: 2-amino-3-methyl pyridine, L4: 2,6-diamino pyridine) was performed by FT-IR, AAS and magnetic
susceptibility analyzes. The intense peak observed at 2045-2167 cm-1 in the spectra corresponds to the asymmetric azide
vibrations, υas(N3-), which indicates that polymeric copper complexes are formed over azide bonds. Cu2+ amounts in the
complexes were found in the range of 26.25%-33.61% from the AAS results. The thermal properties of polymeric copper
complexes were investigated with the TG/DTA combined system. Unpaired electron numbers for copper complexes were found
in the range of 0.89-1.45. Copper complexes are paramagnetic, and the number of unpaired electrons being different from the
expected (n=1) value indicates that the geometry of the complex is distorted.
Keywords: Polymeric metal complexes, pyridine complexes, azide compounds.
1. INTRODUCTION
Metal coordination polymers (CPs) and their complexes are of interest to researchers due to their
interesting structural properties. CPs are also defined as hybrid materials with metal ion-based, organic
binders that bind vertices into 1D, 2D or 3D periodic configurations [1]. These materials have many
properties such as luminescence [2] magnetism [3], nonlinear optics [4] and electrical conductivity [5].
Metal azide complexes have been used extensively recently for the development of new coordination
polymers. Because azido ligand (N3-) is linear coordination linker. However, some forms of bi-cognate
coordination are also possible [6]. Some of these can form porous metal-organic chains that can adsorb
small molecules [7]. However, the chemical reactivity of a metal complex with a monodentate azido
ligand was also studied. Such azido metal complexes give a [3 + 2] cycloaddition reaction with organic
nitriles, isocyanides, isothiocyanides and alkynes and form complexes with a tetrazole or triazole-
containing ligand [8]. Some other interesting reactivities of azido metal complexes have been reported
in the literature [9]. On the other hand, the azide ion N3- can link two metal centers with end-to-end
(EO) or end-to-end (EE) ends, yielding binuclear or multinuclear complexes [10]. Multinuclear metal
azide complexes can be formed by the azide ligand binding two or more metal centers [11]. This
versatility of azide ligands explains the spectral and magnetic properties of metal azido complexes and
the diversity of their stereochemistry [10]. Recently, polymeric 1D cobalt(II) polymeric complexes of
pyridine derivative ligands containing a single azide bond have been synthesized and their structures
elucidated [12]. In addition, [Cu(py)3(N3)](PF6) polymeric complex containing three pyridine molecules
was prepared. In addition, [Cu(4-ethylpyridine)(N3)2]2 polymeric complex was prepared and its structure
was elucidated by spectroscopic, magnetic and crystallographic methods [13]. Azido metal complexes
are thermally and photochemically reactive and can form some reactive intermediates [14]. Basolo et al.
found that photolysis of the [Ir(NH3)5(N3)]2+ complex yielded N2 with the higher reactivity
[Ir(NH3)5(NH)]3+ intermediate [15]. Higher reactivity nitrido complexes can be obtained by photolysis
of azido complexes with tetradentate or five-dentate chelating ligands and azido complexes [16]. In
addition, photolysis of the [Cp*Ir(PR3)(N3)2] (Cp*=nu5-pentamethylcyclopentadienyl) complex results
in the reductive cleavage of the azido ligand, resulting in the coordination-rich intermediate Cp*Ir(PR3).
The versatile behavior of the azido groups and the tendency of the cross-plane copper(II) complexes to
coordinate two additional ligands at the apical position result in the formation of solid-state network
structure. Whereas, most copper(II) compounds containing azido ligands in µ1,1-, and µ1,3- bridge
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2022, 1(1), pp. 143-150, DOI: 10.5281/zenodo.7384181
modes have been frequently studied [17], examples of metal ions bound with azido groups in other
coordination modes are scarce [18].
Bu çalışmada, metal azid bağı içeren piridin türevli polimerik bakır (II) kompleksleri hazırlandı.
[Cu(L)2(N3)2Cl2]n (L1: 3,5-dimetil piridin, L2: 3,4-dimetil piridin, L3: 2-amino-3-metil piridin, L4: 2,6-
diamino piridin) genel formülü ile verilen komplekslerin karakterizasyonu FT-IR, AAS ve manyetik
susseptibilite analizleriyle gerçekleştirildi. In addition, the thermal properties of the synthesized
polymeric copper complexes were investigated with the TG/DTA combined system.
2. MATERIAL AND METHOD

The chemicals used for the synthesis were purchased commercially and used without further
purification. 3,5-dimethyl pyridine, 3,4-dimethyl pyridine, 2-amino-3-methyl pyridine, 2,6-diamino
pyridine, CuCl2.2H2O and NaN3 were obtained from Sigma-Aldrich.
FT-IR (PerkinElmer FRONTIER Model FT-IR (Mid-Far) Spectrometer) was used to elucidate
the structures of the synthesized compounds. In addition, the magnetic properties of the complexes were
carried out using Gouy balance, and thermal analysis studies were carried out using the Shimadzu TG-
60 model combined DAT/TG system.
2.1. Synthesis of polymeric copper(II) complexes
Compounds were synthesized according to the method described in the literature [41]. 0.01 mol of
CuCl2.2H2O was dissolved in 20 mL of ethyl alcohol and then a solution of NaN3 (0.02 mol) in 3 mL
of water was added and heated in a magnetic stirrer for 30 minutes. To this solution, pyridine derivatives
(3,5-dimethyl pyridine, 3,4-dimethyl pyridine, 2-amino-3-methyl pyridine, 2,6-diamino pyridine) (0.02
mol) were added and reacted for 1.5 hours under reflux. . The precipitate formed was filtered and dried
in an oven. The general formula of the synthesized complexes is given in Figure 1.
Cl Cl
M N N N M L
Cl Cl
n
Figure 1. General formula of pyridine-derived polymeric copper (II) complexes containing metal azide bonds

3.1. FT-IR studies
FT-IR spectrophotometer was used for structural characterization studies and important IR peaks are
given in Table 1. Severe peak asymmetric azide vibrations observed at 2045-2167 cm-1 in the spectra,
υas(N3-). The IR peaks observed at 1600-1657 cm-1 correspond to the vibrations of the C-N bond,
υ(C=N). The peak observed at 455-483 cm-1 belongs to copper-nitrogen stretching vibrations (Cu-N),
while 619-688 peaks belong to Cu-Cl vibrations. FT-IR results show that the proposed polymeric
complex structures are formed.
Tablo 1. The selected important FT-IR peaks
Bileşik uas(N3-) (cm-1) u(C=N) u(M-N) u(M-Cl)

(cm-1)
(cm-1) (cm-1)
[Cu(L1)2(N3)2Cl2]n 2081 1601 463 660, 688
[Cu(L2)2(N3)2Cl2]n 2047 1615 463 665, 680
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2022, 1(1), pp. 143-150, DOI: 10.5281/zenodo.7384181
[Cu(L3)2(N3)2Cl2]n 2046 1607 455 655, 683
[Cu(L4)2(N3)2Cl2]n 2059 1616 456 -
3.2. Atomic Absorption (AAS) Studies

Atomic absorption method was used for the determination of metal amounts in complex compounds and
the results are given in Table 2. As a result of the AAS studies of the complex compounds, the metal
amounts and % compositions in the compounds were calculated. Metal amounts were found in the range
of 26.25%-33.61%.
Tablo 2. AAS results
Complexes Cu2+ Amount (g) Cu2+ Amount (%)
[Cu(L1)2(N3)2Cl2]n 7,71.10-3 g Cu2+ 31.74
[Cu(L2)2(N3)2Cl2]n 8,394.10-3 g Cu2+ 26.25
[Cu(L3)2(N3)2Cl2]n 9,052.10-3 g Cu2+ 28.91
[Cu(L4)2(N3)2Cl2]n 0,01042 g Cu2+ 33.61
3.3. Magnetic Susceptibility Studies

Magnetic susceptibility measurements are used to elucidate the structure of coordination compounds,
and to determine the stereochemistry of the metal atom, the bond type, and the oxidation step. Magnetic
susceptibility measurements of the synthesized polymeric complexes were made, µ (B.M.) values and
unpaired electron numbers (n) were calculated. Unpaired electron numbers for copper complexes were
found in the range of 0.89-1.45. Copper complexes are paramagnetic, and the number of unpaired
electrons being different from the expected (n=1) value indicates that the geometry of the complex is
distorted. In addition, the deviation from the expected value also proves the existence of polymeric
complexes. The µ (B.M.) values and unpaired electron numbers (n) of the synthesized polymeric
complexes are given in Table 3.
Tablo 3. Magnetic susceptibility results
Complexes µ (B.M.) n
[Cu(L1)2(N3)2Cl2]n 2.0533 1.28
[Cu(L2)2(N3)2Cl2]n 2.0764 1.30
[Cu(L3)2(N3)2Cl2]n 2.2387 1.45
[Cu(L4)2(N3)2Cl2]n 1.5969 0.89
3.4. Thermal Analysis Studies

Thermal analysis studies of the synthesized polymeric copper complex were carried out at a temperature
range of 25-1000 oC and under nitrogen atmosphere. The heating rate was set as 10 oC/minute and the
amount of substance in the range of 5-10 mg was studied. 10 mg of α-Al2O3 was used as reference
material. It has been observed that complex compounds are stable up to about 200 °C and above this
temperature they decompose very rapidly with great mass loss. The DTA peak positions of the
decomposition reactions, the temperature ranges in which the decomposition is observed, the
experimental mass losses and the leaving groups are given in Table.4.
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2022, 1(1), pp. 143-150, DOI: 10.5281/zenodo.7384181
Tablo 4. DTA peak positions, decomposition temperature ranges, experimental mass losses, and leaving groups
Experimental
Decomposition DTA TG temperature mass loss/%
Complexes Leaving groups
step Peak/oC range/oC
I 212 100-221 84.52 Azide
[Cu(L1)2(N3)2Cl2]n 3,5-
II - 221-492 10.209
dimethylpyridine
Residue - 492-1000 - -
I 220 100-226 52.61 Azide
II - 226-326 8.50 3,4-

[Cu(L2)2(N3)2Cl2]n dimethylpyridine
III - 326-1000 31.25
Residue - 1000 7.64 Polymeric CuCl2
I 154 50-172 94.19 Azide
[Cu(L3)2(N3)2Cl2]n 5.81 2-amino-3-methyl

II - 172-556
pyridine
Residue - 556-1000 - -
I 180 32-211 9.19 H2O
II 369 211-455 44.89 Azide
[Cu(L4)2(N3)2Cl2]n III - 455-620 18.67 2,6-diamino

pyridine
IV - 620-1000 11.56
Residue - 1000 15.69 Polymeric CuCl2
The TG/DTA curves of the [Cu(L1)2(N3)2Cl2]n complex are given in Figure 2. It was determined from
the TG curve that the compound decomposed in two steps. The mass loss of the first step is 84.52%. In
this step, azide and 3,5-dimethylpyridine ligands are separated from the complex compound and pass
into the gas phase. The remaining product is estimated as CuCl2. CuCl2 salt begins to sublime at
temperatures above 350 oC [19].
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2022, 1(1), pp. 143-150, DOI: 10.5281/zenodo.7384181
TGA DTA
% uV
100.00 Start 0.57x10

min
0 50.00
34.75x10
C
0
End 18.74x10
min
0
222.18 x10
C
0
Weight Loss -3.916x10

mg
0
-84.524 0%
x10
0.00
Start 19.15x10
min
0 Start 19.15x10
min
0
50.00 226.11 x10

C
0 226.11 x10
C
0
End 45.88x10
min
0 End 97.45x10
min
0
493.02 x10
C
0 992.02 x10
C
0

mg
0 Weight Loss -0.864x10
mg
0
-10.209 0%
x10 -18.649 x10
%
0
-50.00
0.00
0.00 200.00 400.00 600.00 800.00 1000.00

Temp [C]
Figure 2. TG/DTA curves of [Cu(L1)2(N3)2Cl2]n complex
The TG/DTA curves of the [Cu(L2)2(N3)2Cl2]n complex are given in Figure 3. It has been determined
from the TG curve that the compound decomposes in three steps. The mass loss of the first step is
52.61%, the mass loss observed in the second decomposition step is 8.5% and the third step is 31.25%.
The % mass of the product remaining as a result of the decomposition reactions was determined as 7.64.
In the first three steps, azide ligands and 3,4-dimethylpyridine ligands are separated from the complex
and pass into the gas phase. It is speculated that the remaining product may be CuCl2, which may be
polymerized in itself with chloride ligands.
TGA DTA
% uV
100.00
Start 0.31x10
min
0
33.17x10
C
0
End 18.58x10
min
0
Start 18.77x10
min
0
80.00 223.65 0C
x10
225.60 0C
x10
mg
0
Start 29.38x10
min
0
End 29.03x10
min
0
100.00
-52.615 0%
x10 331.37 x10
C
0
327.94 0C
x10
mg
0 End 97.17x10
min
0
60.00
-8.499x10
%
0 991.91 x10
C
0

mg
0
-31.251 x10
%
0
40.00
0.00
20.00
0.00 200.00 400.00 600.00 800.00 1000.00

Temp [C]
The TG/DTA curves of the [Cu(L3)2(N3)2Cl2]n complex are given in Figure 4. It was determined from
the TG curve that the compound decomposed in two steps. The mass loss of the first step is 94.19%. In
this step, azide and 2-amino-3-methyl pyridine are leaved from the complex and turn into the gas phase.
The remaining product is estimated as CuCl2.
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2022, 1(1), pp. 143-150, DOI: 10.5281/zenodo.7384181
TGA DTA
% uV
100.00 Start 0.37x10
min
0
38.18x10
C
0
50.00
End 12.88x10
min
0
173.37 x10
C
0

mg
0
-94.192 0%
x10
Start 13.21x10
min
0
176.79 x10
C
0 0.00
50.00
End 96.01x10
min
0
987.98 0C
x10
mg
0
-7.757x10
%
0
-50.00
0.00
0.00 200.00 400.00 600.00 800.00 1000.00

Temp [C]
The TG/DTA curves of the [Cu(L4)2(N3)2Cl2]n complex are given in Figure 5. The complex decomposed
in four steps. It is understood that the complex compound is hygroscopic and gives the moisture and
crystal water in its body with a mass loss of 9.19% at temperatures between 32-211 oC. The second
decomposition step takes place between 211-455 oC with a mass loss of 44.89%. Mass losses in the third
and fourth steps were found to be 18.67% and 11.56%, respectively. In the decomposition steps, azide
and 2,6-diamino pyridine are leaved from the complex as the gas phase. The remaining product is
estimated to be polymeric CuCl2 (15.69% by mass).
TGA DTA
% uV
100.00
50.00
Start 40.13x10
min
0
80.00
437.66 0C
x10
End 58.80x10
min
0
620.25 x10
C
0
60.00 Weight Loss -1.400x10

mg
0
Start 0.46x10
min
0
Start 59.15x10
min
0
0.00
32.72x10
C
0 -20.655x10
%
0
623.69 x10
C
0
End 39.97x10
min
0
End 97.83x10
min
0
436.19 x10
C
0 997.22 x10
C
0
40.00 Weight Loss -3.529x10

mg
0
mg
0
-52.066 0%
x10 -11.405 0%
x10
-50.00
20.00
0.00 200.00 400.00 600.00 800.00 1000.00

Temp [C]
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2022, 1(1), pp. 143-150, DOI: 10.5281/zenodo.7384181
4. CONCLUSION
In present study, pyridine-derived polymeric copper (II) complexes containing metal azide bonds were
prepared and characterized via FT-IR, AAS and magnetic susceptibility techniques. FT-IR spectra of
[Cu(L)2(N3)2Cl2]n (L1: 3,5-dimethyl pyridine, L2: 3,4-dimethyl pyridine, L3: 2-amino-3-methyl
pyridine, L4: 2,6-diamino pyridine) complexes showed intense peaks observed at 2045-2167 cm-1
attributed to the asymmetric azide vibrations, υas (N3-), which indicates that polymeric copper complexes
are formed over azide bonds. Copper complexes are paramagnetic, and the number of unpaired electrons
being different from the expected (n=1) value Unpaired electron numbers for copper complexes were
found in the range of 0.89-1.45 which were different from the expected (n=1) value. These indicate that
the complexes geometry is distorted tetrahdral. The findings obtained in this study indicate that
polynuclear polymeric pyridine-derived copper chloride complexes can be obtained via azide bonds.
These complexes may have magnetism, nonlinear optics and electrical conductivity properties and have
the potential to be used in these fields.
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structural characterization of two new copper (II) azido complexes: catena-[μ (N3) Cu (pyridine) 3] n (PF6) n and
dimeric [Cu (4-ethylpyridine)(N3) 2] 2. Polyhedron. 2001. 20(24-25). pp. 2971-2977.
[14] Šima, J. Photochemistry of azide-moiety containing inorganic compounds. Coordination chemistry reviews.
2006. 250(17-18). pp. 2325-2334.
[15] Gafney, H. D., Reed, J. L., Basolo, F. Photochemical reaction of the azidopentaammineiridium (III) ion.
Coordinated nitrene intermediate. Journal of the American Chemical Society. 1973. 95(24). pp. 7998-8005.
[16] Du Bois, J., Tomooka, C. S., Hong, J., Carreira, E. M. Nitridomanganese (V) complexes: Design, preparation,
and use as nitrogen atom-transfer reagents. Accounts of Chemical Research. 1997. 30(9). pp. 364-372.
[17] Mukherjee, P. S., Maji, T. K., Escuer, A., Vicente, R., Ribas, J., Rosair, G., Mautner, F.A., Chaudhuri, N. R.
Three Novel End‐to‐End Single Azido‐Bridged Ferromagnetic Copper (II) Chains: Synthesis, Crystal Structure,
and Magnetic Behavior. European Journal of Inorganic Chemistry. 2002. 4. pp. 943-949.
[18] Zhang, L., Tang, L. F., Wang, Z. H., Du, M., Julve, M., Lloret, F., Wang, J. T. Ferromagnetic coupling in a
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[19] Wehrmeier, A., Lenoir, D., Sidhu, S. S., Taylor, P. H., Rubey, W. A., Kettrup, A., Dellinger, B. Role of copper
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DEVELOPMENT OF AN ECO-FRIENDLY EFFICIENT RECOVERY METHOD

FOR NICKEL CATALYST FROM INDUSTRIAL WASTES
Ruken Esra DEMİRDÖĞEN*1, Fatih Mehmet EMEN2

1
Department of Chemistry, Faculty of Science, Çankırı Karatekin University, Çankırı, Türkiye
2
Department of Chemistry, Faculty of Arts and Science, Burdur Mehmet Akif Ersoy University, Burdur, Türkiye
ABSTRACT
Developing efficient, eco-friendly and cost-effective secondary production or recycling processes have gained much
importance. Thus, in this study the two alternative recovery methods -the wet and the dry method for recovery of nickel
catalysts- are evaluated and a new economic and ecological wet method for recovering nickel catalyst from the waste obtained
from hydrogenation processes is developed. The method entailed a two-step extraction followed by electrolysis. The nickel
obtained in the metallic form via electrolysis of the solution under a current density of 1.5A and 4V with an efficiency of 95
%. Among the seven different alternatives employed for recovery the method which employed CCl4 in the presence of surface
active agent and entailed repetitive extraction and electrolysis. The economic analysis of the systems used was performed via
the quantitative-conceptual-hypothetical economic analysis model which was developed by improving "Life-Cycle Cost
Method" and the "Net Present Value Method". The method, which entailed a two-step extraction and electrolysis of nickel ions,
was determined to be the most economical one. Since the demand for heat and thus energy is lesser while the reagents employed
are by-products of different industries and nickel is obtained in the metallic form the method developed in this study is cost-
effective and environmentally benign.
Keywords Nickel, catalyst, recovery, life-cycle cost method, net present value method
1. INTRODUCTION
The reason we really appreciate the sunset may be the same reason introverts look so natural. That's the beauty of
Social, economic, and industrial development require and acquire production of products with better quality in
greater amounts with the least impact on ecology and economy. Moreover, increasing concern regarding
environment and energy brought about the necessity for making optimization among the factors of production -
cost, labor, energy and material- and the environmental criteria. This brings about the necessity of efficient
resource management and employment of eco-friendly production techniques. In this respect, the requirement of
employing catalysts, among which nickel has a unique place, appears as a prerequisite. However, obtaining
catalysts via primary production means is much costly. In this respect, better performance of production techniques
depends increasingly more on employment of wise materials, the "catalysts". Catalysts, which are employed in a
wide variety of industries (i.e. plastic, pharmaceutical food, chemical and petro-chemical, agricultural) as well as
in environmental correction (i.e., catalytic converters for cleaning up auto exhaust on automobiles) (Fornlan, J.C.,
1996), for obtaining aromatic free diesel fuels and solvents [1] and in catalytic oil refinery processes (i.e., for high-
octane non-leaded, oxygenated or reformulated gasoline). Catalysts are the key members in the hydrogenation
process of unsaturated hydrocarbons, as well as in dehydrogenation, desulfurization, dichlorination processes.
They provide great advantages; such as:
• Maintenance and improvement of the quality of life and infrastructure,
• Allowing the institutions of society- including business- to deliver sustainable solutions,
• Improvement of living environments due to more efficient use of fuels and production of energy producing
sources with higher quality and calorific value, such as fuel cells, which employ hydrogen power obtained from
various sources, such as industrial wastes, vegetable oils, etc.,
• Lowered environmental impact due to reduced consumption of environmental resources and reduced emissions
due to higher efficiencies,
• Lowered operating and unit life-cycle costs,
• Lowered taxes,
• Retained value at the end of product life,
• Lowered food costs,
• Lowered contamination of food and drinks.
Nevertheless, the cost of the catalyst may surpass the advantages that they would provide if they are obtained via
primary production means. On the other hand, heterogeneous catalyst recovery technology has provided millions
of dollars of worth of cost saving with reduced environmental risk for over many years. Although small portions
of-catalysts are used in reactions, the losses are very significant over time as most plants are of very high volume
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facilities. Moreover, the cost and the investment required for disposal are very high. Preventing pollution in its
real place and taking environmental precautions at the stage of investment are both cost-effective and cause the
social masses to possess a positive response toward the environment. Moreover, since catalysts are wise materials,
which are not used up in reactions, their recovery from the industrial wastes would be beneficent with respect to
resource recovery, environmental and economic concerns. Nickel (Ni), which is one of the most preferred catalysts
due to the distinct advantages it offers such as providing
• a cost-efficient means of producing energy from renewable sources. This in tum provides sustainable energy
back-up. For instance, the Raney-Ni catalyst, which is a Ni-Al alloy containing 90% Ni by weight, can generate
hydrogen energy from common plant sources (i.e., olive oil, sugar water obtained from a glucose-rich organic
material from ground-up plant matter) by converting their by-products to CO2, gas and H2, gas. Thus, Ni catalyst
can be efficiently used in fuel cells for production of hydrogen power, which has the highest energy content per
unit mass- 120.7 KJ/g [2].
• energy savings - with its ability to accelerate a reaction even though it cannot start the reaction. This is especially
important in the case of hydrogenation of fats and oils for to obtain margarine -a heterogeneous mixture consisting
of water and/ or milk phase and lipid phase- when the reaction is so imperceptivity slow in the absence of the
catalyst. Thus, the catalyst, which is preferably Ni, is considered as an essential element of the reaction system.
Although there are other methods for saturating the double carbon bonds of the fatty acids of oils to yield fats,
shortening, cover grease and frying oil, which have higher melting points and which are either partly or totally
solid from oils and contain molecules with low boiling points (i.e., interesterification and fractioning),
hydrogenation is the choice of preference [3].
In hydrogenation process, a well refined oil, which is dry and free of free fatty acids, is treated with H2(gas) and
the catalyst in the solid phase. The process involves reacting a carbon-carbon double bond in the vegetable oil with
hydrogen in the presence of a Ni catalyst. In the process after oil is mixed with the catalyst in the reactor, some of
it is taken to the autoclave, where it is heated under constant stirring. When the temperature reaches 120°C, H2(gas)
is delivered into the reaction chamber until the desired solid form is obtained. Followingly, the mixture is filtered
after it is cooled to temperatures below 100°C. In the filtered oil, about 10 mg/kg catalyst can be present in the
dissolved or dispersed form. After the last bleaching this quantity may be decreased to 0.1 mg/kg. This process
can be performed both via batch and continuous techniques. After the process, remains no space on the surface of
the Ni for new reactant molecules to go through the whole process again. However, after regeneration the catalyst,
which remains in the filter presses, can be used again. On the other hand, reusage for many times may decrease
the selectivity and cause longer filtration periods. The type and concentration of the catalyst employed affects the
quality of the hydrogenation process [4]. Since the catalyst -the crucial element in hydrogenation- should be active,
selective, easily removed via filtration, in the isomer form and have long-life. Thus, mostly Ni, which has excellent
separation and transportation properties, is used as the catalyst. In each hydrogenation process, for 1 kg oil, 87 g
or 9% of Ni catalyst is poisoned. However, as this situation is not practical, the catalysts, which are used in common
processes, should consist of porous particles with high surface area. Thus, the surface area of a catalyst is about
50-100 m2 and the quantity of Ni poisoned for 1 tone of oil could be decreased to about 0.2 kg. However, when
the continuity of the process is considered it is a fact that the spent catalyst arises as a problem.
Disadvantages of spent catalyst, which is classified as hazardous waste, caused the spent catalyst to be a problem
and a liability. The Duty of Care, Basel Convention, Trans frontier Shipment of Waste Regulations, and Hazardous
Shipment Rules now mean that most of the edible oil processor is not an easy one. It has become essential to ensure
that such material is properly looked after from cradle to the grave, and the selection of a service provider and
recycler is now working with long-term commitments being built into their future financial projections. The spent
catalyst is hazardous both for the process plant and for the environment. Precautions should be taken against any
possible fire in the plant as nickel oxidizes rapidly and may spontaneously ignite causing a fat fire. Hence, recovery
of the spent catalyst from the waste is dictated by economic and ecologic concerns.
Nickel catalyst can be recovered via two alternative methods: the dry and the wet methods.
A) The Dry Method consists of four stages.
Stage 1. Ni is recovered from the used catalyst after it is deactivated. Deactivation involves adding 15% NaN03(aq)
to the used catalyst.
Stage 2. After agitating and heating the mixture at 40-50°C, it is left for more than an hour. Then it is rinsed with
water.
Stage 3. The used catalyst mixture is ignited three times.
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Step 1. The mixture is ignited at 800°C for 12 hours in a gas shuttle kiln, to remove water and organic matter in
the used catalyst.
Step 2. The catalyst is then roughly ground and ignited at 1000°C.
Step 3. The catalyst is ignited at 1200-1300°C.
Stage 4. The used catalyst is finely pulverized and recovered as nickel oxide.
The dry method has the following advantages.
• The process is safe in operation because the used catalyst is deactivated.
• It produces less waste, since it is disposed off in the dry method.
• Gas emissions are deodorized and made harmless by completely Oeming via a secondary combustion facility.
• Since complete oxidation occurs during a repeated direct oxidation process and pulverization is made, when
compared to the conventional methods of nickel oxide production, the process is both simple and low-cost.
• This process allowed reactivation of nickel oxide.
• The nickel oxide obtained can be used for pigments in the ceramic industry, colored glass, and materials for
ferrite.
Benefit-Cost Analysis
In the benefit-cost (BC) analysis, all of the consequences of the investment are converted to economical terms. For
an investment to be acceptable, the ratio of the benefits to the costs should be greater than 1, since BC(i) = I, is the
minimum usefulness expected from the project.
BC (i) =(All the benefits that the project creates)/(All the costs that the project causes)
As a result of the analysis, the economic advantages that dry method offer are summarized in Table 1.
Table 1. Economic Benefits of the Dry Method
Before (Yens/kg Ni) After (Yens/kg Ni)

Cost 700 600
Value 650 1350
Benefit -50 750
Table 1, indicates that the dry method is not as cost efficient as wet method. Therefore, we developed an efficient
method for wet recovery of Ni catalyst from the industrial wastes of solid fat industry.
B) Wet Method can be performed both with and without removing the oil. In both of the leaching processes HNO3
[5] and H2SO4 are the most preferred leaching agents [6]. Oil can be removed via an organic solvent (i.e., benzene
and/or petroleum ether) and then Ni is extracted by aqueous solution of HNO3 or H2SO4. The extraction process
is usually performed together with application of heat. Followingly, Ni is recovered via DC galvanostatic method
or by roasting the metal just in the same way as accomplished in the dry method. In general, this method, which
recovers 85-95% of the Ni from the waste, consists of seven stages.
Stages I. Purification of the contaminated catalyst by consumption.
Stage II. Leaching and filling the purified waste catalysts with acids (e.g., HCl).
Stage III. Addition of NH4OH to the filtrate for to precipitate Mg compounds to yield MgO by-product. Stage IV.
Removal of NH3 from the filtrate by heating.
Stage V. Addition of Na2CO3 to the precipitated nickel compounds at pH 9.5-10.
Stage VI. Decomposition of the precipitated nickel compounds at 600°C to yield nickel oxide.
Stage VII. Recovery of metallic Ni via reduction of nickel oxide with hydrogen at 600°C. In Figure 1, a three stage
counter current extraction, which is accomplished by 3N HNO3, for recovery of Ni is presented. The composition
of the spent Ni catalyst is
Moisture : 1.5
Oil : 48.5
Ash : 50
I. Acid insoluble Ash : 35.0
II. Nickel : 10.5
III. Other impurities (by difference) : 3.1
Each stage is accomplished at 100°C for 1 hour. Each batch comprises treatment of the spent catalyst, which
contains 10.5% Ni, with 3.0N HNO3. The process provides an economical use of solvent and reduces the
requirement of alkali neutralization step.
2. MATERİAL AND METHODS

2.1. Materials and Reagents
Waste Ni catalyst was obtained from various factories in Middle Anatolia and in the Aegean Regions of Turkey.
NH3, HNO3, HCl, dimethyl glyoxime (DMG), ethanol and tartaric acid, which were obtained from Merck, were
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technical grade. (NH4)2SO4 was obtained from fertiliser industry. Aqua regia -HNO3/HCl (1:3, v/v) -, 1.0 %
DMG solution in ethanol, 10% tartaric acid solutions and 1000 mg.L-1 stock nickel solution were prepared freshly.
Nickel and steel electrodes were used as the cathode and as the anode spiral Pt and PbO2 plated Pb electrodes,
which were prepared via electrolysis of 1.0 M (NH4)2SO4 via Pb electrodes at a current density of 1.0-1.5 A and
under 3.5-4.0 V for 30 min. were used.
2.2. Experimental
The waste catalyst was separated from its oil fraction and then was mixed with a mixture of phoxylate-1-nonyl
phenol and Triton X-100 mixture and then the pH of the solution was adjusted to 10-10.5 via NH3 and (NH4)2SO4.
Extraction was performed under constant stirring and heating at 50°C for 2h. The Ni content of the solution was
determined via AAS measurement. The efficiency of extraction in the first step was found to be 32%. Followingly
the solution was taken into another reaction vessel, where its pH is again adjusted to 10.0-10.5, and (NH4)2SO4
was added into solution in the solid form. Then extraction was performed at room temperature for 4h. After
extraction the concentration of nickel ions in the solution was determined and the efficiency of extraction was
found to be 80%.
2.2.1. Removal of Oil

The waste catalyst was extracted with CCl4 in a Soxhlet extractor the residue was dissolved in HCl at a ratio of
(1:4, v/v) upon heating. Followingly, the mixture was filtered and the filterate was diluted to 500 ml with water.
While in the filtrates the following analysis were made, in the residue the oil content of the waste catalyst was
investigated.
2.2.2. Qualitative Analysis of Waste Containing the Catalyst

In the filtrate 1-5 cation analysis was performed. Si, Al, Fe and Mg were found in the waste.
2.2.3. Quantitative Analysis of Constituents of Waste Containing the Nickel Catalyst

The metal ion content as well as oil, moisture, ash and acid insoluble ash content of the waste was determined.
2.2.4. Nickel Analysis in Waste Containing Catalyst

Nickel was determined both by gravimetric and Flame Atomic Absorption Spectroscopy (F-AAS) analysis. In
gravimetric analysis. 100 ml aliquots, which were taken from the diluted filterates, were reacted with 25 ml 10%
tartaric acid. For to prevent the possible interferences from Fe3+ and Al3+ in the basic solution, the pH of the
solutions were adjusted to 8 by 2 mol.L-1 NH3 at 80-90°C (Tredwell, H., 1955). Ni was precepted from the
medium, which contained NH3, by DMG. The precipitate was filtered and dried at 130°C until constant (cst.)
weight was reached. It was found that the waste contained 11% Ni by weight. Nickel was also analyzed by using
atomic absorption spectrometer equipped with flame atomizer (F-AAS analysis). The conditions were:
Wavelength: 352.4 nm; slit width: 0.2 nm; lamp intensity: 5 mA; flame: air-acetylene; typical sensitivity: 0.34
ppm. The results indicated that 100 g waste contained 10.9 g nickel.
2.2.5. Si, AI, Fe and Mg Analysis in Waste Catalyst

In quantitative determination of Si, Al, Fe and Mg, the matrix effect was investigated. Thus, standard samples, the
composition of which were similar to the industrial waste, were used. 50 mg of sample and standard materials
were heated at 1000°C. Followingly, 1:1 HCl was added while heating was continued. Then, they were washed
with water into volumetric flasks and their final concentration was made to be 1000 mg.L-1. The results given in
Table 2 are expressed as percentages since the composition of the standard sample was presented in percentages.
Table 2. Amount and composition of metal fraction of the waste

Compound % Element %
SiO2 22.8 Si 10.7
Al2O3 4.20 Al 1.11
MgO 0.50 Mg 0.30
Fe2O3 0.52 Fe 0.36
2.2.6 Determination of the Oil Content of the Waste Containing the Catalyst
After extraction the residue was dried until it attained constant weight. The oil content was calculated from the
loss in the weight of the residue before and after drying.
2.2.7. Determination of the Mositure, Ash and Acid Insoluble Fraction of the Ash
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The mositure content was determined via heating samples of waste catalyst at 110°C for 3 hour intervals until they
attained constant weight.
The ash content was determined via heating samples of waste catalyst at 1000°C in porcelain crucibles for 4 hour
intervals until they attained constant weight.
The acid insoluble part of the ash was determined. After the ash obtained in the above step was dissolved in aqua
regia it was filtered. The filtrate was heated until constant weight was attained.
2.2.8. Leaching Nickel from the Waste Containing the Catalyst

Spent Ni catalyst was reacted with (NH4)2SO4. The pH of the solution was made to be 10-10.5 with NH3. The
mixture was heated and kept at constant temperature and stirring, until nickel hexamine complex was formed.
Since the complex is blue in color, its formation could be visually determined. Followingly, the mixture was
filtered, and the filtrate was analyzed for its Ni content. The effect of concentration of (NH4)2SO4 and NH3,
treatment period, temperature and amount of waste catalyst on efficiency of extraction was investigated. 2.0 mol.L-
1 (NH4)2SO4 solution was employed as the extractant. Recovery studies were performed at pH=10.0-10.5 and the
extraction period was 2h.
2.2.9. Recovery of Nickel via Electrolysis

After leaching of the nickel catalyst from 100 g waste in at 50oC and when pH was 9.5-10.0 the solution was
electrolyzed by using PbO2 plated lead electrode or spiral platinum electrode as the anode and the steel or the Ni
electrode as the cathode as depicted in Figure 1.
Figure 1. The scheme for elecgtrolytic recovery of nickel after leaching.
2.3. Recovery of Nickel via Electrolysis
After leaching of the nickel catalyst from 100 g waste in at 50oC and when pH was 9.5-10.0 the solution was
electrolysed by using PbO2 plated lead electrode or spiral platinum electrode as the anode and the steel or the Ni
electrode as the cathode, the following reactions were observed on the cathode and on the anode, respectively.
Anode : 2H2O → O2 + 4H+ + 4 e- E0(H+/H2) = 0 V
Cathode : Ni(NH3)62+ + 2e →- 6 NH3 + Ni(s) E0(Ni+2/Ni) = -0.25 V
2.3.1. The Process Accomplished via Successive Extraction and Electrolysis
50g waste containing the catalyst was reacted with 2.0 mol.L-1 (NH4)2SO4 and the pH of the medium was
adjusted to 10.0-10.5 with NH3. Extraction was carried on for 2h at 50°C, after which the concentration of the Ni
ions in the solution was determined via AAS. Followingly, under 1.5A and 4V, the solution was electrolyzed for
5h by using PbO2 plated Pb electrode as the anode and steel electrode as the cathode. After electrolysis the Ni
content of the solution was determined via AAS measurements. In the second step, this solution was poured onto
the sludge and the same procedure was repeated. The schematic presentation of the process is given in Figure 2.
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Figure 2. Flow-scheme of recovery process of waste catalyst via successive extraction and electrolysis steps.
2.3.2. Extraction of Nickel from Waste Containing the Catalyst via a Two-Step Process
First step: After adjusting the pH of the medium to 10.0-10.5 with NH3, waste catalyst was reacted with 2.0 mol.L-
1 (NH4)2SO4 at 50°C for 2h.
Second step: The solution phase obtained in the first step was separated and reacted with (NH4)2SO4 and the pH
of the solution was adjusted to 10.0-10.5 with NH3. Followingly, the solution was electrolyzed for 6 h under 1.5A.
After the electrolysis, the concentration of nickel ions in the solution was determined via AAS. After electrolysis
the solution was added onto a fresh portion of waste catalyst and the same procedure was repeated. Extraction was
made at 50°C for 24h. In Figure 3, the flow scheme of the process is presented.
Figure 3. Two step extraction of nickel from waste catalyst.
2.4. Extraction of Nickel from Waste Containing the Catalyst After Removing Oil Content
The spent nickel catalyst is recovered after the oil fraction of the waste contain the catalyst was removed via
extraction with CCl4 in a soxhelet extractor. After removing the catalyst from the oil fraction, the pH of the
medium was adjusted to 10.0-10.5 with NH3, and the medium was reacted with (NH4)2SO4 at 50°C for 24h. Then
the solution was electrolyzed via spiral Pt and Ni electrodes under 1.5A for 8h. During electrolysis Ni concentration
was constantly determined via F-AAS analysis.
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2.5. Investigation of the Effect of Leaching Agent on the Efficiency of Extraction

Two different leaching processes were used for removing oil fraction: Saponification, which was performed by
using sodium hydroxide solution as extractant, and extraction via carbontetrachloride. In the other leaching
process, carbon tetrachloride was used as the extractant. The procedure is demonstrated in Figure 4.
Figure 4. The flow-scheme of the extraction processes in the presence and absence of CCl4
For separating the aqueous phase with ease the pH of the waste catalyst was made to be 10.0-10.5 with NH3 prior
to reaction with 1.5 mol.L-1 (NH4)2SO4. The procedure employed is demonstrated in Figure 5. The efficiency of
the first extraction was found by determining the amount of Ni left in the solution via AAS. Then the solution was
electrolyzed under 1.5A and 5V for 5h. Following this, the solution, which also contained CCl4, was added to the
same mixture. The pH of the medium was made 10.0-10.5 with NH3. Extraction was performed for 8h.
Figure 5. Flow-Scheme for repetitive extraction via CCl4.
2.6. Investigation of the Effect of Surface Active Agent and Extraction Period on the Efficiency of Extraction
Phoxylate-1-nonyl phenol and Triton X-100 mixture was employed as the surface active agent. After the pH of
the waste mixture was adjusted to 10.0-10.5 via NH3, (NH4)2SO4 was added and extraction was performed at
50°C in the presence of surface active agent.
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2.7. Continuous Process for Recovery of Nickel in the Presence of Surface Active Agent
The continuous process consisted of two steps. In the first step, which lasted for 4 h, waste catalyst was extracted
in the presence of surface active agent, at 50oC and pH 10.0-10.5. The pH was adjusted via NH3/(NH4)2SO4. In
the second step the leaching was performed at pH 9.5-10.0, 50oC for 4 h. After the electrolysis, which was
performed by using Pt and Ni electrodes at 1.5 A and 4 V for 2 h, the nickel catalyst was recover in the metallic
form. The process is depicted in Figure 6.
Figure 6. Flow-scheme of the extraction and electrolysis made in presence of surface active reagent mixture.
2.8. Step-Wise Method for Recovery of Nickel in the Presence of Surface Active Reagent
A two-step process was employed for extraction of nickel from the waste catalyst.
First Step: Waste catalyst was mixed with surface active agent. Then, the pH of the mixture was adjusted to 10.0-
10.5 with NH3. The mixture was extracted with 2.0 mol.L-1 (NH4)2SO4 at 50°C for 2h.
Second Step: The solution obtained in the first step was decanted and separated from the residue. Then, the pH of
the solution was adjusted to 10-10.5 via NH3 and (NH4)2SO4 was added to the solution. Extraction was continued
for 4h. The concentration of Ni in the solution was determined at certain time intervals. In Figure 7, the flow-
scheme of the two-step extraction in the presence of surface active agents is presented.
Figure 7. Two-step extraction of nickel from the waste catalyst in the presence of surface active agents.
2.9. USING THE LIFE-CYCLE COST (LCC) MODEL

The LCC Model depends on the basis of several types of analyses and decision making: Design Evaluations 1.
Evaluation of Engineering change requests 2. Sensitive analysis and risk assessment 3. Logistic support Analysis
4. Pareto and ABC Analysis 5. Budget and cash flow Analysis
By using a relationship for estimating cost, the effect of alternative decisions regarding LCC of the system can be
analyzed. This can be used as a basis for evaluating the alternatives and making a selection, resource acquisition
and management.
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2.9.1. Economic Analysis of the Recovery Methods for the Nickel Catalyst
The "LCC Method" and the "Net Present Value (NPV) Method", were employed for the economic analysis of the
systems used in the present investigation. In this work, a quantitative-conceptual-hypothetical economic analysis
model was developed by improving the above mentioned methods. This model is a mathematical model, which
takes all the alternatives for recovering Ni catalyst from the waste into consideration. The mentioned model
considers the first investment costs, the renewal or replacement costs, when necessary, and all the management
costs, which may arise during life-cycle and the salvage cost, the environmental cost at the end of each alternative
for recovering Ni catalyst. In other words, this model contains all costs, which may arise throughout the life-cycle
of every recovery system, and among the alternatives, the one with the least cost, is preferred as the most economic
one.
2.9.2. The Properties of the Model

The LCC concept is entirely a cost analysis consisting of all the costs spent during the whole life-time of the below
mentioned alternatives. All alternatives are compared with each other with respect to the unit cost of catalyst as
explained elsewhere [7].
2.9.3. Determination of the Alternatives

In this economic analysis method seven different alternatives were employed. The Ni catalyst is recovered from
industrial waste material.
Alternative 1: After removing the oil part and by employing (NH4)2SO4 for leaching via successive extraction
and electrolysis.
Alternative 2 : Without removing the oil part and by employing (NH4)2SO4 for leaching via successive extraction
and electrolysis .
Alternative 3 : By wet method, which entailed employment of (NH4)2SO4 for leaching via successive extraction
and electrolysis .
Alternative 4 : By wet method, which entailed employment of (NH4)2SO4 for leaching via a two-step process.
Alternative 5 : By wet method, which entailed employment of CCl4 in the presence of surface active agent in two
steps.
Alternative 6 : By wet method, which entailed employment of CCl4 in the presence of surface active agent and
entailed repetitive extraction and electrolysis.
Alternative 7 : By wet method, which entailed employment of CCl4 in the absence of surface active agent and
entailed repetitive extraction and electrolysis.
2.9.4. Assumptions and Mathematical Structure of the Model

1. The alternatives for recovery are considered with respect to their lifetimes.
2. The increase in material prices in the scenarios a and b, which are given below, are taken from the 20-years
trend curves for the steps of two-year-mean values. The 20-year trend curves were calculated according to the data
regarding the catalyst prices or inflation rates of the last 20-years, which are published by Turkish Chamber of
Commerce, Istanbul.
The scenarios are:
a) Scenario 1: The material price increase rates are taken from the 20-years trend curve.
b) Scenario 2: The material price increase rates are taken equal to the inflation rates.
1. When the life times are completed the renewal or replacement costs were considered according to the increase
of credit interest rates in both scenarios.
2. In both scenarios, the NPC's were calculated using the credit interest rates, beginning with an initial value of
76% being the mean of the latest 20 year and by adding I% for each period of two years.
3. The salvage values were taken into consideration

In the quantitative analysis of the constituents of waste containing the nickel catalyst Si, Al, Fe and Mg analysis
was performed. The results, which are expressed as percentages, since the composition of the standard sample was
presented in percentages, are presented in Table 1.
Table 1. Amount and composition of metal fraction of the waste

Compound % Element %
SiO2 22.8 Si 10.7
Al2O3 4.20 Al 1.11
MgO 0.50 Mg 0.30
Fe2O3 0.52 Fe 0.36
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2022, 1(1), pp. 151-165, DOI: 10.5281/zenodo.7384225
The oil content was found to constitute 54.4% of the total mass of the waste containing the catalyst. The moisture
content was found to be 0.89%. The ash content was found to be 47.05%. The acid insoluble part of the ash was
determined. After the obtained ash was dissolved in aqua regia it was filtered and the filtrate was heated until
constant weight was attained. The weight loss on roasting was 52.06%. The composition of the waste containing
the Ni catalyst is presented in Table 2.
Table 2. Composition of the spent nickel catalyst

Content %
Fat (from loss on roasting) 0.90
Ash 52.1
Acid insoluble ash 47.0
SiO2 22.8
NiO 12.2
Al2O3 4.20
Fe2O3 0.50
MgO 0.50
Total 40.2
The spent catalyst –nickel- was leached from the waste. The complex was blue in color and thus its formation
could be visually determined. The following parameters were determined to be critical for the success of the
reaction and the analysis. The effect of concentration of (NH4)2SO4 on efficiency of recovery was examined and
the results are presented in Figure 8.
Figure 8. Effect of concentration of (NH4)2SO4 on efficiency of recovery.
Maximum recovery efficiency, which was 55%, was achieved when the concentration of (NH4)2SO4 was 2.0
mol.L-1. The Effect of Concentration of NH3 and extraction time on the efficiency of recovery was examined and
the results are presented in Table 3.
Table 3. Effect of NH3 concentration and extraction time on efficiency of recovery.

C(NH3) (mol.L-1) Efficiency of Recovery (%)
After 2 h After 4 h After 24 h
1.0 13.0 16.0 13.8
2.0 17.0 21.7 23.5
3.0 28.2 36.1 44.0
4.0 29.9 40.5 59.0
5.0 30.3 50.0 60.5
6.0 34.9 53.0 64.1
Maximum recovery efficiency, which was 64.1%, was achieved when the concentration of NH3 was 6.0 mol.L-1.
However, since the pH of the solution did not remain constant throughout the extraction period, regular pH
measurements were made. In Table 5, the variation in pH of the solutions, to which the indicated concentrations
of NH3 were added initially, with respect to time is presented in Table 4.
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2022, 1(1), pp. 151-165, DOI: 10.5281/zenodo.7384225
TabIe 4. Investigation of change in pH with respect to concentration of ammonia and time

C(NH3) pH
(mol.L-1) 0 min. 30 min. 60 min. 120 min. 240 min. 480 min. 41400 min.
1.0 9.51 9.34 9.30 9.21 9.16 9.15 9.20
2.0 9.90 9.64 9.55 9.50 9.44 9.43 9.44
3.0 10.1 9.90 9.74 9.67 9.62 9.60 9.57
4.0 10.3 9.04 10.0 9.83 9.80 9.78 9.77
5.0 10.4 10.0 9.91 9.83 9.81 9.80 9.74
6.0 10.5 10.2 10.1 10.0 9.97 9.91 9.88
Effect of temperature on leaching and thus the on effiency of recovery is presented in Figure 9.
Figure 9. Effect of temperature on efficiency of recovery.
Maximum recovery efficiency, which was 30%, was achieved when the temperature was 500C.
Effect of Amount of Waste and the pH of the medium and the amount of waste catalyst employed on the efficiency
of Extraction, which is a measure of the success of recovery is presented in Table 5.
Table 5. Investigation of effect of extraction time and amount of catalyst on efficiency of recovery.
Amount of waste Efficiency of Recovery (%)
catalyst (grams) After 1 h After 3 h After 7 h After 23 h
25 32.1 40.1 41.2 61.4
50 23.1 34.0 43.1 59.0
100 19.0 35.0 36.3 55.9
When nickel was extracted from 50 g of waste catalyst the highest recovery efficiency, which was 59.0%, was
achieved after 23 h.
After extraction of the spent catalyst from the waste the extract was electrolysed and the effect of electrolysis
period on the efficiency of recovery is presented in Figure 10.
161
2022, 1(1), pp. 151-165, DOI: 10.5281/zenodo.7384225
Figure 10. The effect of electrolysis period on amount of nickel recovered.
The process was accomplished via successive extraction and electrolysis. The amount of Ni in the solution after
successive extraction and electrolysis was calculated to be 1.26g, which corresponds to an efficiency of recovery
of 26.5%. The amount of Ni left in the solution after the electrolysis was found to be 0.37g. This corresponds to
an efficiency of 70%. After the first extraction, 1.25 g Ni could be recovered. Thus, it was found that 18.3% of the
Ni was transferred to the second step. After the second electrolysis, 56.3% of the Ni in solution could be recovered.
Then the same procedure was carried on for a third time. The efficiency was found to be 0.09%. The spent catalyst
in the waste was extracted from the waste via a two steps process and then the solution was electrolyzed. The
efficiency of recovery was calculated to be 33.8%.
The spent nickel was extracted from waste after the oil content was removed via CCl4 extraction and then was
treated with (NH4)2SO4 at 50°C for 24h. The Ni content of the solution was determined via AAS. The effect of
extraction period on the efficiency of recovery as presented in Figure 11.
Figure 11. Effect of extraction time on the efficiency of recovery.
The efficiency of the extraction in recovery of nickel after removal of the oil fraction of the waste containg the
catalyst via extraction with CCl4 was found to be 70.4%. After electrolysis the efficiency was calculated to be
95%. The effect of electrolysis period on efficiency of recovery is demonstrated in Figure 12.
162
2022, 1(1), pp. 151-165, DOI: 10.5281/zenodo.7384225
Figure 12. Effect of electrolysis period on the amount of nickel recovered.
The effect of surface active agent and extraction period on the efficiency of extraction was investigated. The
surface active agent -the phoxylate-1-nonyl phenol and Triton X-100 mixture- was employed and the effect of
extraction time on efficiency is presented in Figure 13.
Figure 13. Effect of extraction time on the efficiency of extaction in the presence of surface active agent.
The efficiency of recovery in the step-wise method used for recovery of nickel in the presence of surface active
reagents after the first and second steps with respect to effect of extraction period are presented in Figures 14 and
15.
Figure 14. Effect of extraction period on efficiency of extraction for the first step.
163
2022, 1(1), pp. 151-165, DOI: 10.5281/zenodo.7384225
Figure 15. Effect of extraction period on efficiency of recovery.
The economic analysis of the recovery methods for the nickel catalyst, which was performed via the mathematical
structure of the model is described elsewhere (Demirdogen, R.E., et al., 2005), employed seven different
alternatives. The operation, the initial investment, the environmental and the replacement cost for each alternative
was compared. The alternative with the least cost was chosen to be the best alternative. The results are presented
in Table 6. Alternative VI, was preferred over others.
Table 6. Economic analysis results of the seven alternatives under investigation.
The Best Alternative The Better Alternative The Good Alternative

Alternative 6 : employment of Alternative 5 : employment of CCl4 Alternative 7 : employment of CCl4
CCl4 in the presence of surface in the presence of surface active in the absence of surface active
active agents with repetitive agents in two steps. agents with repetitive extraction
extraction and elctrolysis. and electrolysis.
3. CONCLUSION
1) Recovering Ni catalyst via efficient and cost effective methods is of great importance since it is consumed in
great amounts. The yearly nickel consumption of Turkey only through margarine is about 19.800 kg, which would
mean that the yearly burden only by this industry on the economy is about 158.000 USD.
2) When production methods are to be developed the fact that production from the primary sources is neither
ecological nor economical as these sources are depleting, should always be kept in mind. Moreover, the
governments and the waste management policies dictate that waste recovery is of great importance. Only the
wastes, which do not offer any opportunity for recovery, are to be disposed of, while the rest should be evaluated.
3) The recovery of Ni from waste catalyst can be performed by leaching out nickel via employment of (NH4)2SO4
and NH3 as extractant and pH adjustor, respectively. These reagents are by-products of various industries.
However, the efficiency of the newly developed method is about 80 %. This may be due to accumulation of nickel
as nickel oxides rather than as metallic Ni, while the latter remains in the solid phase. Although the efficiency may
seem to be lower than that obtained in the dry method, since the demand for heat and thus energy is Jess and the
reagents employed are by-products of other industries, the newly developed version of the wet method is both eco-
and cost-efficient.
Acknowledgements
The authors would like to thank to Ass. Prof. Dr. Huseyin Yıldıran, to Prof. Dr. Berrin Yenigül, to MSc. Deniz
Arslan Kalender for their support.
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[2] Haryanto, A., Fernando, S., Murali, N., Adhikari, S. Current status of hydrogen production techniques by
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NaSTech

Volume:1 Sayı: 1 December 2022

Volume 1 Number 1 December 2022

Journal of Natural Sciences and Technologies is a peer reviewed journal published.

Duplicate submission and redundant publication

Fabrication and falsification

Authorship and acknowledgements

Conflicts include the following:

Editors and Reviewers

Corrections and retractions

Volume: 1 / Number: 1 / December - 2022

3D PRINTED PAVING STONES: A LAB-SCALE RESEARCH 1

NUMERICAL AND EXPERIMENTAL INVESTIGATION ON THE REPAIR IMPACT OF ARROW-SHAPED AND 24

APPLYING OF THE NEW GENERATION PLASTIC ADDITIVES TO THE KITCHEN APPLIANCES: 56

FLEXIBLE PRINTED STRUCTURES QUALITY MODELS FOR MOBILE ROBOT PLATFORM 57

ROBOT GROUP INTERACTION TECHNOLOGY USING A CLOUD SERVER 85

COMPARISON OF ENERGY EFFICIENCY STUDIES OF TURKEY AND GERMANY 100

3D PRINTED PAVING STONES: A LAB-SCALE RESEARCH

Volkan ARSLAN1,*, Zekeriya DOĞAN2

Keywords: 3D printer, construction technology, construction industry

3. MATERIALS AND METHOD

2.1. 3D Printer Mechanical Part

2.1.1. Software and calibration

2.1. Concrete Mixture Design

4. RESULTS AND DISCUSSION

4.1 3D Printed Paving Stones

4.2 Performance Tests

[1] Ghanbari-Ghazijahani T, Kasebahadi M, Hassanli R, Classen M. 3D printed honeycomb cellular

AN INVESTIGATION OF MOLECULAR SPECTROSCOPY WITH GEOMETRIC

Baghdad Abdulhameed Abdullah AL-BADANI1,*, Abidin KILIÇ2

Department of physics, Faculty of Science, Eskişehir Technical University, Eskişehir, Turkey

!(# + %) = !# + !% Distributive property

!(# + %) = (# + %) Commutative property

!(#%) = #(!%) = %(!#) Combination property

! + 0 = !, !⋅1=! Identity property

! + (−!) = 0, ! ⋅ 1! = 1 Inverse property

Where !, # and % are arbitrary numbers.

The expression of geometric algebra,

Figure 1. Express the Bivectors

1.1. Relations and Geometric Transformations

The e,- exponential, commonly known as a two-dimensional rotor.

1.2. Internal Coordinate Gradients

Furthermore, if γ = γXx2 Y seems to be a scalar-valued function, therefore

2. THE SCHRODINGER EQUATION FOR MOLECULES

Where Τd is the operator of the kinetic energy, V

2.2. The Representation of Coordinates

/%&'( = 0) , /%&') = 0( , /%& = 0% (33)

The translational part

The matrix [Α] is

∇1 Χ: ∧ ≥'̅ = Ø:1 (3 − 8)≥'̅ (68)

P Ü(I& I( ) Ü(I( I' ) = Ø/Q (73)

[4] Pesonen,J.and Halonen,L.Volume-elements of integration: A geometric algebra approach.The

JUSTIFICATION OF THE CHOICE OF CATALYST FOR THE OXIDATION OF C3-

Elmira HUSEYNOVA, Ulkar SHIRALIYEVA, Nasiba IMANOVA, Ziba BAGIROVA,

Keywords: heteropoly acid, acrolein, methacrolein, oxidation, thermal stability.

3. RESULTS AND DISCUSSION

NUMERICAL AND EXPERIMENTAL INVESTIGATION ON THE REPAIR IMPACT OF

Mohammadjavad RANJBARAN1, Seyed Masoud HOSSEINI2

Figure 1: The 600 KN Santam Testing Machine

1.1.2 Experimental Method

Table 1: Measurements and Specifications for Aluminum Samples

Horizontal Vertical Glass Fibers

Figure 2: Positioning the Sample in the Load-cell

1.2.1 Numerical Simulation