The paper describes synthesis of magnetite-alginate composites. The main feature of such biomaterials is the simultaneous formation of magnetite nanoparticles inside the alginate matrix. Obtained samples were characterized by X-ray diffraction and transmission electron microscopy. In several samples the secondary phase of ammonium chloride was observed. The average crystallite sizes of magnetite phase are about 13 nm. The addition of alginate leads to the decrease of microstrains in [h k 0] direction

Kuznetsov, V.N.

Stanislavov, A.S.

Sukhodub, L.B.

Sukhodub, Leonid Fedorovych

Суходуб, Леонид Федорович

Суходуб, Леонід Федорович

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 4 No 2, 02NABM06(2pp) (2015)   2304-1862/2015/4(2)02NABM06(2) 02NABM06-1  2015 Sumy State University Magnetite-polymer Nanoparticles: Structure and Properties  A.S. Stanislavov*, L.B. Sukhodub, V.N. Kuznetsov, L.F. Sukhodub  Sumy State University, 2, Rymsky Korsakov Str., 40007 Sumy, Ukraine  (Received 27 July 2015; published online 29 August 2015)  The paper describes synthesis of magnetite-alginate composites. The main feature of such biomaterials is the simultaneous formation of magnetite nanoparticles inside the alginate matrix. Obtained samples were characterized by X-ray diffraction and transmission electron microscopy. In several samples the sec-ondary phase of ammonium chloride was observed. The average crystallite sizes of magnetite phase are about 13 nm. The addition of alginate leads to the decrease of microstrains in [h k 0] direction.  Keywords: Magnetite, Alginate, X-ray diffraction, Transmission electron microscopy.   PACS numbers: 87.85.J –, 87.64.Bx, 87.64.Ee                                                             * tornado200@yandex.ua 1. INTRODUCTION  Unique properties of magnetite nanoparticles are widely used in medicine for diagnostics and treatment. It is considered that biomagnetite is very important for preservation and processing of data in brains. It was shown that signals, caused by the physiogenic and pathogenic magnetic biominerals, are registered in brain tissues [1]. We have developed several ways to obtain magnetite granules in a polysaccharide shell for medical purposes [2]. For a detailed study of a role of magnetic biominerals in the brain function, it is neces-sary to develop biomimetic technologies of the creation of their synthetic counterparts close to the conditions of the biominerals formation in the living body. This paper describes properties and the synthesis of magnetite-alginate composites obtained by the for-mation of the nanostructured magnetite in the simul-taneously created alginate matrix.  2. MATERIALS AND METHODS  2.1 Materials  Compounds of bivalent (FeSO4 ∙7H2O) and trivalent (FeCl3 ∙6H2O) iron (produced by “Sigma”), sodium algi-nate with the molecular weight of 323 kD (made in China), 25 wt % aqueous solution of ammonia were used. The formation of magnetite Fe3O4 (reference Sample 1) occurred at 80 C according to the following chemical reaction:  2FeCl3 ·6H2O + FeSO4 ·7H2O + 8NH3 ·H2O → → Fe3O4 + 6NH4Cl↓ + (NH4)2SO4 + 23H2O  Magnetite nanoparticles for Samples 2-6 were formed in the presence of the natural polymer of sodium alginate. Fe2 + ions were added on the first stage to 2 wt % aqueous solution of alginate to achieve the equal distribution of magnetite nanoparticles in the alginate matrix for Samples 2-4. We assume that due to the join-ing-up of iron ions and functional groups of alginate the three-dimensional polymeric matrix was formed. Fe2 + ions acted as the centers of the following creation of magnetite. Ammonia solution was added on the differ-ent stages of synthesis at 40 to 80 C. The synthesis of Samples 5 and 6 was focused on ob-taining magnetite nanoparticles as a part of the aque-ous-alginate emulsion. At the same time the alginate solution was added whether on the last stage after magnetite formation involving ammonia (Sample 5), or before its formation (Sample 6).  2.2 Methods  The crystallinity and structure of the synthesized samples were examined using an X-ray diffractometer DRON-3 (Bourevestnik, Inc., Saint-Petersburg, Russian Federation) connected to a computer-aided system for the experiment control and data processing. The current and the voltage of the X-ray tube were 20 mA and 40 kV respectively. All experimental data was processed by means of the program package DIFWIN-1 (Etalon PTC, Ltd., Moscow, Russian Federation). Identification of crystal phases was done using a JCPDS card catalog (Joint Committee on Powder Diffraction Standards). The crystallite sizes L were calculated using the Scherrer equation [3]:   ,cosKL   (2.1)  where K is the form coefficient (K  1),  is the wave-length,  is the peak broadening,  is the diffraction angle. The quantitative phase analysis was performed us-ing the reference intensity ratio (RIR) method [4]:   ,11 nireliiiireliiiIKIIIKC  (2.2)  where Ci is the concentration of the i-phase, Ki is the corundum number of the i-phase, Ii is the peak integral intensity of the i-phase, reliI  is the peak relative inten-sity of the i-phase. Due to the presence of two lines, which correspond to parallel planes of the same reflection order, it is pos-sible. The Williamson-Hall method [3] was used to sep- A.S. STANISLAVOV, L.B. SUKHODUB, V.N. KUZNETSOV, ET AL PROC. NAP 4, 02NABM06 (2015)   02NABM06-2 arate contributions in the peak broadening from small sizes of coherent scattering regions and existing mi-crostrains due to the presence of two lines, which corre-spond to parallel planes of the same reflection order. The extrapolation function method was used to calcu-late a crystal lattice parameter. This method allows to extrapolate the lattice parameter value to the   90 where definition errors of interplanar spaces, as well as the lattice parameter, are extremely low. The Nelson-Riley extrapolation function was used in our studies [3]. Electron microscopic studies were conducted after the ultrasonic dispersion of the samples using the transmission electronic microscope PEM-125K (SELMI, PTC, Sumy, Ukraine) with the 90 kV accelerating volt-age and the 100 A beam current. The linear crystallite particle sizes of samples were measured with the Vide-oTesT-Razmer 5.0 program (VideoTesT, Ltd., Saint-Petersburg, Russian Federation).  3. RESULTS  The X-ray diffraction phase analysis shows that the main phase of all samples is magnetite (JCPDS 75-1609). In several samples, namely 2, 3, 4 and 6, the secondary phase of ammonium chloride (JCPDS 73-1491) is also present. X-ray diffraction spectra are pre-sented on Fig. 1. The quantitative phase analysis was performed to determine phase concentrations. The Sample 3 has the largest quantity of ammonium chlo-ride, while the least one is in the Sample 6.    Fig. 1 – X-ray diffraction spectra of synthesized samples  The average crystallite sizes of magnetite phase by Scherrer of all samples are about 13 nm varying from 11 to 18 nm (see Table 1). Polymer-bearing samples show slightly larger crystallite sizes with the decrease of microstrains as compared to the Sample 1 synthe-sized without alginate. The lattice parameter of Fe3O4 changes insignificantly.  Table 1 – Appointment of special paragraph styles  Samples L (Schrerrer), nm C, % Williamson-Hall Nelson-Riley (2 2 0) (3 1 1) (4 0 0) (5 1 1) (4 4 0) NH4 Fe3O4 L, nm ε·103 a, nm 1 12,7 11,3 11,9 10,5 9,8 – – 18 3,435 0,8342 2 12,1 13 12,8 13,9 11,7 33,8 66,2 12,6 0,411 0,8372 3 – 12,5 – – 10,3 60,4 39,6 – – 0,8366 4 – 13 – 13,5 11,6 43,3 56,7 – – 0,8362 5 – 13,1 – – 11,3 – – – – 0,8355 6 18 17,9 13,7 16,4 18,1 18,7 81,3 17,8 0,061 0,836  TEM microphotographs show particles evenly dis-tributed in an organic matrix (Fig. 2).    Fig. 2 – TEM microphotographs of magnetite nanoparticles, immobilized in alginate matrix: Samples 2 and 3 synthesized with different techniques 4. CONCLUSIONS  It was found that the formation of the unwanted phase of ammonium chloride in several samples de-pends on the temperature conditions of synthesis. The magnetite nanoparticles, evenly incorporated into the alginate matrix, with similar crystallite sizes were ob-tained during researches. The aim of our future devel-opment is to improve the synthesis techniques and to study structural properties of magnetite in biopolymer matrices.    REFERENCES  1. A.B. Brik, Ukr. J. Phys. Opt. 11, 46 (2010). 2. A.S. Stanislavov, A.A. Yanovska, V.N. Kuznetsov, L.B. Sukhodub, L.F. Sukhodub, J. Nano.- Electron. Phys. 7 No 2, 02009 (2015). 3. H.P. Klug, L.E. Alexander, X-Ray Diffraction Procedures: For Polycrystalline and Amorphous Materials (New York: Wiley: 1974). 4. F.H. Chung, J. Appl. Crystallogr. 8, 17 (1975).  а b 

Magnetite-polymer Nanoparticles: Structure and Properties

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 4 No 2, 02NABM06(2pp) (2015) 
 
 
2304-1862/2015/4(2)02NABM06(2) 02NABM06-1  2015 Sumy State University 
Magnetite-polymer Nanoparticles: Structure and Properties 
 
A.S. Stanislavov*, L.B. Sukhodub, V.N. Kuznetsov, L.F. Sukhodub 
 
Sumy State University, 2, Rymsky Korsakov Str., 40007 Sumy, Ukraine 
 
(Received 27 July 2015; published online 29 August 2015) 
 
The paper describes synthesis of magnetite-alginate composites. The main feature of such biomaterials 
is the simultaneous formation of magnetite nanoparticles inside the alginate matrix. Obtained samples 
were characterized by X-ray diffraction and transmission electron microscopy. In several samples the sec-
ondary phase of ammonium chloride was observed. The average crystallite sizes of magnetite phase are 
about 13 nm. The addition of alginate leads to the decrease of microstrains in [h k 0] direction. 
 
Keywords: Magnetite, Alginate, X-ray diffraction, Transmission electron microscopy. 
 
 PACS numbers: 87.85.J –, 87.64.Bx, 87.64.Ee 
 
 
                                                          
* tornado200@yandex.ua 
1. INTRODUCTION 
 
Unique properties of magnetite nanoparticles are 
widely used in medicine for diagnostics and treatment. 
It is considered that biomagnetite is very important for 
preservation and processing of data in brains. It was 
shown that signals, caused by the physiogenic and 
pathogenic magnetic biominerals, are registered in 
brain tissues [1]. We have developed several ways to 
obtain magnetite granules in a polysaccharide shell for 
medical purposes [2]. For a detailed study of a role of 
magnetic biominerals in the brain function, it is neces-
sary to develop biomimetic technologies of the creation 
of their synthetic counterparts close to the conditions of 
the biominerals formation in the living body. 
This paper describes properties and the synthesis of 
magnetite-alginate composites obtained by the for-
mation of the nanostructured magnetite in the simul-
taneously created alginate matrix. 
 
2. MATERIALS AND METHODS 
 
2.1 Materials 
 
Compounds of bivalent (FeSO4 ∙7H2O) and trivalent 
(FeCl3 ∙6H2O) iron (produced by “Sigma”), sodium algi-
nate with the molecular weight of 323 kD (made in 
China), 25 wt % aqueous solution of ammonia were 
used. The formation of magnetite Fe3O4 (reference 
Sample 1) occurred at 80 C according to the following 
chemical reaction: 
 
2FeCl3 ·6H2O + FeSO4 ·7H2O + 8NH3 ·H2O → 
→ Fe3O4 + 6NH4Cl↓ + (NH4)2SO4 + 23H2O 
 
Magnetite nanoparticles for Samples 2-6 were 
formed in the presence of the natural polymer of sodium 
alginate. Fe2 + ions were added on the first stage to 
2 wt % aqueous solution of alginate to achieve the equal 
distribution of magnetite nanoparticles in the alginate 
matrix for Samples 2-4. We assume that due to the join-
ing-up of iron ions and functional groups of alginate the 
three-dimensional polymeric matrix was formed. Fe2 + 
ions acted as the centers of the following creation of 
magnetite. Ammonia solution was added on the differ-
ent stages of synthesis at 40 to 80 C. 
The synthesis of Samples 5 and 6 was focused on ob-
taining magnetite nanoparticles as a part of the aque-
ous-alginate emulsion. At the same time the alginate 
solution was added whether on the last stage after 
magnetite formation involving ammonia (Sample 5), or 
before its formation (Sample 6). 
 
2.2 Methods 
 
The crystallinity and structure of the synthesized 
samples were examined using an X-ray diffractometer 
DRON-3 (Bourevestnik, Inc., Saint-Petersburg, Russian 
Federation) connected to a computer-aided system for 
the experiment control and data processing. The current 
and the voltage of the X-ray tube were 20 mA and 40 kV 
respectively. All experimental data was processed by 
means of the program package DIFWIN-1 (Etalon PTC, 
Ltd., Moscow, Russian Federation). Identification of 
crystal phases was done using a JCPDS card catalog 
(Joint Committee on Powder Diffraction Standards). 
The crystallite sizes L were calculated using the 
Scherrer equation [3]: 
 
 ,
cos
K
L   (2.1) 
 
where K is the form coefficient (K  1),  is the wave-
length,  is the peak broadening,  is the diffraction 
angle. 
The quantitative phase analysis was performed us-
ing the reference intensity ratio (RIR) method [4]: 
 
 ,
1
1










 
n
i
rel
ii
i
i
rel
ii
i
IK
I
I
IK
C  (2.2) 
 
where Ci is the concentration of the i-phase, Ki is the 
corundum number of the i-phase, Ii is the peak integral 
intensity of the i-phase, 
rel
i
I  is the peak relative inten-
sity of the i-phase. 
Due to the presence of two lines, which correspond 
to parallel planes of the same reflection order, it is pos-
sible. The Williamson-Hall method [3] was used to sep-
 A.S. STANISLAVOV, L.B. SUKHODUB, V.N. KUZNETSOV, ET AL PROC. NAP 4, 02NABM06 (2015) 
 
 
02NABM06-2 
arate contributions in the peak broadening from small 
sizes of coherent scattering regions and existing mi-
crostrains due to the presence of two lines, which corre-
spond to parallel planes of the same reflection order. 
The extrapolation function method was used to calcu-
late a crystal lattice parameter. This method allows to 
extrapolate the lattice parameter value to the   90 
where definition errors of interplanar spaces, as well as 
the lattice parameter, are extremely low. The Nelson-
Riley extrapolation function was used in our studies [3]. 
Electron microscopic studies were conducted after 
the ultrasonic dispersion of the samples using the 
transmission electronic microscope PEM-125K (SELMI, 
PTC, Sumy, Ukraine) with the 90 kV accelerating volt-
age and the 100 A beam current. The linear crystallite 
particle sizes of samples were measured with the Vide-
oTesT-Razmer 5.0 program (VideoTesT, Ltd., Saint-
Petersburg, Russian Federation). 
 
3. RESULTS 
 
The X-ray diffraction phase analysis shows that the 
main phase of all samples is magnetite (JCPDS 75-
1609). In several samples, namely 2, 3, 4 and 6, the 
secondary phase of ammonium chloride (JCPDS 73-
1491) is also present. X-ray diffraction spectra are pre-
sented on Fig. 1. The quantitative phase analysis was 
performed to determine phase concentrations. The 
Sample 3 has the largest quantity of ammonium chlo-
ride, while the least one is in the Sample 6. 
 
 
 
Fig. 1 – X-ray diffraction spectra of synthesized samples 
 
The average crystallite sizes of magnetite phase by 
Scherrer of all samples are about 13 nm varying from 
11 to 18 nm (see Table 1). Polymer-bearing samples 
show slightly larger crystallite sizes with the decrease 
of microstrains as compared to the Sample 1 synthe-
sized without alginate. The lattice parameter of Fe3O4 
changes insignificantly. 
 
Table 1 – Appointment of special paragraph styles 
 
Samples L (Schrerrer), nm C, % Williamson-Hall Nelson-Riley 
(2 2 0) (3 1 1) (4 0 0) (5 1 1) (4 4 0) NH4 Fe3O4 L, nm ε·103 a, nm 
1 12,7 11,3 11,9 10,5 9,8 – – 18 3,435 0,8342 
2 12,1 13 12,8 13,9 11,7 33,8 66,2 12,6 0,411 0,8372 
3 – 12,5 – – 10,3 60,4 39,6 – – 0,8366 
4 – 13 – 13,5 11,6 43,3 56,7 – – 0,8362 
5 – 13,1 – – 11,3 – – – – 0,8355 
6 18 17,9 13,7 16,4 18,1 18,7 81,3 17,8 0,061 0,836 
 
TEM microphotographs show particles evenly dis-
tributed in an organic matrix (Fig. 2). 
 
 
 
Fig. 2 – TEM microphotographs of magnetite nanoparticles, 
immobilized in alginate matrix: Samples 2 and 3 synthesized 
with different techniques 
4. CONCLUSIONS 
 
It was found that the formation of the unwanted 
phase of ammonium chloride in several samples de-
pends on the temperature conditions of synthesis. The 
magnetite nanoparticles, evenly incorporated into the 
alginate matrix, with similar crystallite sizes were ob-
tained during researches. The aim of our future devel-
opment is to improve the synthesis techniques and to 
study structural properties of magnetite in biopolymer 
matrices. 
 
 
 
REFERENCES 
 
1. A.B. Brik, Ukr. J. Phys. Opt. 11, 46 (2010). 
2. A.S. Stanislavov, A.A. Yanovska, V.N. Kuznetsov, 
L.B. Sukhodub, L.F. Sukhodub, J. Nano.- Electron. Phys. 7 
No 2, 02009 (2015). 
3. H.P. Klug, L.E. Alexander, X-Ray Diffraction Procedures: 
For Polycrystalline and Amorphous Materials (New York: 
Wiley: 1974). 
4. F.H. Chung, J. Appl. Crystallogr. 8, 17 (1975). 
 
а b 


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