Evaluation of La0.7Sr0.3Mn1-xBxO3 (B=Mo, Ti) nanoparticles synthesized via GNP method for self-controlled hyperthermia

Article abstract of DOI:10.1016/j.jallcom.2018.02.302

This current work deals with the study of the magnetic and biomedical characterization of La_0.7Sr_0.3Mn_1-xB_xO₃ (B=Mo, Ti) nanoparticles for hyperthermia applications. Our nanoparticles were prepared through an aqueous combustion process (Glycine Nitrate Process, GNP), and are characterized with a mean crystallite size about 18 nm. The incorporation of Ti⁴⁺ and Mo⁶⁺ in Mn-site induced a structural transition from rhombohedral structure with R-3 C space group for La_0.7Sr_0.3MnO₃ compound to orthorhombic one with Pnma space group for La_0.7Sr_0.3Mn_0.95Mo_0.05O₃ and La_0.7Sr_0.3Mn_0.95Ti_0.05O₃ compounds. The morphological properties indicated a variation in grain size ranging from 82 to 90 nm with doping extra element in manganese site. All samples exhibit a classical behavior from ferromagnetic (FM) to paramagnetic (PM) state as the temperature increases. A decrease in Curie temperature (T_C) has been remarked from 84 °C to 70 °C and 82 °C for La_0.7Sr_0.3MnO₃, La_0.7Sr_0.3Mn_0.95Ti_0.05O₃, La_0.7Sr_0.3Mn_0.95Mo_0.05O₃ respectively. According to the Arrott plots, the slopes of the curves of all the samples are positive, which is a signature of second order transition. The magnetic heating characteristics in AC field were measured in alternating magnetic fields of 23.89 mT at a fixed frequency of 518.7 kHz. The intrinsic loss power (ILP) has been calculated from SAR values. The different nanoparticles with a high ILP may be useful for the in situ hyperthermia treatment of cancer cells.

Full text of DOI:10.1016/j.jallcom.2018.02.302

Accepted Manuscript
Evaluation of La Sr Mn B O (B=Mo, Ti) nanoparticles synthesised via GNP
.7 0.3 1-x x 3
0
method for self-controlled hyperthermia
Jihed Makni, Kalthoum Riahi, Firas Ayadi, Virginie Nachbaur, Wissem Cheikhrouhou-
Koubaa, Mohamed Koubaa, Muhammad Asif Hamayun, El-Kbir Hlil, Abdelwaheb
Cheikhrouhou
PII:
S0925-8388(18)30798-9
10.1016/j.jallcom.2018.02.302
JALCOM 45178
DOI:
Reference:
To appear in: Journal of Alloys and Compounds
Received Date: 14 November 2017
Revised Date: 25 February 2018
Accepted Date: 26 February 2018
Please cite this article as:
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Evaluation of La Sr Mn B O (B=Mo, Ti) nanoparticles
0.7
0.3
1-x
x
3
synthesised via GNP method for self-controlled hyperthermia
1
1
2
2
Jihed Makni , Kalthoum Riahi , Firas Ayadi , Virginie Nachbaur , Wissem Cheikhrouhou-
1
4
3
5
Koubaa , Mohamed Koubaa , Muhammad Asif Hamayun ,El-Kbir Hlil , Abdelwaheb
1
Cheikhrouhou
1
LT2S Lab (LR16 CRNS 01), Digital Research Center of Sfax, Sfax Technopark, Cité El Ons,
B.P. 275, 3021, Sfax,Tunisia
2
Groupe de Physique des Matériaux (GPM). Adresse UMR 6634 CNRS UFR Sciences et
Techniques Avenue de l’Université - BP12, 76801 Saint Etienne du Rouvray, France
3
Magnetism Laboratory, Department of Physics, COMSATS Institute of Information
Technology, 45550 Islamabad, Pakistan
4
Institut Supérieur de Biotechnologie de Sfax, Université de Sfax, B.P. 261, 3000 Sfax, Tunisia
5
Institut Néel & Université Grenoble Alpes, B.P. 166, 38042 Grenoble Cedex 9, France
Abstract:
This current work deals with the study of the magnetic and biomedical characterization of
magnetic La Sr Mn B O (B=Mo, Ti) nanoparticles for hyperthermia applications. Our
0
.7 0.3
1-x
x
3
nanoparticles were prepared through an aqueous combustion process (Glycine Nitrate
Process, GNP), and are characterized with a mean crystallite size about 18 nm.
4
+
6+
The incorporation of Ti and Mo in Mn-site induced a structural transition from
rhombohedral structure with R-3 C space group for La Sr MnO compound to
0
.7 0.3
3
orthorhombic one with Pnma space group for La Sr Mn0.95Mo0.05O3 and
0
.7 0.3
La Sr Mn0.95Ti0.05O compounds. The morphological properties indicated a variation in
0
.7 0.3
3
grain size ranging from 82 to 90 nm with doping extra element in manganese site. All samples
exhibit a classical behavior from ferromagnetic (FM) to paramagnetic (PM) state as the
temperature increases. A decrease in Curie temperature (T ) has been remarked from 84 °C to
C
7
0°C and 82°C for La La Sr MnO , La Sr Mn0.95Ti0.05O , La Sr Mn0.95Mo0.05O3
0 0.7 0.3 3 0.7 0.3 3 0.7 0.3
1

ACCEPTED MANUSCRIPT
respectively. According to the Arrott plots, the slopes of the curves of all the samples are
positive, which is a signature of second order transition.
The magnetic heating characteristics in AC field were measured in alternating magnetic fields
of 23.89 mT at a fixed frequency of 518.7 kHz. The intrinsic loss power (ILP) has been
calculated from SAR values. The different nanoparticles with a high ILP may be useful for
the in situ hyperthermia treatment of cancer cells.
Keywords: Nanoparticles; Magnetic properties; Hyperthermia
*
Corresponding author:
Jihed Makni-Chakroun
LT2S Lab, Digital Research Centre of Sfax,
Sfax Technopark, BP 275,
3
021 Sakiet-Ezzit, Tunisia
Tel/Fax: (216) 74 863 042 / (216) 74 863 041
E-mail: makni.jihed@yahoo.fr
Introduction
The cancer is still one of the biggest challenges facing the medical research in our time [1]. It
is considered as a difficult disease to be treated due to the fact that the available treatment
options are limited and, in many cases, the timely diagnosis and the lack of prognosis are
difficult. Moreover, the approaches usually used for cancer treatment such as surgery,
radiotherapy and chemotherapy present considerable harmful side effects. In this context, a lot
of effort has been devoted to find novel approaches for both diagnosis and therapy [2]
.
Hyperthermia is a therapeutic method for cancer treatment; the term “hyperthermia” is
derived from two Greek words, “hyper” and “therme,” meaning “rise” and “heat,”
respectively [3]. Busch et al [4] have reported that cancer cells are sensitive to high
temperatures; the growth of these cells can be destroyed at temperatures ranging from 41 °C
to 47 °C for at least 20 min to 60 min [5, 6]
.
The hyperthermia treatment includes a list of steps, firstly the magnetic nanoparticles (MNPs)
have been to be injected into the human body, delivering them to the tumor area, and once the
MNPs are disseminated inside the tumor, then an external AC magnetic field is applied, and
the nanoparticles transform the electromagnetic radiation into heat [7]. Finally, the generated
2

ACCEPTED MANUSCRIPT
heat rises the temperature in the tumor area and, in this way, damages or even kills and
eradicates cancerous cells with minimally affecting the healthy ones, since healthy cells has a
better resistance to high temperature than cancer cells [8-9]. In this manner, the patient can
receive a localized and highly efficient cancer therapy, without suffering from the treatments
of chemotherapy or radiotherapy.
Another mechanism of heating, which is different from the local magnetic hyperthermia
effect, is the magnetocaloric effect (MCE) [10– 11]
.
At the present time, the main research activity in the field of MCE and magnetocaloric
materials is directed to magnetic refrigeration. However we try to use another perspective
application of these materials in the field of medicine. The MCE occurs as the result of the
alignment of magnetic moments with an external applied magnetic field. The alignment
reduces the magnetic randomness, or the magnetic component of the total entropy. This
reduction of magnetic entropy must be compensated by the increase of another form of
entropy and, in the case of magnetocaloric materials, is channeled into phonons, or heat. Since
the mechanism of heating in this case is different from that of the conventional magnetic
hyperthermia, it is named as “magnetocaloric hyperthermia” [12]. There are three quantities
that are usually reported for MCE: the magnetic entropy change (
capacity (RC), and the adiabatic temperature change ( T). For a thermodynamic Carnot
cycle, the energy observed in one cycle in a magnetocaloric material is calculated as [13,14]
⋅ꢀ SM
ꢀSM), the refrigeration
ꢀ
:
ꢀQ = ꢀT
Thus, the magnetocaloric contribution to heating in this type of hyperthermia is significant for
a material with large MCE parameters.
Magnetic losses in magnetically ordered ferro- and ferri-magnetic materials have a number of
advantages as they diminish at the Curie temperature (T ). As a result, magnetic hyperthermia
C
treatments could be free from external temperature control when T is tuned to the therapeutic
C
temperature range. In order to prevent the overheating of normal cells, the development of
magnetic materials which are not affected by alternating magnetic field above 318 K (45 °C)
has become essential.
In literature, different MNPs have been reported for magnetic fluid hyperthermia, bio-
separations and magnetic resonance imaging including superparamagnetic iron oxides [15]
and ferrites of manganese, cobalt, nickel and zinc, etc. [16]
.
In this field researchers are mainly interested in iron oxides thanks to their low toxicity,
however such compounds are limited as application in hyperthermia because they do no
exhibit specific physical properties and it is difficult to adjust their properties. Recently,
3

ACCEPTED MANUSCRIPT
ferrite core-based magnetic nanoparticles are being used for clinical cancer treatment
(
MagForce Nanotechnologies AG, Berlin, Germany) with a magnetic field strength of up to
.0225 T at 100 kHz, in combination with radiotherapy, inducing an increase in the median
survival time of the patients, but unfortunately no full recovery has been achieved yet [17]
0
.
To overcome this challenge, magnetic nanoparticles with perovskite structure were suggested
thanks to the ability to control their physical properties and to tune their temperature transition
in the desired temperature range. This is due to the fact that this kind of magnetic material
provides more heating in the ferromagnetic state (below TC) and less heating in the
paramagnetic state (above TC). Thus the Curie temperature acts as a temperature control
switch and maintains a constant desired temperature in the tumor region.
Strontium doped lanthanum manganite (La Sr MnO ) nanoparticles are one of the best
1
-x
x
3
candidates for self-controlled hyperthermia applications. Their magnetization is higher than
that of most materials for such applications and their Curie temperature can be tuned to be in
the range 41.85 - 46.85 °C (315 – 320 K) [18]
.
To underline the fascinating properties of such ferromagnetic material, in physical point of
view, the incorporation of atoms into the manganese site of La Sr MnO can destroy the
0
.7 0.3
3
long range interaction. Different effects can be produced upon Mn-site doping in
ferromagnetic manganites. As reported in the literature, the substitution effect of Mn cations
by non-magnetic ions such as Al, Ti, Ga, Sc and Ta [19–20], generally destroys the double
exchange ferromagnetism in the samples, leading to a steady decrease of TC.
The dependence of the physical and chemical properties of magnetic materials on the shape,
and size of nanoparticles and the thermal history of sample preparation as well have always
motivated the study of new synthetic routes to produce these materials. This is a key factor
since the effective morphology, the chemical composition and the grain size distribution
deeply affect the physico-chemical properties of the materials [21]. Hence the synthesis,
sintering, and characterization of the nanoparticles have become a vital part of ceramic
research. Particularly, the synthesis of oxides with perovskite crystal structure requires high
◦
temperature (
≥
700 C). This creates difficulties in terms of shape and individual properties of
particles [22]. As a result, soft chemical methods of synthesis will offer some advantages in
this regard, in particular the Glycine nitrate process (GNP) ‘auto-combustion’ presents a
considerable asset in comparison with other conventional methods. In fact, it is a low-
temperature initiated exothermic and self-propagating process. Combustion reaction is a
vigorous exothermic redox reaction between a suitable fuel, which also acts as a complexing
agent and an oxidizer. The GNP has the advantage of high temperatures, fast heating rates and
4

ACCEPTED MANUSCRIPT
short reaction times, thus inhibiting particle size growth and promoting the formation of
homogeneous, crystalline nanopowders.
The main goal of this current work is to study the magnetic and biomedical characterization of
magnetic nanoparticles for hyperthermia applications of the molybdenum and titanium
substitution on manganese site of La Sr MnO (LSMO), La Sr Mn0.95Ti0.05O (LSM-Ti-
0
.7 0.3
3
0.7 0.3
3
O), La Sr Mn0.95Mo0.05O (LSM-Mo-O) nanoparticles prepared via auto-combustion
0
.7 0.3
3
process.
The parent compound LSMO exhibits a ferromagnetic-paramagnetic transition with a value of
4
+
6+
T about 357 K. We used the (Ti ) and (Mo ) ions to partially substitute the manganese site.
C
We expected a decrease of T in order to be able to destroy the affected cells by tumor, as a
C
4
+
4 +
regard to the ionic radius r <Mn > = 0.53 Å and r <Ti >= 0.605 Å. The titanium ion
4
+
4 +
exhibits a valence state (Ti ) .The choice of Ti is based on the fact that the substitution of
4
+
4+
3 +
Mn reduces the ratio of the Mn / Mn ions, so the double exchange interactions will be
4
+
4 +
affected. The complete substitution of Mn
by Ti
excludes the double exchange
3
+
4 +
4 +
interactions Mn -O-Mn since the 4s state of Ti is inaccessible to the conduction
4
+
electrons due to its low spatial occupation. As a consequence, the Ti ions would become a
site of high dispersion, known as the magnetic dilution of the lattice. Among all the
substitutions of the Mn site, the Mo effect was considered to be particularly interesting
6
+
0
because of its high valence state (Mo ) and its electronic configuration d . Even the slight
amount of Mo is expected to induce a large variation in the valence of Mn, since molybdenum
(Mo) can exist with different states of valency and may also induce different valences of Mn.
2
. Experimental techniques
2
.1 Combustion synthesis
The La Sr Mn B O (B=Mo, Ti) ( B=Ti and Mo; x=0.00 and 0.05) samples have been
0
.7 0.3
1-x
x
3
synthesized by the autocombustion method in aqueous solution. This method is also called
Glycine Nitrate Process (GNP). We started by choosing the two "oxidizing and fueling"
reagents. Elsewhere, researchers used nitrates as oxidant and urea, citric acid and glycine as
fuels [23, 24]
.
In our case we have chosen the glycine of formula NH CH COOH. The G/N molar ratio has
2
2
been chosen was equal to 0.56 in order to improve the chelation while maintaining a flame
temperature sufficient to induce the crystallization of our compounds.
5

ACCEPTED MANUSCRIPT
Stoichiometric amounts of La(NO ) , 6H O; Sr(NO ) , 4 H O; Mn(NO ) ,4 H O, and glycine
3
3
2
3 2
2
3 2
2
(
C H NO ) were dissolved in water. Titanium oxide TiO and molybdenum oxide MoO were
2 5 2 2 3
dissolved in nitric acid to obtain titanium nitrate and molybdenum nitrate were added to the
mixture. The nitrate solution was thoroughly mixed by stirring and dehydrated by heating on a
hot plate at T = 100 ° C for 2 hours. A transparent viscous gel is formed. The temperature of
the heating of the gel is increased to T = 350 ° C, which favors its autocombustion. The
materials are obtained in the form of very bulky black ash. The ashes are crushed and calcined
at 1000 ° C for 12 hours. All previous steps are resumed in Figure.1.
2
.2 Characterization methods
X-ray diffraction
X-ray powder diffraction using PANalytical X’Pert Pro’diffractometer with Cu Ka radiation,
was used to determine the phase compositions, lattice parameters and crystallite sizes of for
LSMO, LSM-Ti-O, LSM-Mo-O nanoparticules.
The scanning electron microscope
The surface morphology and elemental analysis were carried out by scanning electron
microscopy (SEM) and energy dispersive X-ray technique (EDX) in the GPM laboratory
(France)
The magnetometer BS1
The magnetocaloric parameters (magnetic entropy changes and hysteretic effects) have been
studied using BS1 magnetometer developed in Néel Institute (CNRS Grenoble).
The variations of the magnetization as a function of magnetic field at different temperatures
have been measured between 0 and 5 T and in a temperature range around the TC.
Hyperthermia study
To demonstrate hyperthermia effect of the prepared magnetic dispersions, magnetic
hyperthermia (or magnetothermia) measurements were made on one of the selective sample
designated as ML T640, using a Nanotherics Magnetherm in COMSATS Institute of
Information Technology (Pakistan). An RF induction unit operating at a frequency of 518.7
kHz and AC field amplitude of 23.89 mT was used for adiabatic magnetothermia
6

ACCEPTED MANUSCRIPT
measurements. Powder samples were placed in a thermally insulated vial and the heating
curves were measured using a Neoptix fiber optic temperature sensor.
3
. Results and discussion
3
.1. Structure and morphology
The powder X-ray diffraction patterns of LSMO, LSM-Ti-O, LSM-Mo-O materials are shown
in Figure 2.
Using the “X'Pert HighScore Plus”software, we succeeded to identify that the main phase is
attributed to the parent compound LSMO with a small secondary phase attributed to the
presence of SrCO and La(OH) impurities is observed. The LSM-Ti-O compound is a single-
3
3
phase manganite. While the LSM-Mo-O compound, presents a majority of manganite phase
with a low intensity La (OH) as a secondary phase.
3
The formation of these impurities is explained by the role played by glycine in this method of
preparation. The ratio G/N (and more particularly the amount of glycine) influences the
phenomena of complexations in solution. If the amount of glycine is insufficient, the non-
chelate cations crystallize in the form of salts (mainly nitrates or carbonates) during the
heating step inducing the progressive evaporation of the solvent [25]. It is interesting to notice
that these impurities are only based on lanthanum and strontium, which reflects a preferential
chelation of manganese, and seems contradictory with the work of Chick and Peng
announcing a preferential chelation of manganese by the amine function [26]. Our results are
similar to those found obtained by Epherre et al, in which they where the authors were deeply
interested in the synthesis of manganite nanoparticles by autocombustion [23].
The structure refinement has been carried out by Rietveld analysis [27] of the X-ray powder
diffraction data using the FULLPROF software [28].
The positions of the Bragg reflections are marked by vertical lines in blue for the manganite
phase and in red and green for the secondary phases. Differences between the observed and
4+
6+
the calculated intensities are shown in Figure 2. The incorporation of Ti and Mo in Mn-
site induced a structural transition from rhombohedral structure with R-3C space group for
LSMO, compound to orthorhombic one with Pnma space group for LSM-Ti-O and LSM-Mo-
O compounds. This structural transition may be attributed to the mismatch of the cationic
4
+
4 +
+6
sizes of the Mn , Ti and Mo ions. The results of this refinement are shown in Table.1.
7

ACCEPTED MANUSCRIPT
Since, we have two different structures, we cannot it is difficult to compare the different
volumes between them, so we choose to compare the volumes of the form groups in each
mesh. In fact, we have divided the volume of each compound by the multiplicity of its
structure (Z = 4 for the orthorhombic structure and Z = 6 for the rhombohedral one). The unit
3
cell volume per formula unit (V/Z) varies slightly from 58.32 Å for LSMO to 58.16 and
3
5
8.22 Å for LSM-Ti-O and LSM-Mo-O respectively. This is can be explained by the
presence of the secondary phases in the parent compound.
The crystallite sizes have been calculated by the Debye Scherrer‘s formula:
ꢃꢄ
ꢀꢁꢂ
=
(1)
ꢅ ꢆꢇꢈ ꢉ
D : is the average size of the crystallites;
SC
K: is the Scherrer constant (0.86 for the perovskites);
: is the full width at half maximum of the most intensity diffraction peak;
: is the wavelength of the radiation (1.5406Å);
: is the angle of the strongest characteristic peak.
Free-compound and the substituted ones are marked with nanometric crystallites size about
7nm and 20nm.This result is expected with GNP autocombustion.
β
λ
θ
1
The morphology and grain size of LSMO, LSM-Ti-O and LSM-Mo-O samples, revealed by
SEM, are shown in Figure 3. One can observe that grains are spherical. It is further observed
that the grain size in the samples is ranging from 82 to 90 nm with doping extra element in
manganese site (Table 2). In addition, the particle size increases with substitution in B-site.
This increase can be explained by the effect of the mean ionic radius <r > of B site, since the
B
4
+
6 +
average radii of the ions <Ti > = 0.605 Å and <Mo > = 0.59 Å are greater than ionc radii
4
+
that of <Mn > = 0.53 Å.
Using DSEM and DXRD values, it is possible to calculate the agglomeration degree (grain
size/crystallite size) for each sample as mentioned in Table.1 [29]. The grain sizes obtained by
SEM (DSEM) are much larger than those calculated by the broadening of the diffraction peaks
(DXRD), which indicates that each grain observed by SEM basically consists of several
crystallites [30]. In order to confirm the presence of molybdenum, titanium and the cationic
stoichiometry, EDX analyses have been carried out at several spots on the surface. We can
notice that our synthesized samples contain all expected chemical elements and show a
nominal composition close to the desired one.
3
.2 Magnetic measurements:
8

ACCEPTED MANUSCRIPT
In order to study the magnetic properties of our samples, we measured the magnetization as a
function of the applied magnetic field temperature under 0.05 T (Figure 4). All samples
exhibit a classical behavior from ferromagnetic (FM) to paramagnetic (PM) transition as the
temperature increases.
The value of Curie temperature T is identified by the minimum of dM/dT curve versus
C
temperature and it is found to be 357; 343 and 355K for LSMO, LSM-Ti-O and LSM-Mo-O
respectively.
The steady decrease of T in LSM-Ti-O sample is greater than that observed for LSM-Mo-O
C
4
+
one. This behavior can be explained by the fact that the substitution by Ti ions weakens the
3
+
4 +
6 +
interactions of the double exchange between the Mn and Mn ions, whereas Mo ion
4
+
2+
substitution decreases the Mn concentration and induces the presence of the Mn ions, thus
2
+
3 +
3 +
established Mn -O-Mn ferromagnetic interactions with the Mn ions.
On the one hand, we note that this transition is marked with a steady decrease in
magnetization with titanium doping. This result is in agreement with that reported by Kallel et
al. [31] and F. Ben Jemaa et coll [32]. A similar behavior was observed for (La Sr )Mn
1-
0
.7 0.3
Cr O manganite [33] and (La Ca )Mn Co O [34]. On the other hand, we also notice an
x
x
3
0.7
0.3
1-x
x
3
increase in magnetization with molybdenum substitution. This later agrees very well with the
results of Chen et al. [35] in which they where the authors observed that the substitution of
manganese by the molybdenum in La Ca Mn Mo O compounds induces an increase in
1
/2
1/2
1-x
x
3
magnetization.
The isotherms of the magnetization as a function of the magnetic field applied in the range of
00 - 380K are gathered in Figure 5.
2
We note that for T <T , the magnetization reaches high values at low magnetic field and tends
C
to saturate when the field increases. For the higher temperatures, the magnetization curves are
of the same type, whereas the saturation magnetization decreases due to the thermal agitation.
We have plotted a hysteresis loop measured under an applied magnetic field rising from -7 to
7
T at 10 K, as shown in Figure 6 a. All the samples show a ferromagnetic state at low
temperatures. It can be seen that the M–H hysteresis loops present a typical soft
ferromagnetic (FM) behavior, with very low remanences and coercivities (Figure 6 b). The
small values of coercive field confirm that the magnetic domains can rotate easily to the
direction of the applied magnetic field [36]
.
9

ACCEPTED MANUSCRIPT
A zoom rising from - 0.2 to + 0.2 T has been made to clarify the hysteresis cycle. At low
temperatures, the saturation magnetization values Ms(exp), determined by extrapolation of
the M versus H data in the high field to zero field, are found to be 38.5 , 34 and 64.5emu/g for
LSMO, LSM-Ti-O, LSM-Mo-O respectively. It was marked with a decrease for LSM-Ti-O
sample and an increase with LSM-Mo-O one.
The curves for the studied observed behavior of our systems (see in Figure 7) demonstrate the
maximum magnetization observed for the LSMO, LSM-Ti-O, LSM-Mo-O under
investigation with respect to the as concentration of conduction electrons per atom (e/A). The
e/A parameter has been calculated using a common approach “Vasil ev”, as number of outer
shell electrons introduced into conduction by each compound's chemical elements over the
average number of atoms in the compound. For example, the electronic structure of
La Sr MnO is formed (see periodical table) as:
0
.7 0.3
2
3
1
2
5
2
2
4
0
.7•[6s 5d ]La+0.3•[5s ]Sr+1•[3d 4s ]Mn+3•[2s 2p ]O=2.1eLa+0.6eSr+7eMn+18eO =27.7e.
Thus, for this compound e/A=27.7 e/A.
The obtained magnetization result shows a maximum of magnetization similar to that in the
other Slater-Pauling curves. Thus, the observed decrease in transition temperatures for the
4
+
both substitutions (see Figure 4) and in the magnetization with Ti doping (Figure 6) can be
3
+
2-
4+
related to the decrease in the Mn -O -Mn exchange interaction and the observed increase
6
+
magnetization with substitution by Mo can be related to arises from the presence of
2
+
2-
3 +
ferromagnetic interactions of Mn -O - Mn .
2
To check the nature of magnetic transition for our samples, we plot the Arrott curves M [37]
2
represented by the curves of the given by the magnetization square (M ) as a function of ꢁ0H /
M (Figure 8) using the isotherms M = f (ꢁ0H, T). According to the criterion of Banerjee [38]
,
if the slope is positive, the transition is of second order, if it is negative; it is of the first order.
From to the Arrott plots, the slopes for all the samples are positives, so indicating that the
transition is of the second order.
3
.2 The Magnetocaloric effect (MCE)
Tishin et al. [39] have related physics and medicine via the magnetocaloric material as a
‘
magnetotherapy’ method. This later consists of injecting nanoparticles exhibiting a high
maximum) MCE into a tumor, wherein the material has a magnetic ordering temperature
(
close (approximately) to the human body temperature and is selected from a group containing
1
0

ACCEPTED MANUSCRIPT
precious metals, rare-earth elements (metals) and alloys or intermetallic compounds. This
property makes it possible to destroy cancer cells without damaging healthy cells.
A low concentration of magnetocaloric material particles in the nanosize domain
(characteristic radius e.g. 200 nm) is demanded for a characteristic heating of a tumor to
approximately 42 °C [39]
.
When a magnetic material is subjected to a high magnetic field, the magnetic moments of the
atoms become reoriented. If the magnetic field is applied adiabatically, the temperature of the
material rises, and when the magnetic field is removed, the temperature decreases. This
behavior is called the magnetocaloric effect (MCE) [40]
In order to investigate this idea, we calculate the magnetic entropy changes (
results from spin ordering (i.e., ferromagnetic ordering). We can calculated the variation of
SM with temperature, when the magnetic field is varied from 0 to ꢁ0 Hmax using the following
expression SM [41]
.
∆SM), which
∆
∆
:
ꢕ ꢗ
ꢖ
ꢘ
ꢎꢊ
∆
ꢊꢋ = ꢌ ꢍ ꢐ ꢒμ ꢏꢔꢔꢔꢔ(2)
ꢓ
ꢎꢏ
ꢑ
ꢕ ꢗ
ꢖ
ꢙ
From Maxwell’s thermodynamic relationship [41]
ꢎꢊ
ꢎꢚ
ꢍ
ꢐ =ꢔꢍ ꢐ ꢔ(3)
ꢎꢏ
ꢎꢛ
ꢑ
ꢗ
Equation (2) can be rewritten as follows:
ꢗ
ꢘ
ꢝꢋ
∆
ꢊ (ꢛ, ꢏ) = ꢜ ( )ꢒꢏ (4)
ꢋꢔ
ꢗ
ꢝꢑ
ꢙ
The numerical integration of the latter gives the values of ꢀSM at different values of fields and
temperatures:
ꢞꢟꢠꢡꢢꢞꢟ
∆
S = ∑ꢟ ꢣꢟꢠꢡ
∆H (5)
i
ꢤꢣꢟ
Where Mi + 1 and M represent, respectively, the magnetizations at the temperatures Ti + 1 and
i
T under a field H .
i
i
For more precision, we used calculation software based on an integral instead of a summation.
As part of this work, we used the following equation:
ꢣꢡꢥꢣꢦ
ꢦ
ꢡ
ꢧꢩꢪꢫ
ꢧꢩꢪꢫ
∆
S (
) =
[ꢜꢬ
ꢞ(ꢣ , ꢧ)ꢨꢧ −ꢔꢜ
ꢞꢔ(ꢣ , ꢧ)ꢨꢧ]
(6)
M
ꢦ
ꢡ
ꢣꢦꢤꢣꢡ
ꢬ
1
1

ACCEPTED MANUSCRIPT
Figure 9 displays the temperature dependence of the isothermal magnetic entropy change for
all the samples under an applied field of 5 T and 2T, the -
Curie temperature TC.
ꢀSM exhibits a maximum, near the
These curves show that the variation of entropy
ꢀS as a function of temperature has a
relatively large peak around the Curie temperature T . This is typical of materials with a
C
second order transition. We can also note that the magnetic and the negative entropy for all
our samples is due to the ferromagnetism encountered in these samples.
The maximum value of │ꢀSM
│ under a field ꢁ0H = 5T is found to be 0.90; 0.60 and
2
.17(J/kg K) for LSMO, LSM-Ti-O and LSM-Mo-O respectively. Those results are
considered as acceptable values since for ‘magneocaloric hyperthermia’ a high value of
magnetocaloric response is too much requested.
To explain the wide variation of magnetic entropy in manganites, the model of the double
exchange of Zener is strongly recommended [42]. The effect of the double-exchange
3
+
4 +
3+
4 +
interactions between the Mn and Mn ions is closely related to the Mn /Mn ratio during
the substitution process. Guo et al. suggested that this large variation in entropy in perovskites
may be due to spin-network coupling [43]. All subsequent studies [44] indicate that MCE is
enhanced in systems where the spin-lattice interaction is strong at the transition temperature
TC, irrespective of the magnetic nature of cation B as long as the substitution level is low. For
a high substitution rate, (ie) the antiferromagnetic interaction dominates the interaction of
ferromagnetic double exchange, the change of magnetic entropy is reduced.
In order to investigate the calorific capacity variation of our studied compounds, we used the
indirect method from the
S, we have evaluated the variation of specific heat or calorific capacity
compound using the formula (7) (Figure 9):
ꢀ
S curves. After determining the variation of the magnetic entropy
ꢀ
ꢀCp for each
ꢯ∆ꢁꢞ
ꢯꢣ
∆
ꢭ (ꢣ, ꢧ) = ꢭ (ꢣ, ꢧ) − ꢭ (ꢣ, ꢬ) = ꢣ
ꢔ [45] (7)
ꢮ
ꢮ
ꢮ
Figure 10 displays the variation of specific heat as a function of temperature under different
magnetic fields for LSMO. C is positive for T <T (energy absorption) and becomes
negative beyond T (release of energy). The maximum / minimum value of
ꢀ
P
C
ꢀ
C under a 5T
C
P
magnetic field for the compounds LSMO, LSM-Ti-O and LSM-Mo-O are listed in (Table 3).
These results show that the variation of the specific heat differs from zero on each side of
magnetic transition. We also note that the values of ꢀCꢰꢱꢲꢳꢔ/ꢔꢱꢴꢵꢔ increase simultaneously
with the increase of ꢁ0H.
1
2

ACCEPTED MANUSCRIPT
3
.3 Magnetic hyperthermia measurement
For magnetic hyperthermia study, heating measurements were carried out on 40, 45 and 50
mg powder for LSMO, LSM-Ti-O and LSM-Mo-O respectively under an alternating
magnetic field of frequency about 518.7 kHz and amplitude 23.89 mT, the obtained results
are shown in Figure 11.
One of the most important features of materials used for magnetic hyperthermia is the value
of SAR, giving an idea of the heating power of particles.
This parameter can be calculated according to the equation given as following:
ꢩꢶꢪꢩꢷꢸꢹ ꢨꢣ
SAR=ꢭ ∗ ꢩꢩꢪꢺꢻ ( )ꢼꢽꢬꢔ(ꢾ)
ꢨꢼ
Where C is the specific heat of the sample (C=660J/kg.K), mmag is the weight fraction of
magnetic element, msample is the weight of sample and (dT/dt)t=0 is the slope of the curve
temperature vs time, see Ref. [7]
.
In the present case, an increase of temperature followed by stabilization of temperature
without variation has been observed in Figure 11.
The SAR is equal to 10.363 W/g for the LSMO however it is about 8.927 and 9.135 W/g for
LSM-Ti-O and LSM-Mo-O respectively as shown in Figure 12.
Based on literature for magnetic oxides applied to hyperthermia, SAR is the major parameter
to be maximized. If the SAR’s value is very high, the dose of nanoparticles to be injected into
the patient will be low.
In a recent report, Kallumadil et al. [46] suggested a new parameter, intrinsic loss power
(
ILP) defined as:
ILP= SAR/H²f (9)
In order to get a perfect comparison on SAR’s values measured in different laboratories and at
different AC field strength and frequency, the ILP calculated for the samples in this study are
gathered in Table.3 with samples from literature for comparison.
Further experiments are currently in progress to evaluate the cytotoxicity of the nanoparticles
and to improve their surface by hydrophilic macromolecules grafting, prior to in vitro and in
vivo experiments.
1
3

ACCEPTED MANUSCRIPT
Conclusion
To sum up, the structural, magnetic and heating behaviors of La Sr MnO (LSMO) doped
0
.7 0.3
3
with 5% molybdenum and titanium (LSM-Mo-O and LSM-Mo-O) were studied. A decrease
in T accompanied by an increase in molybdenum substitution magnetization and its decrease
C
with titanium substitution was observed .We can notice a decrease in T for both compounds
C
whereas the magnetization increases for LSM-Mo-O and is reduced for LSM-Ti-O. In
addition, a hyperthermia method based on the magnetocaloric effect was discussed. The
specific absorption rate (SAR) and the intrinsic loss power (ILP) values were obtained for
these samples and found to be comparable to those of magnetite and some commercial
ferrofluids. We can thus be able to improve their properties by using another percentage of
doping or another substitution either in site A or site B (ABO : the perovskite structure) and
3
which can be used as heat-sealed by adjusting the Curie points to obtain a thermal self-
regulation, thus eliminating the expensive and invasive thermometry associated with
hyperthermia treatments.
Acknowledgements:
This work was supported by the Tunisian Ministry of Higher Education and Scientific
Research. The author Dr. Kalthoum Riahi would like to thank Dr. Sadia Manzoor for the
magnetic hyperthermia measurements in COMSATS Institute of Information Technology
(Pakistan).
References
[1] C. Eheman, S. J. Henley, R. Ballard-Barbash, E. J. Jacobs, M. J. Schymura, A.-M. Noone,
L. Pan, R. N. Anderson, J. E. Fulton, B. A. Kohler, A. Jemal, E. Ward, M. Plescia, L. A. G.
Ries and B. K. Edwards, Cancer. 118 (2012) 2338–2366.
1
4

ACCEPTED MANUSCRIPT
[2] K. Michele, A. Lima-Ten´orio Edgardo, M. G´omez Pineda Nasir, Ahmad Hatem Fessi
Abdelhamid Elaissari , Magnetic Nanoparticles: In Vivo Cancer Diagnosis and Therapy, Int.
J. Pharm. 493 (2015) 313.
[
3] Y. Javed, K. Ali, Y. Jamil, Magnetic Nanoparticle- Based Hyperthermia for Cancer
Treatment: Factors Affecting Heat Generation Efficiency,
Complex Magnetic Nanostructures (2017 ) 393-424.
4] Busch, W., 1867, "Aus der sitzung der medicinischen " Berl Klin Wochenschr, 13(5), p.
37.
5] H. Chiriac, T. Petreus, E. Carasevici, L. Labusca, D.-D. Herea, C. Danceanu, N.Lupu, "In
[
1
[
vitro cytotoxicity of fe–cr–nb–b magnetic nanoparticles under high frequency electromagnetic
field," J. Magn. Magn Mater. 380 (2015) 13-19.
[
6] P. Moroz, S. Jones, B .Gray, "Magnetically mediated hyperthermia: current status and
future directions," Int. J. Pharm.18 (2002) 267-284.
7] R. Hergt, S. Dutz, R. Müller, M. Zeisberger, Magnetic particle hyperthermia: nanoparticle
magnetism and materials development for cancer therapy, J. Phys. Condens. Matter. 18
[
(2006) S2919–S2934.
[8] R. Cavaliere, E.C. Ciocatto, B.C. Giovanella, C. Heidelberger, R.O. Johnson, M.
Margottini, B. Mondovi, G. Moricca, A. Rossi-Fanelli, Selective heat sensitivity of cancer
cells. Biochemical and clinical studies, Cancer. 20 (1967) 1351–1381.
[
9] E. M. Levine, E. B. Robbins, Differential temperature sensitivity of normal and cancer
cells in culture, J. Cell. Physiol. 76 (1970) 373–379.
10] A. M. Tishin, Y. I. Spichkin, The Magnetocaloric Effects and Its Applications, Series in
Condensed Matter Physics, Institute of Physics Publishing, Bristol, 2003 ISBN 0 7503 0922
[
9
.
[
11] A. M. Tishin and Y. I. Spichkin, “Recent progress in magnetocaloric effect: Mechanisms
and potential applications,” Int. J. Refrig 37 (2014) 223-229.
12] A. M. Tishin, Method for Carrying Out a Magnetic Therapy of Malignant Neoplasm,
006, WO 2006/135270 Al
13] E. Zatsepina, A. Tishin, P. W. Egolf, D. Vuamoz, in: Proceedings of the Third
International Conference on the Magnetic Refrigeration at Room Temperature, USA, May
.
[
2
[
(2009) 12–15.
[14] M. Johannesen, U. Gneveckow, L. Eckelt, A. Feussner, N. Waldoenfer, R. Scholoz, S.
Deger, P. Wust, S.A. Loening, A. Jordan, Clinical hyperthermia of prostate cancer using
1
5

ACCEPTED MANUSCRIPT
magnetic nanoparticles: presentation of a new interstitial technique. Int. J. Hyperth. 21 (7)
(2005) 637–64.
[15] S. Laurent, S. Dutz, U. O. Häfeli and M. Mahmoudi, Magnetic fluid hyperthermia: focus
on superparamagnetic iron oxide nanoparticles, Adv. Colloid Interface Sci. 166 (2011) 8–23.
16] J. Xie, Y. Zhang, C. Yan, L. Song, S. Wen, F. Zang, G. Chen, Q. Ding, C. Yan and N.
[
Gu, High-performance PEGylated MneZn ferrite nanocrystals as a passive-targeted agent for
magnetically induced cancer theranostics, Biomaterials. 35 (2014) 9126–36.
[
17] B. Thiesen, A. Jordan, Clinical applications of magnetic nanoparticles for hyperthermia,
Int. J. Hyperth. 24 (2008) 467e474.
18] S. Mornet, S. Vasseur, F. Grasset, E. Duguet, Magnetic nanoparticle design for medical
diagnosis and therapy, J. Mater. Chem. 14 (2004) 2161.
19] J. Blasco, J. Garc´ıa, J. M. de Teresa, M. R. Ibarra, J. Perez, P. A. Algarabel, C.
[
[
Marquina, C. Ritter, Structural, magnetic, and transport properties of the giant
magnetoresistive perovskites La Ca Mn Al O , Phys. Rev. B. 55 (1997) 8905
2
/3
1/3
1-x
x
3−δ
[20] L. S. Lakshmi, K. D¨orr, K. Nenkov, A. Handstein, K-H. M¨uller, V. S. Sastry,
Suppression of itinerant ferromagnetism and cluster-glass behaviour of colossal
magnetoresistive Ta-substituted La0.67Ca0.33MnO J. Phys.: Condens. Matter. 19 (2007)
3,
2
16218.
21] L. Malavasi, M. C. Mozzati, S. Polizzi, C. B. Azzoniand, G. Flor, Lattice Disorder,
Electric Properties, and Magnetic Behavior of La Na MnO Manganites, Chem. Mater. 15
[
1
-x
x
3+δ
(2003) 5036.
[22] O. V. Melnikov, O. Y. Gorbenko, M. N. Markelova, A. R. Kaul, V. A. Atsarkin, V. V.
Demidov, C . Soto, E. J. Roy, B. M. Odintsov, Ag-doped manganite nanoparticles: New
materials for temperature-controlled medical hyperthermia, J. Biomed. Mater. Res. A 91
(2009) 1048.
[23] R. Epherre, E. Duguet, S. Mornet, E. Pollert, S. Louguet, S. Lecommandoux, C. Schatzcd
and G. Goglio, Manganite perovskite nanoparticles for self-controlled magnetic fluid
hyperthermia: about the suitability of an aqueous combustion synthesis route, J. Mater. Chem. 21
(2011) 4393.
[24] M. Soleymani, A. Moheb, E. Joudaki, High surface area nano-sized
La Ca MnO perovskite powder prepared by low temperature pyrolysis of a modified
0
.6
0.4
3
citrate gel, Cent. Eur. J. Chem. 7 (2009) 809.
25] R. Peng, X. Fan, Z. Jiang, C. Xia, Characteristics of La0.85Sr0.15MnO3–δ Powders
Synthesized by a Glycine-Nitrate Process, Fuel Cells. 6 (2006) 455.
[
1
6

ACCEPTED MANUSCRIPT
[26] L. Chick, L. Pederson, G. Maupin, J. Bates, L. Thomas, G. Exarhos, Glycine-nitrate
combustion synthesis of oxide ceramic powders, Materials Letters. 10 (1990) 6.
27] H.M. Rietveld, A profile refinement method for nuclear and magnetic structures, J. Appl.
Crystallogr. 2 (2) (1969) 65.
28] T. Roisnel, J. Rodriguez-Carvajal, in: A Windows Tool for Powder Diffraction Patterns
[
[
Analysis Materials Science Forum Proceedings of the Seventh European Powder Diffraction
Conference, 2000. EPDIC 7.
[29] M. Soleymani, A. Moheb, E. Joudaki, Cent. Eur, High surface area nano-sized
La0.6Ca0.4MnO3 perovskite powder prepared by low temperature pyrolysis of a modified
citrate gel, Cent. Eur. J. Chem. 7 (2009) 809.
[
30] S. Das, T.K. Dey, Structural and magnetocaloric properties of La1−
prepared by microwave processing, J. Phys. D: Appl. Phys. 40 (2007) 1855.
31] N. Kallela, M. Oumezzine, H. Vincent, Neutron-powder-diffraction study of structural
and magnetic structure of La Sr Mn Ti O (x= 0, 0.10, 0.20, and 0.30), J. Magn. Magn.
yNayMnO compounds
3
[
0
.7 0.3
1-x
x
3
Mater. 320 (2008) 1810.
[32] F. Ben Jemaa, S. H. Mahmood, M. Ellouze, E. K. Hlil, F. Halouani, Structural, magnetic,
magnetocaloric, and critical behavior of selected Ti-doped manganites, Journal of ceramics
international (2015).
[
33] N. Kallel, J. Dhahri, S. Zemni, E. Dhahri, M. Oumezzine, M. Ghedira, H. Vincent, Effect
of Cr Doping in La Sr Mn Cr O with 0 0.5, phys. stat. sol (a). 184 (2001) 319.
34] N. Gayathri, A. K. Raychaudhuri, S. K. Tiwary, R. Gundakaram, Anothony Arularj, C.N.
≤ x ≤
0
.7
0.3
1–x
x
3
[
R. Rao, Electrical transport, magnetism, and magnetoresistance in ferromagnetic oxides with
mixed exchange interactions: A study of the La Ca Mn Co O system, Phys. Rev. B. 56
0
.7
0.3
1−x
x
3
(1997) 1345.
[35] J.W. Chen, G. Narsinga Rao, Induced ferromagnetic metallic state and Griffiths phase in
La Ca Mn Mo O compounds, Mater. Chem. Phys. 136 (2012) 254.
1
/2
1/2
1-x
x
3
[36] M. H. Ehsani , P. Kameli, F. S. Razavi, M. E. Ghazi, B. Aslibeiki, Influence of
Smdoping on the structural, magnetic, and electrical properties of La0.8-x SmxSr0.2MnO3
(0 < x < 0.45) manganites, J. Alloys . Compd 579 (2013) 406.
[37] A. Arrott, J. E. Noakes, Approximate Equation of State For Nickel Near its Critical
Temperature, Phys. Rev. Lett. 19 (1967) 786.
38] B.K. Banerjee, On a generalised approach to first and second order magnetic Transitions,
Phys. Lett. 12 (1964) 16.
[
1
7

ACCEPTED MANUSCRIPT
[39] A.M. Tishin, Y.I. Spichkin, V.I. Zverev , P.W. Egolf, A review and new perspectives for
the magnetocaloric effect: New materials and local heating and cooling inside the human
body, Int. J. Refrig. 68 ( 2 0 1 6 ) 177–186.
[
40] Manh-Huong Phana, Seong-Cho Yub, Review of the magnetocaloric effect in manganite
materials, J. Magn. Magn. Mater. 308 (2007) 325.
41] N. Pavan Kumar, G. Lalitha, E. Sagar, P. Venugopal Reddy, Magnetocaloric behavior of
rare earth doped La0 67Ba0 33MnO3. Physica B. 457 (2015) 275.
42] A.H. Morrish, The Physical Principles of Magnetism, Wiley, New York, 1965.
43] Z. M. Wang, G. Ni, Q. Y. Xu, H. Sang, Y. W. Du, Magnetocaloric effect in perovskite
[
.
.
[
[
manganites La À Nd Ca MnO and La Ca MnO3, J. Appl. Phys. 90 (2001) 5689.
0
.7
x
x
0.3
3
0.7
0.3
[
44] Z. B. Guo, Y. W. Du, J. S. Zho, H. Huang, W. P. Ding, D. Feng, Large Magnetic Entropy
Change in Perovskite-Type Manganese Oxides, Phys. Rev. Lett. 78 (1997) 1142.
45] M. H. Phan, H. X. Peng, S. C. Yu, N. D. Tho, N. Chau, Large magnetic entropy change
in Cu-doped manganites, J. Magn. Magn. Matter. 285 (2005) 199.
46] M. Kallumadil, M. Tada, T. Nakagawa, M. Abe, P. Southern, Q. A. Pankhurst,
Suitability of commercial cooloids for magnetic hyperthermia. J. Magn. Magn. Mater. 321
[
[
(2009) 1509-1513.
[47] Amin ur Rashid, Ashfaq Ahmed, S.N. Ahmad, S. A. Shaheen, Sadia Manzoor, Study of
Specific Absorption Rate of Strontium Doped Lanthanum Manganite Nanoparticles for Self
Controlled Hyperthermia Applications, J. Magn. Magn. Mater. 347 (2013) 39-44.
[
48] A.A. Kuznetsov, O.A. Shlyakhtin, N.A. Brusentsov, O.A. Kuznetsov, “SMART”
MEDIATORS FOR SELF-CONTROLLED INDUCTIVE HEATING, Eur. Cells Mater. 3
Suppl. 2) (2002) 75.
(
1
8

ACCEPTED MANUSCRIPT
Tables Captions
Table 1: The refined structural parameters for La Sr Mn B O (B=Mo, Ti; x=0.00 and
0
.7 0.3
1-x
x
3
0
.05) samples after the Rietveld refinements of X-ray diffraction data at room temperature.
min/max
Table 2: T , M , ∆S and ∆CP
values for LSMO, LSM-Ti-O and LSM-Mo-O
C
sat
max
compounds under magnetic applied fields of 2T and 5T.
Table 3: Comparison of the specific absorption rate of classical materials and manganese
perovskite.
Tables
Table 1:
Compounds
Space Group
LSMO
R3-C
LSM-Ti-O
LSM-Mo-O
Pnma
Pnma
Lattice parameters
a (Å)
b (Å)
c (Å)
5.501 (7)
5.501 (7)
5.461 (7)
7.722 (10)
5.515 (10)
232.64 (9)
5,465 (3)
7,735 (3)
5,508 (11)
232,89 (2)
13.352 (20)
349.96 (8)
3
V (Å )
Structural parameters
<
dMn, M-O> (Å)
1.975 (3)
1.910
1.982
<
θMn,M-O-Mn,M> (°)
158.16 (13)
157.2
165.55
Agreement Factors
2
Χ
4.15
1.95
1.64
Rbragg
RF
Particle size from XRD
nm) DRXD
Grain size from SEM
nm) DSEM
6.76
5.27
2.03
2.52
17
1.94
1.72
20
1
7
(
8
2
90
85
(
Agglomeration
degree
4.82
5.29
4.25
(grain size/
crystallite size)
1

ACCEPTED MANUSCRIPT
Table 2:
compounds
TC (K)
LSMO
357
38
LSM-Ti-O
343
LSM-Mo-O
355
M (emu/g)
34
64
sat
∆
Smax (2T/5T)
0.33/0.90
0.23/0.61
0.90/2.20
-1
-1
(
Jkg K )
Tmin/max
258/373
313/363
314/365
∆
Cp
2T
5T
-0.4/3
-0.9/5
-0.33/2.20
-0.85/3.75
-4/12.65
-8/18
min/max
-1
(
Jkg )
Table 3:
SAR
2
Samples
H(mT) f (kHz)
ILP(nHm /Kg) T (K)
refrences
C
(
W/g)
10.363
8.927
9.135
6.9
0.5
1
0.9
42
La Sr MnO
23.89
La Sr Mn0.95Ti0.05O3 23.89
518.7
518.7
518.7
108
214
214
214
880
880
0.055
0.047
0.048
0.012
3.3
357
327
355
316 [23]
320 [46]
319 [46]
340 [46]
750 [47]
850 [47]
This work
This work
This work
0
.7 0.3
3
0
.7 0.3
La Sr Mn0.95Mo0.05O3 23.89
0
.7 0.3
*
La0.82Sr0.18MnO3
88
1
1
1
9
La0.85Sr0.15MnO3
La Sr MnO
6.1
0
.8 0.2
3
La0.73Sr0.27MnO3
5.7
0.925
0.992
*
*
γ-Fe O3
2
Fe O4
9
45
3
(* is calculated from their own data)
2

ACCEPTED MANUSCRIPT
Figures Captions
Figure 1: The steps of Glycine Nitrate Process (GNP).
Figure 2: Observed (°) and calculated (solid lines) X-ray diffraction pattern for LSMO, LSM-
Ti-O and LSM-Mo-O Compounds.
Figure 3: SEM images and EDX analyses for (a) LSMO, (b) LSM-Ti-O and (c) LSM-Mo-O
Compounds.
Figure 4: (a) Temperature dependence of the magnetization, recorded at 0.05 T, for
La Sr Mn B O (B=Mo, Ti; x=0.00 and 0.05) and (b) the plot of dM/dT curve for
0
.7 0.3
1-x
x
3
determining TC.
Figure 5: Magnetization M variation versus magnetic field at different temperatures for
La Sr Mn B O (B=Mo, Ti; x=0.00 and 0.05)compounds.
0
.7 0.3
1-x
x
3
Figure 6: Hysteresis loops for La Sr Mn B O (B=Mo, Ti; x=0.00 and 0.05) at 10K. (a)
0
.7 0.3
1-x
x
3
Complete field range (-6 to 6T) and (b) zoom in from - 0.2 at + 0.2 T.
Figure 7: Magnetization as a function of conduction electrons concentration (e/A)
La Sr Mn B O (B=Mo, Ti; x=0.00 and 0.05) manganites (Slater-Pauling curves).
0
.7 0.3
1-x
x
3
2
Figure 8: Arrott plot (H/M vs. M ) at different temperatures of La Sr Mn B O (B=Mo,
0
.7 0.3
1-x
x
3
Ti; x=0.00 and 0.05) compounds .
Figure 9: Magnetic entropy change (ꢀS ) of La Sr Mn B O (B=Mo, Ti; x=0.00 and
M
0.7 0.3
1-x
x
3
0
.05) samples as a function of temperature up on magnetic field (a) 2T and (b) 5T.
Figure 10: The specific heat changes ∆C as a function of temperature for La Sr Mn B O
3
P
0.7 0.3
1-x
x
(
B=Mo, Ti; x=0.00 and 0.05) samples under an applied magnetic fields of (a) 2 T and (b) 5T.
Figure 11: Heating curves of La Sr Mn B O (B=Mo, Ti; x=0.00 and 0.05) samples in an
0
.7 0.3
1-x
x
3
AC magnetic field of amplitude 23.89 mT and frequency 518.7 kHz.
Figure 12: Specific absorption rate of LSMO, LSM-Ti-O and LSM-Mo-O nanoparticles.
1

ACCEPTED MANUSCRIPT
Figures
Figure 1
2

ACCEPTED MANUSCRIPT
Figure 2
3

ACCEPTED MANUSCRIPT
Figure 3
4

ACCEPTED MANUSCRIPT
La Sr MnO
.7 0.3
0
3
0,0
0,1
0,2
0,3
0,4
0,5
3
2
1
0
0
0
0
(
a)
(b)
La Sr Mn
Ti
O
0.7 0.3 0.95 0.05 3
-
-
-
-
-
La Sr Mn Mo
O
0.7 0.3 0.95 0.05 3
TC=343K
La Sr MnO
.7 0.3
0
3
La Sr Mn O
.7 0.3 0.95 0.05 3
Mo
0
TC=357K
La Sr Mn Ti
O
3
0
.7 0.3 0.95 0.05
TC=355K
1
00 150 200 250 300 350 400 450
2
00
300
400
500
600
T(K)
T(K)
Figure 4
40
30
20
10
0
200K
La Sr MnO
0
.7 0.3
3
∆
T=5K
380K
0
1
2
3
4
5
6
µ H(T)
0
5

ACCEPTED MANUSCRIPT
La Sr Mn
Ti
O
200K
La Sr Mn
Mo
O
270K
25
20
15
10
5
0
0.7 0.3 0.95 0.05 3
50
40
30
20
10
0
0.7 0.3 0.95 0.05 3
∆
T=5K
∆
T=3K
380K
420K
0
1
2
3
4
5
6
0
1
2
3
4
5
6
µ H(T)
µ H(T)
0
0
Figure 5
La Sr MnO
3
8
0
La Sr MnO
80
0.7 0.3
0.7 0.3
3
(a)
(b)
La Sr Mn
0.7 0.3
Ti
O
La Sr Mn
.7 0.3
Ti
O
0.95 0.05
Mo
3
0
0.95 0.05
Mo
3
60
60
40
La Sr Mn
0.7 0.3
O
La Sr Mn
.7 0.3
O
0.95
0.05
3
0
0.95
0.05
3
40
T=10K
T=10K
20
20
0
0
-
20
40
60
80
-20
-40
-60
-80
-
-
-
-
8
-6
-4
-2
0
2
4
6
8
-0.2
0.0
0.2
µ0H(T)
µ0H(T)
Figure 6
6

ACCEPTED MANUSCRIPT
Figure 7
1
1
1
1
600
400
200
000
2
00K
200K
La Sr MnO
La Sr Mn
Ti
O
0.7 0.3
3
0
.7 0.3 0.95 0.05 3
6
4
2
00
00
00
0
∆
T=5K
TC
∆
T=5K
800
600
400
200
0
TC
380K
3
80K
0,0
0,1
0,2
0,3
0,4
0,5
0
,0
0,5
µ H/M(T.g/emu)
1,0
µ H/M(T.g/emu)
0
0
7

ACCEPTED MANUSCRIPT
270K
La Sr Mn
Mo
O
2
2
1
1
500
000
500
000
0
.7 0.3 0.95 0.05 3
∆
T=3T
T
C
500
420K
0
0,0
0,1
0,2
0,3
0,4
µ H/M (T.g/emu)
0
Figure 8
La Sr MnO
.7 0.3
La Sr MnO
0.7 0.3
3
0
3
(
a)
(b)
La Sr Mn
Ti
O
La Sr Mn
Ti
O
0.7 0.3 0.95 0.05 3
0.7 0.3 0.95 0.05 3
2
1
1
0
,0
,5
,0
,5
0
0
0
,8
,4
,0
La Sr Mn
Mo
O
La Sr Mn
Mo
O
0
.7 0.3 0.95 0.05 3
0.7 0.3 0.95 0.05 3
2
T
5T
2
00
250
300
350
400
200
300
400
T(K)
T(K)
Figure 9
8

ACCEPTED MANUSCRIPT
2
1
0
0
0
La Sr MnO
.7 0.3
La Sr MnO
0.7 0.3
3
0
3
(
a)
La Sr Mn
Ti
O
La Sr Mn
Ti O
(b)
0
.7 0.3 0.95 0.05 3
0.7 0.3 0.95 0.05 3
1
0
5
0
5
La Sr Mn Mo
O
La Sr Mn
Mo
O
0
.7 0.3 0.95 0.05 3
0.7 0.3 0.95 0.05 3
2
T
5T
-10
-
2
40
280
320
360
240
280
320
360
T(K)
T(K)
Figure 10
9
8
7
6
5
4
3
2
0
H = 23.89 mT, f = 518.7 kHz
0
0
0
0
0
0
0
La Sr MnO
.7 0.3
0
3
La Sr Mn
Ti
O
0
.7 0.3 0.95 0.05 3
La Sr Mn Mo
O
0
.7 0.3 0.95 0.05 3
-
50
0
50 100 150 200 250 300 350 400
Time (s)
Figure 11
9