1. Art and Diseño

Advances in Materials
2015; 4(1): 11-15
Published online January 28, 2015 (http://www.sciencepublishinggroup.com/j/am)
doi: 10.11648/j.am.20150401.13
ISSN: 2327-2503 (Print); ISSN: 2327-252X (Online)
Study on the controlled growth of lanthanum hydroxide
and manganese oxide nano composite under the presence
of cationic surfactant
Neeraj Kumar Verma
Centre of Excellence, Material Science & Engineering, Department of Metallurgy, OP Jindal Institute of Technology, Raigarh Chhattisgarh,
India
Email address:
[email protected]
To cite this article:
Neeraj Kumar Verma. Study on the Controlled Growth of Lanthanum Hydroxide and Manganese Oxide Nano Composite under the Presence
of Cationic Surfactant. Advances in Materials. Vol. 4, No. 1, 2015, pp. 11-15. doi: 10.11648/j.am.20150401.13
Abstract: Lanthanum hydroxide and manganese oxide nano composite are synthesized by chemical routes. Physical
characterization is done by TEM to look at the size and dispersion of the nano particles in the composite. Chemical
characterization is done by X ray diffraction technique and FTIR to ascertain the attachment of the functionalities and bond
stretching. Further thermal analysis is done by thermo gravimetric analysis to find the tendency of the thermal decomposition
in the elevated temperatures range of 0-1000°C. Proper analysis and correlation of the various results obtained suggested the
controlled growth of crystalline without agglomeration and good stability in the various temperature ranges of the composite.
Keywords: Nanoparticles, XRD, TEM
1. Introduction
Nano-materials being unique in their morphology when
compared from their bulk form impart them with tremendous
range of properties not ordinarily expected. Depending on the
morphological configuration and size distribution various
manufacturing routes for such nano materials have been
established in laboratories [1].The synthesis of nanoparticles
is based on the preparation of hydroxide colloidal precipitates
and hydrothermal treatment at particular temperature. The
particle morphology has been altered by changing the process
[2] and various nanoparticles of manganese oxide. These
manganese oxide nanoparticles owing to their excellent
electric, magnetic, and catalytic properties[3],rechargeable
lithium ion batteries[4],magnetic[5],molecular adsorption,
low price, and environmental compatibility play a vital role
as a building block for the nanocomposite. Especially
manganese oxide is known as an effective catalyst for deNOx systems [6]. The synthetic procedures are used for these
materials in order to study the influence of particle size on
their properties, including conventional solid state reaction,
co -precipitation [7],Sol–gel [8]and molten salts reactions [9].
Hydrophilic and hydrophobic methods for the synthesis of
Mn2O4 nanoparticles [10] and Sono-synthesis of Mn3O4
nanoparticles in different media are done without any
additives [11]. These Mn3O4 nanoparticles find their
application in the investigation of High resolution electron
energy loss spectroscopy [12]. Mn3O4 nanocubes at room
temperature when undergoes appropriate thermal recycling
behave as a catalyst [13]. In some cases of the Mild aqueous
synthesis of octahedral Mn3O4 ,nanocrystals are showing
varied oxidation states [14].Effect of organic solvents on
particle size of Mn3O4 nanoparticles synthesized by a
solvothermal method have been studied in detail[15]. At
room temperature these Mn3O4 nanoparticles undergoes
hydrothermal transformation to g-MnO2 nanorods [16]. It is
generally accepted that the preparation of lanthanum
hydroxide nanoparticles has been used in the synthesis of
oxides or sulfides through dehydration due to straightforward
approach [17] Further it has been reported that La2O3 and La
(OH)3 are very susceptible to surrounding condition with
CO2 . Under such appropriate condition of temperature and
pressure the process of carbonation occurs which leads the
formation of surface carbonates or hydroxycorbonates [18]
&[19].Furthermore, the synthesis and Characterization of
Lanthanum Oxide nanoparticles could be done from the
thermolysis of a nano-sized Lanthanum (III) Supra molecule
as a novel precursor [20]. The objective of this paper is to
study on the controlled growth of Lanthanum Hydroxide and
Manganese Oxide Nano Composite under the presence of
12
Neeraj Kumar Verma: Study on the Controlled Growth of Lanthanum Hydroxide and Manganese Oxide Nano
Composite under the Presence of Cationic Surfactant
cationic surfactant trimethylammonium bromide and tetra
butylammonium bromide.
The synthesized particles of lanthanum hydroxide and
Manganese Oxide nanocomposties are characterized by
Powder X-ray diffraction (XRD), Thermogravimetric
Analysis (TGA), Fourier Transform infrared Spectroscope
(FTIR) and Transmission electron microscopy (TEM) .The
characterizations of the composite confirm nano rods which
could help in the conductivity of biofluids proteins by
suitable attachment of these nanoparticles.
2. Experimental
2.1. Synthesis of Lanthanum hydroxide- Manganese Oxide
Nanocomposite
For synthesis of nanocomposite, 5.6 mmole of KMnO4
(0.89020gm) with varying concentrations of La(NO3)3.
6H2O(1.4651gm), CTAB(1.7223 gm) and TBAB (1.81119
gm) are dissolved into 100 ml of distilled water. The mixture
becomes homogenous under slow stirring for few minutes
(40min) in order to avoid bubble formation and then
monohydrate hydrazine are added rapidly to the
salt/surfactant solution under vigorous magnetic stirring.
varying concentration of KMnO4,La(NO3)3,CTAB, TBAB
and N2H4.H2O used for synthesis with appropriate amount.
The color of the solution immediately changes from dark
purple to black/brown then to orange/brown. The system is
heated at 70ºC for 1 hr and cooled down to room temperature
by removing the heat source. An orange/brown material is
precipitated and separated out by centrifugation. The solid
solution washed four times with ethanol and dried under
vacuum rotavapour at 45ºC at 170 pressures. The variation in
concentration of lanthanum nitrate used for the synthesis of
nanocomposite from 0.05 mmole to 6 mmole resulted in the
change in the color (from light brown to dark brown) of
nanocomposite.
3. Result & Discussion
synthesis route. The particle size measurement has been
carried out using XRD and a Fourier Transformation infrared
(FTIR) recorded in the range from 500 to 4000 cm-1. The
thermal behavior has been characterized by TGA Instrument
in the temperature range 0 to 10000C and the morphological
study has been carried out by TEM.
3.1. XRD Analysis
X-ray diffraction pattern of synthesized sample of
lanthanum manganese oxide composite after annealing is
shown in Figure 1(a). This pattern clearly indicates about
pure crystalline nature of composite. Figure1 ( b ) shows
room temperature x-ray diffraction pattern of synthesized
lanthanum
manganese
oxide
composite
before
annealing .This pattern shows diffraction peaks for Mn3O4
plane which are marked(*).The peaks are found to be
broadened. This indicates that Mn3O4 and La(OH) 3 in the
composite material are in crystalline form. The use of
higher concentration of lanthanum oxide shows up with the
increased intensity of the (101) planes than corresponding to
(211) diffraction line of manganese oxide in patterns. This
resembles with the pattern of La0.93MnO3 ceramic mixture
after annealing at 1000 0C for 1 hour .The XRD pattern of
nanocomposite after annealing consist of diffraction by (012),
(110), (104), (202) (006), (024), (211), (122), (116), (214),
(018), (220), (208), (306) planes of rhombohedral
La0.93MnO3 along with diffraction by (112), (211), (220),
(224) and (400) planes of tetragonal Mn3O4.The average
crystallite size d of the nanoparticles is calculated using
the modified Scherrer formula
t = 0.9 λ / Cos θB (BM - BS)
Here λ = wavelength of x-ray used, θB = Bragg’s angle,
BM = Full width at half maximum of the peak, B S = Full
width at half maximum of the same peak from a standard
material. Using the modified Scherrer formula the average
crystallite size turns out to be 21 nm and 12 nm. The
broadening of peaks shown in the fine crystal size is due to
the growth of nanocrystals with respect to surfactant.
The Nanocomposite has been synthesized using the chemical
Figure 1(a). XRD Patterns of nano composite [La(OH)3 /Mn3O4 with aspect ratio (5/3)] after annealing.
Advances in Materials 2015; 4(1): 11-15
13
Figure 1(b). XRDPatterns of nano composite [La (OH)3 /Mn3O4 with aspect ratio (5/3)] before annealing.
3.2. Fourier Transformation Infrared (FTIR) Study
Figure 2. Fourier Transform Infrared Spectra of nano composite.
The FTIR spectrum of nanocomposite is depicted in the
above Fig.2. Analysis of the FTIR spectra clearly indicates
that a peak appeared at 504.4 cm-1 which is attributed to the
distortion vibration of Mn-O in octahedral site. The La-OH
deformation and Mn-O stretching mode at tetrahedral sites
appeared as a combined overtone at 623.9 cm-1. The broad
band at 3410.7 cm-1 is due to combined vibration of
physioabsorbed molecules of water. The peak at 2923.2 cm-1
is due to C-H asymmetrical stretching. The peak at 1629.1 is
ascribed to physioabsorbed water molecules. The bend
appeared at 1473.4cm-1 is attributed to the C-H asymmetrical
bending [21]. The band at 1383.2 cm-1 can be attributed to CH3 streching of tertiary butyl of surfactant. The C-C skeletal
vibration appeared at 1120.0 cm-1. The presence of C-H
stretching, C-H bending and C-C skeletal vibrations
confirmed the capping of tertiary butyl of surfactant and
ammonium bromide surfactants at the surface of
nanoparticles.
14
Neeraj Kumar Verma: Study on the Controlled Growth of Lanthanum Hydroxide and Manganese Oxide Nano
Composite under the Presence of Cationic Surfactant
3.3. Thermogravimetric Analysis
Figure 3. Weight loss as function for nano composite.
In Thermogravimetric analysis the mass of a given
material were measured as a function of temperature by
heating the material at a constant rate. The prepared sample
of composite was heated at a rate of 1 0 0 C per minute for
this analysis. The variation of weight loss of the sample as
a function of temperature is shown in Figure 3. This figure
shows three step weight loss transitions. The first step weight
loss transition (2.02%) in the temperature range 25- 1200C is
ascribed to expulsion of physically adsorbed water molecules
at the surface of nano-Mn3O4. The second step weight loss
transition (5.83%) in the temperature range 120-4000C is
ascribed to loss of surfactants molecules that were capped the
nano-particles. In other words the decomposition of the
composite is almost complete at about 6000C and above the
6000C third step weight loss transition (9.23%) is attributed
to the loss of O2 due to conversion of Mn3O4/La(OH)3 nano
composites to La0.93MnO3 which is almost equal to
theoretical weight loss value according to following reaction:
2Mn3O4 + 5.58 La(OH)3 → 6La0.93MnO3 + 6.74 H2O + 1.63 H2
It is clear from the analysis that the conversion of Mn3O4/
La(OH)3 nano composite to La0.93MnO3 is confirmed using
diffraction pattern of XRD.
3.4. Transmission Electron Microscope Analysis
Figure 4. Transmission electron microscope of nanoparticles (a) Images of nanocomposite (Mn3O4/La(OH)) (b) measurements of composite in rod with 9-12
nm in width and 30-40 nm in length.
It is clear from transmission electron microscope image
(Fig 4.a, b) that the nanoparticles are uniform size and pebble
like in shape. The diameter of nano-particles varies in the
range of 12-15 nm. The electron diffraction pattern for nanoparticles is also in agreement with XRD results. The clearly
uniform size of nano-particles are attributed to the surfactant
Advances in Materials 2015; 4(1): 11-15
15
capping which is also confirmed from TGA and FTIR
analysis
The micrographs of Composites represents the formation
of randomly dispersed La(OH)3 nanorods. The highmagnification image of a typical individual La(OH)3 nanorod,
in which the width and length of the lanthanum hydroxide
nanorod are around 10 nm and 36 nm respectively. The size
of the La(OH)3 nanorod was controlled by surfactant
nanorods. The driving force for the anisotropic growth of
La(OH)3 nanorod is derived from the inherent crystal
structure of La(OH)3 materials and their chemical potential in
solution [22,23] and also shows that Mn3O4/La(OH)3
nanocomposite, the composite is in the rod like shaped. The
above results indicates the presence globular Mn3O4
nanoparticles in the close vicinity of nanorods La(OH)3
which are well attached and are around 26 nm and 200 nm in
width and length respectively confirm the synthesis of
Mn3O4/La(OH)3 nanocomposite. The study of all the samples
shows that in the case of nanocomposite rods of La2O3 have
grown in size and particles are attached at their edges.
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4. Conclusion
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Lanthanum
hydroxide
and
manganese
oxide
nanocompoiste were successfully prepared through chemical
route. .X-ray diffraction confirms the pure crystalline nature
of the nanocomposte. `Bragg’s diffraction peaks
corresponding to both Lanthanum and manganese. The
intensity corresponding to lanthanum (101) was found to be
higher than that of Manganese (201) diffraction at
2θ .Thermogravimetric analysis on the sample showed that
the nanocomposite underwent complete decomposition at
about 6000C.The concentration of samples were confirmed
with Lanthanum/Manganese aspect ratio as 5:3 with the
anlysis of FTIR. Further more it was confirmed that the LaOH deformation and Mn-O stretching mode at tetrahedral
sites were present due to cationic surfactants with
monohydrate hydrazine .
Hence the findings of the present work gives an detail
account of the growth pattern of Lanthanum and Manganese
nano particles in the presence of cationic surfactant. These
results suggest the potential application of Lanthanum and
Manganese nanoparticles towards fabrication of temperature
sensitive sensors.
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