CHAPTER-1

1.1.1. INTRODUCTION.

The majority of ammonia produced is used in fertilizer, which helps feed billions of

people around the world. Now, Ammonia is also utilized extensively in various areas such as

refrigeration systems, food and beverage industries, explosives, wastewater treatment and in

the production of pharmaceuticals. In most of these industries, To avoid vaporisation,

ammonia is stored under high pressure as a liquid. Corrosion, faulty sealing, welding defects,

and operational errors may lead to a leaking accident.

Ammonia's nature is irritant and corrosive. When ammonia comes into contact with moisture

in the skin, eyes, mouth, or respiratory tract, it reacts immediately. Ammonium hydroxide

causes tissue necrosis (saponification) and cellular death by disrupting cell membrane lipids.

Water is extracted as cell proteins break down, causing an inflammatory response that causes

additional damage. The detection of ammonia gas can be done with a metal oxide gas sensor,

a conducting polymer, a catalytic gas sensor, or an optical absorption. Conducting polymer

Polyaniline (PANI) is mixed with thermoplastic polymers to create composite materials with

a low conductivity percolation threshold. As a result, the composites produced effectively

combine the mechanical properties of the thermoplastic polymer matrix with the electronic

properties of PANI, and can be used as organic gas sensors.Polyaniline (PANI) is a very

promising conducting polymer. PANI is distinguished from other conducting polymers by its

higher stability and lower cost The integration of the PANI matrix has improved the

electrochemical properties of the Metal Oxide Strontium oxide (SrO) structure..

1
Carbon nanotubes (CNTs) is known for its remarkable structural, mechanical, and electronic

properties, CNTs attracted a lot of interest for use in fabricating advanced materials. To

improve selectivity and sensitivity for various applications, polymer composites, metal, metal

oxide decoration, and different functional groups were introduced into carbon nanotubes. In a

recent study, polymer composites, metal, metal oxide decoration, and various functional

groups were introduced into carbon nanotubes to boost selectivity and sensitivity of

Ammonia gas. Similar to PANI, conjugated Schiff base polymer has also caught the attention

of researchers owing to the high thermal stability, high mechanical properties, excellent

nonlinear optical properties, electrical conductivity and remarkable photo and

electroluminescence.Heused2-(4,6-dimethoxypyrimidine-2-ylimino)methyl)-6-

methoxyphenol as a schiff base polymer.The Combination of MWCNT/PANI/SrO/DPMM is

a promising material for Gas sensing where each Material shows excellent conducting and

electrochemical property which leads to a better stability in sensing.This sensor is best suited

to sense industrial gas leakage, Medical devices and can even placed in mobile phones to

sense gas nearby. The physical properties of the sample were characterized by using scanning

electron microscopy

We have fabricated an Unique composition of sensor with multiwalled carbon nanotube

MWCNT/PANI/SrO/3-MPASA to achieve high sensitivity, good selectivity, stability

overtime and fast response. To the best of our knowledge, no such composition is made for a

sensing element. Due to their relatively high sensitivity, relative simplicity of synthesis, light

weight, and ability to detect gases at ambient temperature.

1.1.2.SENSOR.

The design and production of solid-state materials that can be used as sensitive elements is a

critical part of meeting these requirements. With the use of additives and composite

2
materials, it is possible to tune material dimensionality, implement dopants, settle

morphology at different scales, exploit hierarchical structures, and build customised

interfaces. Controlling all of these features and converting their interactions into practical

properties is, on the other hand, a difficult task. For scientists, the synthesis of these

possibilities and obstacles offers a powerful stimulus.As a result, the gas-sensor group has

developed unique and intelligent solutions that can meet the demands of applications.This

Special Issue will attempt to provide an overview of recent achievements in the field by

putting together the approaches produced by various research groups in order to advance

solid-state gas sensors.Original research articles, letters, and review papers on all

experimental and theoretical aspects of this subject are welcome to be submitted. The

following are some of the most important arguments:Nanoparticles, nanowires, hierarchical

nanostructures, and pure and doped/functionalized metal oxide nanostructures are all

examples of metal oxide nanostructures.Graphene and associated nanostructures, MoS2,

WS2, and phosphorene are examples of 2D materials.Composite and hybrid materials;

Organic nanostructures, such as carbon nanotubes, polymers, porphyrins, and

metalloporphyrins; Composite and hybrid materials Models and simulations for the

interaction of gases and nanostructures.

1.1.3. CARBON NANOTUBE.

Carbon nanotubes (CNTs) are cylinder-shaped molecules made up of single-layer carbon

atoms that have been rolled up (graphene). They can be single-walled (SWCNT) with a

diameter of less than 1 nanometer (nm) or multi-walled (MWCNT) with diameters of more

than 100 nm, consisting of many concentrically interconnected nanotubes. They can be

millimetres or even micrometres long. CNTs are chemically bonded with sp2 bonds, which

are an extremely strong type of molecular interaction, much like their building block

3
graphene.This property, combined with carbon nanotubes' natural tendency to rope together

due to van der Waals forces, allows for the development of ultra-high strength, low-weight

materials with highly conductive electrical and thermal properties. This makes them really

appealing for a wide variety of applications.

fig.1.Schematic of how graphene could roll up to form a carbon nanotube.

The electrical properties of nanotubes are determined by the rolling-up direction (rolling-up

or chiral vector) of the graphene layers. The hexagonal carbon-atom lattice of the nanotube's

chirality defines the angle of the nanotube's hexagonal carbon-atom lattice. Armchair

nanotubes, so named because of their armchair-like shape, have similar chiral indices and are

4
highly sought after for their perfect conductivity. They differ from zigzag nanotubes, which

are thought to be semiconductors. A simple 30 degree rotation of a graphene sheet transforms

the nanotube it shapes from armchair to zigzag or vice versa.[21]

1.1.4. UNIQUE CHARACTERS OF MWCNT.

CNTs have special thermal and mechanical properties that make them interesting for the

production of new materials, in addition to their electrical properties, which they inherit from

graphene:

● Their mechanical tensile strength can exceed that of steel by 400 times;

● They are extremely light, with a density one-sixth that of steel.

● They have a higher thermal conductivity than diamond.

● They have a high aspect ratio of more than 1000.

Meaning that they are incredibly thin in relation to their length; a tip-surface area near the

theoretical limit (the smaller the tip-surface area, the more concentrated the electric field, and

the greater the field enhancement factor); and, like graphite, they are chemically stable and

resist virtually any chemical impact unless they are simultaneously exposed to several

chemicals.Carbon nanotubes are suitable candidates for electronic devices,

chemical/electrochemical and biosensors, transistors, electron field emitters, lithium-ion

batteries, white light sources, hydrogen storage cells, cathode ray tubes (CRTs), electrostatic

discharge (ESD), and electrical-shielding applications because of all of these characteristics.

Three main methods are currently available for the production of CNTs: arc discharge, laser

ablation of graphite, and chemical vapor deposition (CVD).

In the first two processes, graphite is combusted electrically or by means of a laser, and the

CNTs developing in the gaseous phase are separated. All three methods require the use of

metals (e.g. iron, cobalt, nickel) as catalysts.

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CVD process.The CVD process currently holds the greatest promise, since it allows the

production of larger quantities of CNTs under more easily controllable conditions and at

lower cost. In the CVD process, manufacturers can combine a metal catalyst (such as iron)

with carbon-containing reaction gases.

1.1.5. PURIFICATION OF MWCNT.

MWCNTs were initially acid treated using H2SO4/HNO3 mixture under reflux conditions, to

improve their dispersion and surface reactivity and also to remove other carbonaceous

materials produced during synthesis [26]. Briefly, 0.1 g of MWCNTs was treated with a

mixture of sulphuric acid (3 M) and nitric acid (3 M) (3:1 ratio) in a round bottom flask

equipped with a condenser. The mixture was ultra sonicated for 30 minutes followed by

stirring for 30 minutes and further refluxed at 120℃ for 8 h. The resulting mixture was

diluted in water and washed till neutral pH was achieved. The sample was dried in the oven at

60℃ overnight.

1.1.6. SYNTHESIS OF POLYANILINE:

PANI was made using APS as an oxidant in a chemical oxidative polymerization process. In

a 200-ml beaker, 1 ml aniline monomer was dissolved in a 1.5 M, HCl solution (70 ml). 2 g

of APS was dissolved in 20 ml deionized water in a separate beaker. The aniline solution was

then dropped by drop with the prepared APS solution. The solution switches colour from

straw to deep green.The whole solution was then stirred at constant speed for 5 h at room

temperature.The entire solution was then stirred at room temperature for 5 hours at a steady

pace. To make green emeraldine salt of PANI granules, the entire solution was filtered,

6
washed with deionized water and ethanol several times, and dried at 608C after full

polymerization.[27]

1.1.7. METAL OXIDE(STRONTIUM OXIDE):

Metal oxides are desirable for detecting various hazardous, poisonous, and explosive gases

because of their stable chemical transduction properties, which can reversibly convert

chemical reactions on a surface, and their stable chemical transduction properties, which can

reversibly convert chemical reactions on a surface. The development of gas sensors, which

account for nearly 21% of all metal oxides used in the field, is accelerating. Because of their

distinct characteristics, such as low cost, long lifespan, quick response time, and high

sensitivity. However, some limitations in these structures have been identified, such as the

background gas effect, poor selectivity, and power consumption in high temperature

environments, which may not be sufficient.[23].Because of their stable chemical transduction

properties, which can reversibly transform chemical reactions on a surface, metal oxides are

attractive for detecting various toxic, poisonous, and explosive gases. The production of gas

sensors is accelerating, accounting for nearly 21% of all metal oxides used in the field.

Because of their unique features, such as low cost, long lifespan, fast response time, and high

sensitivity.The optical and electronic properties of materials change drastically due to the

quantum confinement of the charge carriers within the particle. SrO, an important wide band

gap metal oxide (MOX) has attracted much attention. Jose et al. [24] reported the glass

system of SrO for new broadband Raman gain media. Due to the inherent high-energy

phonons in silicate-based glasses, usable rare-earth ions, which are optically active for optical

amplification, are limited in silicate-based fibers.In this fabrication, we reduce SrNO 3 into

SrO3 Using IN of NaOH solution.

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1.1.8. SCHIFF BASE LIGAND.

Schiff base ligands have been used as auxiliary scaffolds in a number of metal-based catalysts

for quite some time. However, the full potential of these interesting ligands can only be

realised when they are combined with metal ions. Schiff bases and metal centres proved

particularly useful, not only because their steric and electronic properties can be easily

tailored, but also because they can be used as modular building blocks in the construction of

more complex architectures.

These unique features make them universal templating agents, not only binding metal centers

as a central ion, but also forming a variety of multinuclear molecular and supramolecular

structures. Molecular metal complexes incorporating simple or modified (by addition

appropriate functional group) Schiff base ligands may also lead to noncovalent interaction-

driven self-assembly of molecular entities, which appears a highly attractive strategy for

constructing new interesting supramolecular materials. Specifically, polydentate Schiff bases

and functionalized Schiff base-based metallic ligands can act as linkers connecting other

metal centers, which may result in forming coordination networks of various dimensionality.

The design strategies and self-assembly possibilities described in this article shed light on the

versatility of structures and properties of Schiff base-metal-based systems; however, the

8
search for novel properties and the use of these species in application-oriented research

remains a considerable challenge.

1.1.9. SYNTHESIS OF SCHIFF BASE LIGAND:

To a solution of 2-amino-4,6-dimethoxypyrimidine (1 mM) in ethanol, an ethanolic solution

of 2-hydroxy-3-methoxybenzaldehyde (1 mM) was added. For 2 hours, the reaction mixture

was stirred and refluxed. The resulting solution was evaporated in a water bath before being

washed in cold ethanol. From hot chloroform, the obtained orange-colored precipitate was

recrystallized.

2.1.0. LITERATURE REVIEW.

Sakshi sharma et al (2014) has fabricated MWCNT-conducting polymer poly(3,4-

ethylenedioxythiophene)–polystyrene sulfonic acid(PEDOT:PSS)based ammonia gas

sensors.Sensor recovery posed a great problem at room temperature and a new approach is

proposed to get complete recovery, exclusively tested in polymer–CNT composite sensor, to

lessen the heat dependence and improve the cycling behavior. Here, she investigated both

MWCNT–PEDOT:PSS and MWCNT–PANI composites and found that MWCNT–

PEDOT:PSS composite is more sensitive and recovered completely.

Biji pullithadathil et al (2015) has reported that(PANI/MWCNTs) based nanocomposite has

produced excellent response for trace level detection of ammonia (NH 3) gas under room

temperature.The temperature-dependent electrical measurement showed that PANI

governed the electrical properties in the composites.

Sahal saad ali et al (2020) has demonstrated ammonia detection in a humid environment with

MWCNTs/PMMA/PS composites functionalized PANI. (PANI/PMMA/PS/MWCNTs)

composite showed the best sensor performance.

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Ali habibi et al (2021) has fabricated ZnO-MWCNT nanocomposite sensor and investigated

ammonia gas sensing properties at room temperature.His result indicates that the sensitivity

of ZnO-MWCNT sensor to NH3 is higher and more stable.Their studies show that nanotubes

fill the porous spaces between ZnO nanoparticles and make the surface of the film rough.

Hence, the surface area of the sensor and the probability of contact between gas and sensor

increase. However, The response time and recovery time of ZnO-MWCNT sensor is much

higher than other composite.

Li Li et al(2019) has also fabricated Polyaniline/multi-walled carbon nanotube composites

with core–shell structures as supercapacitor electrode materials.This Composite show’s high

conductivity and specific capacitance.The strong interaction in such conjugated systems

greatly improves the charge-transfer reaction between polyaniline and the carbon nanotube.

2.1.1.CHEMICALS REQUIRED

● Ammonium Hydroxide

● Aniline.

● Ammonium persulphate.

● H2SO4

● Hcl

● HNO3

● Ethanol

● Strontium oxide

● NaOH

● MWCNT

● Polyaniline

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 ● Schiff base polymer

● Methanol

● Distilled Water

2.1.2.ANALYTICAL INSTRUMENTS

● Magnetic Stirrer.

● UV Sonicater.

● Oven.

● Dryer.

● UV-Vis Spectrometer.

● Scanning Electron Microscope with EDAX.

● Cyclic voltammetry(Gas Sensing).

● XRD.

● FTIR.

Various combination of gas sensors

COMBINATION AUTHOR

SakshiSharma,Sukhbir Singh,S.S.Islama
MWCNT–PEDOT:PSS

Li Li,Yu Zang,Ling Feng Wang,ye leng wu

PANI/MWCNTs

Sahal saad ali et al

PANI/PMMA/PS/MWCNT

LeilaVatandoust,AliHabibi,HamidSajedeh,
ZnO-MWCNT Mohammadi

MWCNT/WO3 VuTruongDuongabCong,TuNguyen,Dr.aDu
c ChienNguyen

RuO2/PANI/MWCNT Chan Hee Jung,ab Chung-Yul Yoo, a Jong-

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 Nam Kim

Cellulose–TiO2–MWCNT SeongcheolMun,YiChen,JaehwanKim

Fe3O4/MWCNT-polyaniline Ashish Kumar Singh, Minni Singh, Neelam

Verma

Schiff base-ETHYL CELLULOSE Sevinc Zehra, Topal, Kadriye ertekin

TABLE1. Various combination of gas sensors

2.1.3.PROBLEM DEFINITION.

Ammonia is one of the most commonly produced chemical. It's known as anhydrous

ammonia in its purest form. Ammonia is a gas that is formed in the human body as well as in

nature. It acts as a building block for proteins and other complex molecules in the body.

Ammonia is produced naturally in soil through bacterial processes. It's also created by the

decomposition of plants, livestock, and animal waste.

Ammonia is a colourless gas with a suffocating odour that is extremely irritating. It dissolves

quickly in water to form ammonium hydroxide, which can irritate and burn the skin. Under

strain, ammonia gas compresses quickly and forms a smooth, colourless liquid. It's normally

shipped in steel cylinders as a compressed liquid. While ammonia is not highly flammable, it

can explode when exposed to high heat.

The majority of people are exposed to ammonia by inhalation of its gas or vapours. Since

ammonia occurs naturally and is also used in cleaning materials, contamination from these

sources is possible. Due to the extensive use of ammonia on farms, in industrial and

commercial settings, exposure can occur as a result of an unintentional release or a deliberate

terrorist attack.Since ammonia gas is lighter than air and rises, it rarely settles in low-lying

areas. Ammonia, on the other hand, may form vapours that are heavier than air in the

12
presence of moisture. These vapours have the potential to disperse over the ground or other

low-lying areas.

The detection of ammonia gas is the solution to safeguard from the ammonia gas

exposure.The sensing Material can be done with a metal oxide gas sensor, a conducting

polymer, a catalytic gas sensor, or an optical absorption.We developed a sensor with a

specific composition of multiwalled carbon nanotubes (MWCNT/PANI/SrO/DPMM) to

achieve high sensitivity, good selectivity, long-term stability, and fast response. No such

composition exists for a sensing function, to the best of our knowledge.With high sensitivity,

relative ease of synthesis, light weight, and ability to detect gases at room temperature this

gas sensor stands out with better results.

2.1.4. OBJECTIVES.

The objective of our project is,

● To Design a Highly sensitive Ammonia gas sensor with MWCNT and low cost

polymers.

● To Utilize MWCNTs Unique properties for sensing and establish it as one of the ideal

materials for detection.

● To Reinforce MWCNTs with Electrically conducting polymer Polyaniline

(PANI) and Schiff base polymer P(DPMM).

● To dope MWCNTs with Metal oxide(SrO) Nanoparticles that facilitates the charge

transfer.

● To Measure the difference in electrical resistance and Produce Characterization for

sensors.

● To Produce Characterizations for the sensor with the Analysis such as SEM with

EDAX,X-ray diffraction(XRD),CyclicVoltammetry(CV),FTIRspectroscopy.

13
 CHAPTER-2

MATERIALS AND METHODS

3.1.0. PURIFICATION OF MWCNT.

fig.2.Schematic diagram of purification of MWCNT.

14
 Fig.3.Purification step of MWCNT.

3.1.1. CHARACTERISATION OF MWCNT

Field emission scanning electron microscope:

Field emission scanning electron microscope (FESEM, FEI NovaNano SEM-600) and energy

dispersive X-ray (EDX) were used for characterization the morphology of synthesized

composite. X-ray powder diffraction (Shimadzu XRD 6000) wasused for the structure phases

and average size of the synthesized nanomaterial. Infrared absorption spectra were measured

at room temperature on a Fourier transform infrared absorption spectrometer (FTIR). Sample

were prepared by gently mixing 10 mg with

300 mg of KBr powder and compressed into discs at a force of 17 kN for 5 min using a

manual tablet presser.

15
Fig.4. Field Emission Scanning electron microscopy (FESEM) image of o-MWCNTs;

(a) Energy dispersive X-ray (EDX) spectrum of o-MWCNT

Fourier transfer infrared (FTIR):

Fig.5.Interpretation of Fourier transform infrared (FTIR) spectra.

Fourier transfer infrared (FTIR) spectra were investigated

with a PerkinElmer Paragon 500 spectrometer using a KBr

pellet with scanning 50 times from 400 to 4000 cm−1 at room

temperature. Thermogravimetric analysis (TGA) system was

performed with PerkinElmer Pyris 1 series under O2

atmosphere with a heating rate of 10 ◦C min−1 to estimate

contents of functional groups in MWCNTs.

16
 TABLE2. Fourier transform infrared (FTIR) Representation.

3600 – 2700 cm-1 X-H (single bonds to hydrogen)

2700 – 1900 cm-1 X≡X (triple bonds)

1900 – 1500 cm-1 X=X (double bonds)

1500 – 500 cm -1 X–X (single bonds)

Fig.6. FTIR spectra of raw MWCNT

X-ray diffraction:

The phase and structure of the composite was investigated by XRD. The strong graphite peak

of plane 002 at 2 = 25.8◦ is clear in both XRD patterns of o-MWCNTs.The other diffraction

peaks related to MWCNTs at the angle 2 of 42.7◦, 43.9◦, 53.5◦ and 77.5◦ can be indexed to

the (1 0 0), (1 0 1),(0 0 4) and (1 1 0) planes of MWCNT.

17
 Fig.7. XRD pattern of o-MWCNT

The elemental quantitative analysis:

The elemental quantitative analysis is done by EDX set for pure MWCNT

nanocomposite.The only presence element in MWCNTs is carbon.

Fig.8. The EDX analysis of MWCNT

3.1.2. SYNTHESIS OF POLYANILINE:

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 Fig.9. Synthesis step of polyaniline.

3.1.3.CHARACTERISATION OF PANI:

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 Fig.11. FTIR spectra of raw polyaniline

X-ray diffraction:

The X-ray diffraction (XRD) patterns of the PANI composite are shown in Fig. 1. The

diffraction peaks of emeraldine salt polyaniline powder are located at 2θ = 21.5◦, 25.7◦ and

28.1◦ which indicate of polycrystalline polyaniline.The PANI crystallinity is due to

benzenoid and quinoid rings repetition in PANI chains. The broad peak 2θ =

25.7◦corresponds to [110] plane of PANI indicates of nanocrystallite size of PANI.

20
 Fig.12. XRD image of PANI

scanning electron microscope

Figure 4 shows the scanning electron microscopy (SEM) images of PANI nanoparticles.From

image, there is interlocking arrangement and network morphology of PANI particles.

Fig.13. SEM of PANI nanoparticles

Atomic force microscopy

Among the important factors which have an effect on the optical and electrical properties in

application to sensing devices is morphology. The 3D AFM images of the PANI

nanocomposites with five percentages of shown in Fig. 5. From this figure the PANI

nanoparticles are uniform in the array and the grains with spherical structure. Measurement

21
larger than crystallite size obtained by XRD, that refers to that grains aggregation of many

crystals.

Fig.14. The 3D AFM images of the PANI nanoparticles.

(a) (b)

Fig.15. Sensitivity and Conductivity images

(a) Gas sensitivity for Ammonia with operation temperature of PANI.

(b)Resistance changing with the time of PANI

TABLE 3.Interpretation From Sensitivity and Conductivity images

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3.1.4.SCHIFF BASE LIGAND:

Fig.16.Synthesis step of schiff base ligand.

3.1.5.Characterization of Schiff base ligand (DPMM)

Here, new Schiff base ligand prepared from pyrimidine derivatives. The synthesized

Schiff base was characterized by elemental analysis, 1H-NMR and mass spectrometric

methods. The obtained yield and color of the DPMM was 80% and orange.

23
Elemental analysis

Elemental analysis data are as follows: Anal. Cald (%) for C14H15N3O4: C, 58.14; H,

5.19; N, 14.53; Found (%): C, 58.01; H, 5.01; N, 14.05.

1
H-NMR spectroscopy

In 1H NMR spectrum of the DPMM was shown in Figure 17 The singlet peak signal

appeared at 8.4 ppm due to the presence of imine proton of DPMM. In addition, the aromatic

proton signals appeared in the region of 6.4–6.9 ppm, pyrimidine moiety proton signal at 6.1

ppm, hydroxyl proton observed at 5.4 ppm and methoxy proton signal at 3.6–3.9 ppm.

Fig.17.H-NMR spectrum of DPMM Mass spectra

Mass spectrum of DPMM shown in the Figure 18. The molecular ion peak of DPMM

is predicted at 289 (m/z).

Based on the analytical and spectral techniques result shows that the proposed

structure of the ligand is given.

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 Fig.18. Mass spectrum of DPMM

3.1.6.SYNTHESIS OF STRONTIUM OXIDE FROM STRONTIUM NITRATE:

Scanning electron microscopy (SEM)

The SEM image of the SrO NPs. The shape of the SrO NPs is a nearly spherical

arrangement on the smooth surface which bound parallel together as small layer

formation with the diameter in the range of 25–50±2.5 nm and having an average

diameter of 75±2.5 nm. In combustion method has 1–30 µm in size particles with smooth

surface square alumina-like aggregates.

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 Fig.19. Scanning electron microscopy image of strontium oxide nanoparticles

Fourier transfer infrared (FTIR):

Figure 19 depicts the FTIR spectra of SrO NPs. SrO NPs have peaks between 500 and

1000 cm1 due to bending vibrations of Sr-O at 428.20 cm1, 732.95 cm1, 810.10 cm1,

and 856.39 cm1 [22]. O-H bending and C-O stretching vibrations are represented by the

sharp absorption bands at 1330.88 cm1, 1433.11 cm1, 1737.86 cm1, and 3383.14 cm1.

The O-H and C-O stretching bonds in the FTIR spectrum are very close to the FTIR

spectrum of OS leaf extract that we previously mentioned. The presence of C-O, O-H, C-

C, and C-N peaks suggests that all SrO NPs were made with OS leaf extract as a

reducing agent and capping agent on the surface of metal oxide nanoparticles.

26
Fig.20. Fourier-transform infrared spectrum of strontium oxide nanoparticles

Energy dispersive X-ray (EDX) spectroscopy:

Energy dispersive X-ray spectroscopy was used to determine the elemental composition

of SrO NPs. The presence of Sr and O elements is suggested by EDX analysis, but no

other impurities are found. In the SrO NPs obtained from EDX analysis, the Sr/O atomic

ratio was 1:1, which was compatible with the metal oxide formula. The EDX study

confirms that the SrO particles only contain metal and oxygen, indicating that the

synthesised sample is pure.

27
Fig.21.Energy dispersive X-ray spectrum of strontium oxide nanoparticles

Fig.22. Energy dispersive X-ray spectrum of strontium oxide nanoparticles

Optical properties:

28
UV-Visible absorbance and reflectance spectra of SrO NPs synthesised with OS leaf

extract in this analysis. The synthesised SrO NPs had a UV-Vis absorption peak at 274

nm and a transmittance peak at 296 nm. The transmittance peak indicates the regulated

size of particles and purity of the sample, and the peak at 274 nm is due to the quantum

size effect of monodispersed colloidal particles. The UV-Vis spectrum has wide

spectrum at 265 nm and 290 nm, which is due to the quantum size effect and surface

morphology of the particles, respectively. The peak at 290 nm is also explained as a sign

of particle purity and size regulation.

Fig.23. UV-visible spectrum of strontium oxide nanoparticles. (a) Absorbance (b)

reflectance spectrum

The band gap energy is measured using the Kubelka– Munk function F(R) = (1-R)2/2R

and the diffuse reflectance (R) of the respective metal oxide nanoparticles. To obtain for

a direct permitted transitions, a plot of (F(R)*hv)2 versus h is drawn, and the linear

regions are extrapolated to the zero ordinate.

Tauc's plot of SrO NPs is seen. According to Fig. 6, the band gap energy of SrO NPs is

5.39 eV, which is higher than the band gap energy of bulk SrO (1.8 eV). The pattern of

decreasing particle size affects the increase in the band gap energy of the sample due to

the quantum confinement effect.The SrO NPs generated in this study are in the

29
nanophase.

Fig.24.(αhν)2 versus (hν) spectra of strontium oxide nanoparticles.

Fig.25.Photoluminescence spectrum of strontium oxide nanoparticles

30
4.1.0.SENSOR COMBINATIONS WITH FTIR RESULTS:

4.1.1.MW01:

Fig.26.MW01composition :PANI + Sr(NO3)2+1N of NaOH

FTIR research tests a sample's absorbance of infrared light at different wavelengths to

determine the material's molecular composition and structure by exposing it to infrared

radiation (IR). The Fourier transform spectrometer converts the raw data from a broad-

band light source into the absorbance level for each wavelength.Good, liquid, and

gaseous samples can all be analysed with FTIR. A viable analysis usually only requires a

small amount of material, and most analyses can be completed quickly with little sample

preparation.There Were more than five peaks, informing that the analyzed chemical is

not a simple chemical.Here MW01 combination has Polyaniline + Strontium nitrate+1N

of NaOH where in the first peak shoots at 3433.96 cm-1 implies Dimeric OH stretch in

Strontium nitrate while reacted with 1N of NaOH and the second peak shoots at 1600.76

cm-1 indicates Primary amine NH bend in Polyaniline.After which the following peaks

such as 1513.32cm-1 , 1407.43cm-1 clearly shows the They appeared as two sets of

absorption bands around 1600cm-1 and 1500 cm-1 . These aromatic rings are usually

followed by the existence of weak to moderate absorption.The Fingerprint region also

exist between 1600.76cm-1 -1407.43cm-1 Wavelength.

31
 Fig.27.Fourier-transform infrared spectrum of MW01.

4.1.2.MW02:

Fig.28. MW02 composition:PANI + Sr(NO3)2+MWCNT+1N of NaOH

Figure 28 shows the Composite MW02 Represents Polyaniline + Strontium nitrate

+Multiwalled CarbonNanoTube+1N of NaOH.To understand the appearance peaks in the

FTIR below,a step-by-step process can be used.

Regarding the number of peaks, there are more than five peaks, informing that the

analyzed chemical is not a simple chemical.The first peak shoots at 3435.22 cm-1

implies Dimeric OH stretch in Strontium nitrate while reacted with 1N of NaOH and the

second peak 1598.53 cm-1 Primary amine NH bend in Polyaniline As like MW01

32
Composite.After which the following peaks C-H bending vibration with the intensity of

medium absorption to strong which sometimes has single or multiple absorption bands

found in the area between 1407.43cm-1 and 880.92cm-1.

Fig.29.Fourier-transform infrared spectrum of MW02.

4.1.3.MW03:

Fig.30.MW03 COMPOSITION :PANI + Sr(NO3)2+MWCNT+DPMM+1N of NaOH

Figure 30 shows the Composite MW03 Represents Polyaniline + Strontium nitrate

+Multiwalled CarbonNanoTube+DPMM+1N of NaOH.To understand the appearance

peaks in the FTIR below,step-by-step process can be used.There are more than five peaks

in the number of peaks, indicating that the examined chemical is not a simple

33
chemical.The number of absorption bands in the entire IR spectrum is determined. The

compounds studied are simple organic compounds with inorganic compounds, the

sample has a simple spectrum if less than 5 absorption bands. The sample is a complex

molecule if the FTIR spectrum has more than 5 absorption bands.The first peak shoots at

3434.01 cm-1 implies Dimeric OH stretch in Strontium nitrate while reacted with 1N of

NaOH and the second peak shoots at 2359.60 cm-1indicates triple bond region (C≡N)

Due to the MWCNT presence with schiff base where in 1630.63 cm-1 and 1451.36

cm-1 represents the fingerprint region.Also the presence of Alkenyl C=C stretch and

Vinyl C-H in-plane bend where known from this region.

Fig.31.Fourier-transform infrared spectrum of MW03.

4.1.4.MW04:

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 Fig.32.MW04 COMPOSITION :Sr(NO3)2+MWCNT+1N of NaOH

Figure 31 shows the Composite MW03 Represents Strontium nitrate +Multiwalled

CarbonNanoTube+1N of NaOH.The number of peaks is greater than five, meaning that

the chemical under investigation is not a simple chemical. The total number of

absorption bands in the IR spectrum is found out. The compounds analysed are simple

organic compounds with inorganic compounds; if there are less than five absorption

bands, the sample has a simple spectrum. If the FTIR spectrum has more than 5

absorption bands, the sample is a complex molecule.The first peak shoots at 3992.84 cm-

1implies Dimeric OH stretch in Strontium nitrate while reacted with 1N of NaOH and

the second peak 3438.46 cm-1 H-bonded OH stretch.Now,The other peaks where in

1626.96 cm-1 and 1470.47 cm-1 represents the Fingerprint region.Also the presence of :

Identifying the double bond region (1500 cm-1 - 2000 cm-1 ) Double bound can be as

carbonyl (C = C)1850 cm-1 - 1650 cm-1 for carbonyl compounds were known from this

region.

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Fig.33.Fourier-transform infrared spectrum of MW04.

CHAPTER – 3

36
 RESULT & DISCUSSION

5.1.0.AMMONIA GAS SENSING:

Measurement of gas sensing property The gas sensing properties of MWCNT and

MWCNTs/PANI/DPMM/SrO were tested by measuring the change in the initial resistance of

the sensor upon controlled exposure to NH3 gas.The experimental setup used for gas sensing

property measurement is depicted. The sensor was loaded into a stainless steel chamber,

where the electrical resistance of the sensor was measured as a function of time using two-

probe configuration. All experiments were performed at room temperature (28 ± 2oC at 65 ±

3%RH) under atmospheric pressure conditions. The sensor was purged with dry nitrogen

(N2) gas before exposing to the target analyte in order to clean the surface by removing the

impurities and moisture, if absorbed any. A gas generator (OVG-4, Owlstone Nanotech) was

used as the source for ammonia gas generation through permeation tube technology to

produce trace level concentration. In this system, NH3 permeation tube was pre-calibrated at

different temperatures and flow rate to deliver desired concentration and it is traceable to

standard NIST. For the preparation of NH3 permeation tubes, liquid-phase NH3 (99.99%

purity, Sigma Aldrich) was sealed inside a Teflon tubes. Gas phase NH3 subsequently

diffuses through the Teflon tube wall into the ultra-pure dry N2 carrier gas, flowing at 100

sccm. The mixing ratio of ammonia in N2 was pre-calibrated with respect to the temperature.

The outlet of the OVG-4 gas generator (dry N2+NH3) is then fed in to the sensor test

chamber for further measurements. The gas flow was set at a constant flow rate of 100 sccm

for all measurements and the flow of the gases was controlled using mass flow controllers.

The resistance of the nanocomposite films as a function of time was continuously measured

by a two-probe configuration using digital multimeter (Agilent 34401A) which was

connected to computer by USB interface for data acquisition. The sensor response (S) is

defined as the ratio of the change in resistance upon exposure to target analyte to the

37
resistance (Ra) of the sensor in clean carrier (dry N2) gas. 100% g a a R R S R - = ´ where,

Rg and Ra are the resistances of the sensor in the presence of NH3 and in pure carrier gas

(dry N2) respectively. The response time and recovery time were calculated as the time taken

for the sensor to attain 90% of total resistance change (T90) from its initial resistance.

6.1.0.CONCLUSION.

38
 PANI/MWCNT/DPMM/SrO nanocomposite was synthesized by in-situ chemical

oxidative polymerization of aniline monomers on carboxylated MWCNTs. The

morphological and structural characteristics of the PANI/MWCNT/DPMM/SrO

confirmed the formation of PANI uniformly wrapped around MWCNTs. Comparative

gas sensing property analysis of the MWCNT and PANI/MWCNT/DPMM/SrO

nanocomposite based gas sensors revealed excellent sensor performance for

PANI/MWCNT/DPMM/SrO nanocomposite based sensor compared to MWCNTs in

the concentration range of 2-10 ppm of NH3 which is attributed to the presence of

functional polyaniline on the surface of MWCNT. Moreover, fast response and good

reversibility was observed for the PANI/MWCNT/DPMM/SrO based sensor

compared to the MWCNT which can be mainly attributed to the enhanced charge

transfer through the thick polymer layer on MWCNT. The effects of humidity and

oxygen showed minimal interference on the sensor response. The

PANI/DPMM/SrO/MWCNT nanocomposite was found to be highly selective towards

NH3 gas compared to cross-interfering gases. The study explores the possibility of

using PANI/MWCNT/DPMM/SrO based low cost, room temperature sensor for trace

level detection of NH3 g.

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