fax:040-23156128 ph: off: 040-23155413

e-mail: kmukkanti@yahoo.com. res:040-23156955

cell:9346325591

dr.k.mukkanti ph.d
professor & head
________________________________________________________________________
to 24thaug2007
the registrar
jnt university
kukatpally,
hyderabad – 500 072.
sir, (through proper channel)
sub: request to permit for submission of the r & d project entitled “detection of
ammonia in the environment by using swcnt/s-pani composite thin
film sensor ” to ugc – and issue the forwarding certificate - reg

i am submitting a r & d project proposal “detection of ammonia in the

environment by using swcnt/s-pani composite thin film sensor ” .
this project work if sanctioned will be carried out at jntu, hyd. i request you to permit for the
same and issue a forwarding certificate for submission to ugc, new delhi.
thanking you,
yours faithfully,

(k.mukkanti)

1
 date: 23rd aug 2007
to,
the secretary
university grants commission
new delhi

sir,

a research project entitled “detection of ammonia in the environment by

using swcnt/s-pani composite thin film sensor ”
1. it is certified that same project or the investigator has not submitted project with
similar objectives to any other funding agency.
2. we have carefully read the terms and conditions of sanctioning the project and agree
to abide by them.
3. the organization will provide all necessary infrastructure facilities (both laboratory
and administrative) if the project is sanctioned.
4. the organization is fully responsible in regard to matters pertaining to the project.
5. certified that the equipments proposed in the project are not available in our
institution.

yours faithfully,
place : hyderabad
date :

(registrar)
fax:040-23156128 ph: off: 040-23155413
e-mail: kmukkanti@yahoo.com. res:040-23156955
cell:9346325591

dr.k.mukkanti ph.d
professor & head
________________________________________________________________________

certificate by the principal investigator/co-investigator

1. certified that at present we are not receiving any funds from the ministry for any other project.

2. certified that the equipments proposed in the present project proposal are not available in my
laboratory/ institution

dr.k.mukkanti

place : hyderabad
date :
(principal-investigator)

3
 appendix 1

proforma of application for research grants

(please read carefully the guidelines to investigators before filling

this proforma)

1 research station / institution

name centre for environment

address centre for environment,

institute of science &

technology, jnt university,

kukatpally,

hyderabad- 500085

telephone 040-23155413

fax 040-23155413

e-mail kmukkanti@yahoo.com

nearest rail head/airport hyderabad

2 principal investigator

name dr.k.mukkanti
designation professor & head
address centre for environment,

institute of science &

technology, jnt

university, kukatpally,

hyderabad-500085

telephone 040-23155413

fax 04023155413

e-mail kmukkanti@yahoo.com
3. brief bio-data of the investigators

(enclosed at the end of the proposal)

4. project title (keep it as short as possible) -

“detection of ammonia in the environment by
using swcnt/s-pani composite thin film sensor ”
5 track record and workload assessment of the pi

list all the research and consultancy schemes, whether funded by mowr or
any other agency, in which the present pi is/was principal investigator, in
following groups.

a. schemes completed -1 (m

b. schemes foreclosed with reasons for foreclosure

c. schemes ongoing -2

6 if the scheme is sanctioned, in whose name the cheque is to be

issued. (write precise title of the account)

director, ist, jnt university

7 category of r&d activity (tick those which are applicable)

a. basic research

b. applied research -

c. action research

d. education & training

e. mass awareness programme

f. infrastructure development

g. creation of centres of excellence

5
8 description of the proposal
polyaniline (pani) was another extensively studied conducting polymer which
has high stability, good conductivity and reversible redox property.
sulfonated polyaniline (spani) has sulfonic groups on its backbones, so it is
soluble in water. spani with methoxyls on its benzene rings has been used as
the dopant for ppy and the resulting composite film exhibited improved
cathodic expansions. herein, we report the syntheses and characterizations
of ppy/spani self-standing films by direct oxidation of pyrrole in the aqueous
solution of spani. these films showed unique electrochemical properties and
high performance on ammonia gas sensing.

a novel conductive polyaniline is synthesized using poly (4-styrenesulfonate-

co-maleic acid) as counter ion and template. the resistance of this electro
active polymer increases in the presence of gases such as ammonia. this
transducing property is exploited and spin-cast film of this material on glass
substrate is established as ammonia gas sensor module, for gas
concentrations in the range 5–250 ppm. in this range, the response and
recovery times are typically 50–1000 s. the resistance response (r/r0) at
short time scales of about 150 s, is shown to vary linearly with the ammonia
concentration. qualitative and quantitative analysis of chemical and
biochemical substances present in the environment have tremendous
importance in connection with environmental monitoring, personal
protection, safety and process control. development and fabrication of
systems for this purpose are of great contemporary interest. choice of
suitable sensing materials along with efficient microelectronics for the
detection system is the key step in such efforts. a wide range of materials of
organic and inorganic origin are used as sensing elements. inorganic
materials such as the oxides of tin and zinc have been used extensively. one
of the practical problems with oxide sensors is the need to adopt high
operating temperatures. organic compounds as sensor active materials
circumvent this limitation since they operate at ambient temperatures.
several types of organic materials have been used for gas sensing. these
include porphyrins, phthalocyanines and conjugated polymers. conducting
conjugated polymers offer major advantages because of the facility with
which the recognition elements can be tailored by chemical synthesis and
thin film fabrication techniques. an ammonia sensor based on conducting
polypyrrole was one of the early practical realizations of conducting polymer
sensors. its sensitivity, however, was relatively low and the response not
very reversible.

we have recently investigated the control of spani formation using

polyelectrolyte templates.
in recent years, a lot of attention has been given to the use of conducting
polymers in chemical sensors, as sensing layers for gases detection, because
of merits such that easy fabrication, low power consumption, and low
poisoning effect.
sno2 and fe2o3.

the principal advantages of such materials include high dependence on the

detecting environments. however, the presented optical method shows
independence from environmental interference.
the polyaniline films show significant optical transmittance changes upon
exposure to ammonia gas at room temperature. this study demonstrates the
optical property advantage of polyaniline (pani) over metal oxide.

9 objectives. classify the objectives of proposed research under

one or more of following and explain the objectives briefly.

polyaniline (pani) was found to be a better choice for gases such as ammonia

because of its higher sensitivity, reversible response and shorter response

time. the effect of ammonia and water on the conductivity of polyaniline has

been investigated along with the polymer adsorption capacity. the

transducing behavior of polyaniline has been exploited in thin film sensors

for several gas molecules as well as volatile organic compounds. in spite of

the various advantages of conducting polymer based gas sensors, some

fundamental problems persist. the fabrication of good quality films is often

hampered by solubility problems. long-term mechanical and chemical

stability of the polymeric materials are points of concern in many instances.

sensitivity of the responses is not always satisfactory. in such a case

ammonia sensors based on swcnts/sulphonated pani (s-pani) there will a

considerable improvement of reversibility and reproducibility of the

processes involved in the sensing action.

7
10 putting the research to use

a. identify the possible end-users for the results of proposed research.

b. list the actions that will be necessary to put the results to use.

c. list the difficulties/problems that may be encountered in putting the

results to use.

d. are the possible end users being involved in the research ? if yes then
describe how, if not then explain why not.

11 present state of art

conducting polymers constitute a new class of sensing materials, that are

prepared by a simple oxidative polymerization method. since their discovery,

intrinsic conducting polymers (icps) have been investigated intensively

because of a select group of properties that they exhibit: electronic

conduction, environmental stability on the conducting state, reversible redox

reactions, electrocromism, and electroluminescence. conducting polymers

offer themselves as an excellent sensing materials, among the many,

polypyrrole (ppy) is the most extensively used in the designing materials for

chemical gas sensors. versatility of this polymer is determined by a number

of potential applications: strong absorptive properties towards gases, dna

proteins, catalytic activity and, corrosion protection properties etc. ppy and

ppy doped with copper films revealed increasing the resistance by exposure

of reducing gases such nh3, h2 and co.

references:

1. b. li, g. sauvé, m. c. iovu, m. j.-el, r. zhang, j. cooper, s. santhanam, l.

schultz, j. c. revelli, a. g. kusne, t. kowalewski, j. l. snyder, l. e. weiss, g. k.
fedder, r. d. mccullough, and d. n. lambeth, volatile organic compound
detection using nanostructured copolymers, nano lett., 6 (2006) pp.1598
-1602.
2. wiley periodicals, inc. j appl polym sci 92: 37–42, 2004
3. k. potje-kamloth, chemical gas sensors based on organic semiconductor
polypyrrole, critical rev. anal. chem. 32 (2002) pp. 124-140.
4. m.m. chehimi, m.l. abel, c. perruchot, m. delamar, s.f. lascelles and s.p.
armes, synth. met. 104 (1999) pp. 51-59
5. b. saoudi, c. despas, m.m. chehimi, n. jammul, m. delamar, j. bessiere
and a. walcarius, sens. actuators b 62 (2000) pp. 35-42
6. azioune, f. siroti, j. tanguy, m. jouini, m.m. chehimi, b. miksa and s.
slomkowski, electrochim. acta 50 (2005) pp. 1661-
1667http://www.sciencedirect.com/science?_ob=articleurl&_udi=b6tg0-4dvbdy8-
2&_user=2354535&_coverdate=02%2f15%2f2005&_fmt=summary&_orig=search&_cdi=5
240&view=c&_acct=c000057047&_version=1&_urlversion=0&_userid=2354535&md5=3
3d995df5ca8474fbaf52abaae
7. v.g. khomenko, v.z. barsukov and a.s. katashinskii, electrochim. acta 50
(2005) pp. 1675-1688
8. n.t.l. hien, b. garcia, a. pailleret and c. deslouis, electrochim. acta 50
(2005) pp. 1747.
9. l. torsi, m. pezzuto, p. siciliano, r. rella, sabbatini, l. valli, p. g. zambonin,
conducting polymers doped with metallic inclusions: new materials for
gas sensors, sens. acuators, b, chem. 48 (1998) 362-367
10.matsuguchi, m.; io, j.; sugiyama, g.; sakai, y. synth met 2002, 128, 15
11.chabukswar, v. v.; pethkar, s.; athawale, a. a. sens actuators b 2001, 77,
657.
12.jin, z.; su, y.; duan, y. sens actuators b 2001, 72, 75.
13.li, d.; jiang, y.; wu, z.; chen, x.; li, y. sens actuators b 2000, 66, 125.
14.agbor, n. e.; petty, m. c.; monkman, a. p. sens actuators b, 1995, 28,
173.
15.nicho, m. e.; trejo, m.; garcia-valenzuela, a. sens actuators b, 2001, 75,
18.
16.oh, k. w.; hong, k. h.; kim, s. h. j appl polym sci 1999, 74, 2094.
17.lee, d. s.; rue, g. r.; huh, j. s.; choi, s. d.; lee, d. d. sensactuators b 2001,
77, 95.
18.muellerleile, j. t.; freeman, j. j. j appl polym sci 1994, 54, 135.
19.macdiarmid, a. g.; chiang, j. c.; richter, a. f.;epstein, a. j.synth met 1987,
18, 317.
20.hu, h.; trejo, m.; nicho, m. e.; saniger, j. m.; garcia-valenzuela, sens
actuators b 2002, 82, 14.

9
21.gasser, r. p. h. an introduction to chemisorption and catalysis by metal;
oxford science publications: oxford, uk, 1985; pp.1–76.
22.paterno, l. g.; manolache, s.; denes, f. synth met 2002, 130, 85.

12 methodology
1. among organic conducting polymers, polyaniline (pani) is regarded as

one of the most technologically promising conductive polymers because the

monomer is inexpensive, the polymer can be easily prepared by oxidative

polymerization with high yield, and products are stable under ambient

conditions.6 promising results have also been shown for application in gas

sensors. this mechanism is attributed to the _-conjugated system in the

conducting polymer chain. the interaction between the organic material and

gas molecules results in an increase/decrease of polaron and/or bipolaron

densities inside the band gap of the polymer. therefore their modification

implies both electrical and optical property changes in the conducting

polymer.

polyaniline (pani) was found to be a better choice for gases such as ammonia

because of its higher sensitivity, reversible response and shorter response

time. the effect of ammonia and water on the conductivity of polyaniline has

been investigated along with the polymer adsorption capacity. the

transducing behavior of polyaniline has been exploited in thin film sensors

for several gas molecules as well as volatile organic compounds. in spite of

the various advantages of conducting polymer based gas sensors, some

fundamental problems persist. the fabrication of good quality films is often

hampered by solubility problems. long-term mechanical and chemical

stability of the polymeric materials are points of concern in many instances.

sensitivity of the responses is not always satisfactory. in such a case

ammonia sensors based on swcnts/sulphonated pani (s-pani) there will a

considerable improvement of reversibility and reproducibility of the

processes involved in the sensing action.

these films were then deposited by means of dip coating over two comb-like

inter-digitated gold electrodes screen-printed on an alumina chip substrate.

the change in resistance of spani on exposure to aqueous ammonia has been

utilized for the study of a prototype chemical sensor. these properties make

possible their use in several practical applications, including batteries,

antistatic coatings, electromagnetic interference shields, display, and

capacitors for example.

a. preparation of spani

pani (in emeraldine form) was synthesized by chemical oxidation of

aniline with ammonium persulfate at 00c . pani was sulfonated with

chlorosulfonic acid and finally hydrolyzed into spani.

swcnt’s ( single walled carbon nanotube)

additional of swcnts are mainly to enhance the signal to measure

lower levels of ammonia. the swcnts were synthesized in the lab or

obtained laboratory.

11
b. uv photo polymerization

appropriate weight of monomer aniline was added to 100 ml of

ethyl alcohol to form solution. approximately quantity of agno3 was

added to the solution and stirred thoroughly making it equally

distributed in the pyrrole alcohol matrix and available for

polymerization. subsequently, chips will be dip coated with the

monomer material. the chip was made of an alumina substrate with

dimensions of 10mm × 5mm on which pair of comb-like inter-

digitated gold electrodes were screen printed (see fig.), and

followed by uv treated to photo polymerize at room temperature for

few hours. polymerisation will be confirmed by uv spectroscopy.

c. swcnt/spani thin film preparation

swcnt/spani composite films were prepared by mixing required

weight percentages of swcnts with spani, and then the mixture is

taken into teos solution along with ethanol and water in the ratio

5:16:2. subsequently the chips were dip coated with the mixture

solution.

d. sensing chip

an alumina chip with dimensions of 10 mm by 5 mm comprising of a

pair of comb-like inter-digitated gold electrodes previously screen

printed over the substrate was used to dip coat ppy thin films as

shown in the figure. sensing material is over the gold electrodes.

 these ends of the gold electrodes were connected to the wiring

through platinum electrodes.

e. characterization

i.uv/vis spectroscopy for confirmation of completion of

polymerization

ii.infrared spectroscopy that provides the fingerprint of a

molecule. the fingerprint consists of a unique series of energy

absorbance across a wavelength range of 2.5 to about 14

micrometers (μm). ftir was also used to note the spectral

signature of the ammonia in this study.

2. fabrication of the test sensor

the ammonia sensing performance lm will be studied by measuring electric

resistance changes of the swcnt/spani composite thin film in the gas flow of

ammonia/nitrogen. these two comb like electrodes were connected to a

potentiostat under computer control. the current signal was recorded by applying a

13
constant voltage between these two electrodes. the concentration of ammonia was

controlled by a mass flow controller . the total flow was 1000 sccm (standard cubic

centimeter per minute), and the ammonia concentration was modulated to be 20,

40, 60 or 80 ppm by mixing 1000 ppm source ammonia gas with nitrogen flow

under mfc control. the mixed gas was led to a glass chamber with a volume of 500

ml in which the sensing device was fixed ammonia gas was 1 min on and then cut

off to leave the device under nitrogen flow until the current of the device recovered

to its original value. the response was defined by the slope of the current time curve

recorded during the period.

3. nh3 gas sensing

the developed sensor to monitor the ammonia sensing by the polymer thin

film at room temperature; a schematic view is shown. a 2 l round bottom

flask fitted with a stopper was used for this experiment. electrical

connections for the sensing element and air-circulating fan were introduced

through the stopper and passage was provided for evacuating and

introducing the ammonia gas. ammonia–air mixture was taken from the

headspace of a bottle containing ammonia solution. the ammonia

concentration in the mixture was estimated by trapping a known volume in

ice-cold dilute hydrochloric acid solution that was titrated with standardized

sodium hydroxide before and after the ammonia trapping. uniform

distribution of gas inside the round bottom flask was achieved using the fan.

sensor element was fabricated by fixing four electrical probes on the

swcnt/s-pani film using silver paint or sublimed aluminum. a constant

current source and multimeter were used to apply current and measure the

voltage drop respectively. prior to the introduction of ammonia gas into the

round bottom flask it was evacuated and nitrogen gas was introduced to

create oxygen-free environment. the resistance of the film in this state is

denoted as r0. a known volume of ammonia gas (concentration calibrated as

discussed above) was introduced. the fan was operated to distribute the gas

uniformly. the resistance was monitored every 10 s till saturation was

attained. then the sensor element was removed from the flask and kept in

ammonia-free atmosphere to monitor the conductivity recovery. the

ammonia exposure and cut-off cycles were repeated several times to check

the reversibility and reproducibility of the sensor element.

4. conclusion

the use of modified conducting polymer (spani) composites as sensing elements in

chemical sensors is an intensive area of research because of their high sensitivity

on electrical or optical changes when exposed to diverse types of gases or liquids.

this characteristic holds promise for successful designs of different types of sensor

transducers based on conducting polymers. several reports revealed that

conducting polymers as chemical sensors for air-borne volatile organic compounds

(especially m ,alcohols, ethers, halocarbons, ammonia, no2, and co2) have a lower

detectable limit in the range of a few tens of parts per millions, and the potential to

operate at or near room temperature.

15
13. cost estimates

item 1st 2nd year 3rd total (rs.)

year year
fellowship jrf 1,15,2 1,15,200 1,44,0 3,74,400
(chemistry) 00 00

travel (within 20,00 20,000 20,000 60,000

india) 0
consumables

a. chemicals 60,00 50,000 50,000 3,10,000

0
b. glassware 25,00 25,000 25,000
0
c. commercial gold 25,00 25,000 25,000
chips 0

equipment

atomic force 3,50,000 4,00,000

microscopy
computer 50,000

50,000

sputtering 50,000
machine
quartz crystal 2,50,000 3,00,000
microbalance
mass flow 50,000
controllers -2

total 14,94,400

17
14 work schedule

a. probable date of commencement – immediate after sanction

b. duration of study -3 years

c. stages of work and milestones
identifiable milestones of months from amount to be released
progress start
start 0 (amount of first
instalment)

1 literature survey 0-6

50% of the amount to be

sanction at the begining

2 procuring instruments

3. preparation of polymer
thin films
4. study of proprties

5. manufacturing of sensing from remaining 25% to be

chip & characterization sanctioned at the end os
the first year

6. fabrication of test sensor

7. nh3 gas sensing and

application
8. report preparation remaining amount to be
sanctioned at the end of
 the 2nd year.

notes:

a. the work should be divided into milestones 3 to 6 months apart.

b. the milestones are mainly for the purpose of monitoring of progress

and release of funds. the funds to be released on achieving various
milestones should be indicated.

c. normally there may be only one release of funds in a financial year.

15 declaration

1. i have carefully read the terms and conditions of the research grant
and agree to abide by them.

2. this is to certify that i have neither submitted this proposal elsewhere

for financial support nor have undertaken it at the request of any
commercial agency or as a consultancy.

date signature of pi
place name
designation

19
16 endorsement from the head of the institution
1. the institute / organization welcome the participation of
dr.k.mukkanti, professor & head as principal investigator for above
project.

2. the necessary equipment and institutional support as described in item

13.3 will be made available as and when required for the purpose of
the project to ensure that the work is taken up on priority and
completed on schedule.

3. in the event of foreclosure /discontinuation /cancellation of the scheme

for any reason , the entire amount released for the scheme will be fully
refunded to the mowr along with the interest prescribed till the date of
return by the institute/ organisation.

4. the register of permanent and semi-permanent assets acquired out of

grants from mowr will be maintained in form gfr-19.

5. the assets acquired out of this grant shall be transferred to the desired
destination in good & working condition as and when required.

date : seal
and signature of the
place: head
of the organisation