Study of filtering Ag liquid sample by chitosan biomembrane using laserinduced breakdown spectroscopy (LIBS).
Study of filtering Ag liquid sample by chitosan biomembrane using laserinduced breakdown spectroscopy (LIBS)
Ni Nyoman Rupiasih, Hery Suyanto, Made Sumadiyasa, Christine Prita Purwanto, and Rendra Rustam Purnomo
Citation: AIP Conf. Proc. 1555, 32 (2013); doi: 10.1063/1.4820987
View online: http://dx.doi.org/10.1063/1.4820987
View Table of Contents: http://proceedings.aip.org/dbt/dbt.jsp?KEY=APCPCS&Volume=1555&Issue=1
Published by the AIP Publishing LLC.
Additional information on AIP Conf. Proc.
Journal Homepage: http://proceedings.aip.org/
Journal Information: http://proceedings.aip.org/about/about_the_proceedings
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Study of Filtering Ag Liquid Sample by Chitosan
Biomembrane Using Laser-Induced Breakdown
Spectroscopy (LIBS)
Ni Nyoman Rupiasih1,*, Hery Suyanto2, Made Sumadiyasa2,
Christine Prita Purwanto1 and Rendra Rustam Purnomo1
1
Biophysics Laboratory, 2 Applied Physics Laboratory, Department of Physics,
Faculty of Mathematics and Natural Sciences, Udayana University, Denpasar, 80361, Indonesia
*Email: rupiasih69@yahoo.com
Abstract. The capability of Laser-Induced Breakdown Spectroscopy (LIBS) to resolve filtration process of Ag liquid
sample by chitosan biomembrane is demonstrated. The biomembrane was prepared by inversion method used to filter
Ag liquid using pressurized technique samples which were then analyzed by monitoring the emission corresponding to
Ag (I) at wavelength of 328 nm. The experiment was conducted by varying the laser energy i.e. 80, 120, and 160 mJ,
where, subsequently, and its effect on the depth-profile from 20 - 200 μm was characterized by LIBS. The results
showed that the physical processes of pressurized filtration led a homogeneous Ag in the membrane from the surface to
a depth of 200 μm. The optimum condition was obtained at laser energy of 120 mJ. The adsorption occurred only on
the surface of the membrane i.e. 20 μm depth, but there was no inclusion. Improvement of the detection performance of
adsorption process was done by heating the dripped membrane at 35 oC and was resulting in increase in emission
intensity as expected.
Keywords: Chitosan biomembrane; pressurized filtration; liquid Ag; Laser-Induced Breakdown Spectroscopy
PACS: 82.35Pq
one requires a pulsed laser for generating microplasma on the target surface and elemental analysis is
accomplished by studying the emission of the plasma
plume. The performance of LIBS depends on several
parameters including laser wavelength, pulse energy,
pulse duration, time interval of observation, and
geometrical configuration of collecting optics, target
features, and properties of ambient medium. Extensive
work has been devoted to optimize these parameters
for the best experimental and commercial realization
of this technique.
The main disadvantage of LIBS is the high limit of
detection, about 500 ppm but 1ppm can be reached for
some elements [4].
LIBS is a very versatile technique and have been
used in siderurgy, industrial process control [4-7],
environmental geochemistry, biohazard material
detection, forensic science, microbiology, odontology,
archaeology, cultural heritage and art conservation [812].
Several papers dealing with LIBS applications in
depth-resolved analysis have also reported [5, 9-13].
In their reports, the laser was focused to a different
extent resulting in high irradiances (typically in the
order of 109 - 1011 Wcm-2).
In this study, the main purpose is to explore the
capability of Laser-Induced Breakdown Spectroscopy
INTRODUCTION
Chitosan is the most abundant natural polymer
after cellulose. It is a partially deacetylated product of
chitin, which has many useful features such as nontoxic,
biocompatibility,
biodegradability,
and
antibacterial property. Due to its features, chitosan has
been widely applied in many industries including
weastewater treatment. Chitosan has the ability to
form complexes with metals. It exhibits higher
adsorption capacity for metal ion compared to that of
chitin owing to the amino group content. However, the
serious drawback of chitosan for metal ion adsorbent
from practical utilization is that it is soluble in acidic
media [1-2].
Laser induced breakdown spectroscopy (LIBS) or
laser induced plasma spectroscopy is a useful method
to determine the chemical composition of a wide
range of materials including metals, liquids, aerosols,
plastics, minerals, biological tissues, etc. [3]. As an
analytical technique, LIBS presents some advantages
to other techniques: no sample preparation, real time
analysis, contactless analysis, apparatus or
experimental simplicity, inexpensiveness, robustness,
and quickness are interesting properties which makes
LIBS an attractive analytical technique. In many cases
is a non destructive technique [1]. In this technique
International Conference on Theoretical and Applied Physics (lCTAP 2012)
AIP Conf. Proc. 1555, 32-35 (2013); doi: 10.1063/1.4820987
© 2013 AIP Publishing LLC 978-0-7354-1181-4/$30.00
32
Downloaded 05 Sep 2013 to 114.79.59.195. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://proceedings.aip.org/about/rights_permissions
(LIBS) too resolve filtrration processs of Ag liquiid
sample byy chitosan bio
omembrane ussing pressurizeed
technique. Depth profilee analysis was conducted by
b
varying laser energy from
m 80 to 160 mJ
m each for 20 to
t
200 μm depth.
d
Variouss methods off the adsorptioon
process off Ag solution in the membrranes were alsso
carried ouut i.e. control (w
without treatm
ment) is called as
a
Sample-1; natural adsorp
ption as Sampple-2; adsorptioon
by heatingg as Sample-3
3; adsorption after
a
heating as
a
Sample-4; and adsorption
n with pressuree as Sample-5.
d. Laser-In
nduced Breaakdown
Specttroscopy (LIIBS)
Lasser induced brreakdown specctroscopy was used
to probbe the present of Ag elemennt in the pressuurized
treatedd chitosan biom
membrane at various
v
depths from
the surrface. The LIB
BS 2500-7 pluss model was ussed. It
uses Nd-YAG
N
Laseer (1064 nm (wavelength), 7 ns
(pulse width), 200 mJ
m (max. energgy)) and echellle HR
2500 spectrometer
s
w specifications such as, range
with
of the spectrum 200--980 nm, with 7 channels, FW
WHM
n using 7 deetectors with 2048
resoluttion of 0,1 nm
elemennt linier siliconn CCD arrayss that given tootal of
14336 pixels. The ouutput of the speectrometer anaalyzed
OLIBS and OOIICOR softwarees that displeyyed on
by OO
the moonitor.
In the
t present stuudy, the delay time
t
used was 1 μs,
4 pulses of each scaan, and 0 pulsee cleaning (to avoid
unneceessary scan). The
T laser energgy density (fluuence)
employyed in the expperiments was in the range 600-180
mJ. Thhe pulse to pullse energy variation throughoout all
measurements perforrmed, was no > ± 5%. The saample
was pllaced approxim
mately 2 cm inn front of the focal
point and
a a relativelly wide spot (aapprox. 1 mm) was
used in the LIBS measurement
m
inn order to obttain a
represeentative averaage of the maaterial compossition.
Emissiion spectra were recorded separately for each
one off successive laaser pulses andd were subsequuently
analyzzed.
MAT
TERIALS AND
A
METH
HODS
a. Ma
aterials
The materials
m
used are
a Chitosan powder
p
with
characterisstics i.e. 87,9% deacetylateed and their
solubility in acetic acid is 99,4%; aceetic acid and
sodium hyydroxide p.a. All
A reagents weere analytical
grade and were used with
hout further puurification.
b. Prep
paration of Chitosan
C
M
Membrane
The chhitosan solution
n of 4% (w/v) was
w prepared
by dissolvving 10 g of chiitosan powder in 250 ml of
1% acetic acid solution
n. The mixturee was stirred
for 8 houurs at room teemperature to obtain dope
solution. The
T dope solutiion was pouredd into a glass
plate and dried
d
at room temperature
t
forr 6 days. The
membranee was in the NH
H3+ form. It was
w dipped in
1% sodiuum hydroxidee solution too reach the
unchargedd amino form, washed
w
with diistilled water
3 times to eliminate the excess of sodium
d.The thickneess of the
hydroxide, then dried
membranee was around 236 μm.
RESULTS
S AND DISC
CUSSION
Figgure 1 shows LIBS
L
spectra off control (Sampple-1)
and pressurized
p
t
treated
chitoosan biomem
mbrane
(Sampple-5) scanned with
w laser enerrgy of 120 mJ in the
range 327 - 329 nm. It shows a peak at wavelenggth of
328 nm
n in Samplee-5 which is known as attomic
emission line of Ag (I), whereas no
n peak observves in
the control membranne (Sample-1). This explains that
mple-5 that adm
mitted by presssure.
there is Ag in the Sam
c. Membrane Treatm
ments
In this study, the chiitosan biomem
mbranes have
been treatted in 5 diffeerent ways i.ee. Sample-1:
control (w
without treatm
ment), Sample-2: Ag 1000
ppm droppped on the meembrane and allow
a
to dry
naturally (natural
(
adsorp
ption), Samplee-3: Ag 1000
ppm droppped on the mem
mbrane and heeated to 35°C
(adsorptionn by heatin
ng), Sample-44: heat the
membranee to 35°C then dropped wiith Ag 1000
ppm (adssorption after heating), andd Sample-5:
membranee exposed to Ag
A 1000 ppm
m solution by
filtration method with
h pressure ~ 50 kPa
(adsorptionn with pressuree).
FIGUR
RE 1. LIBS sppectra of controol (Sample-1) and
a
pressurrized treated chhitosan biomem
mbrane (Sample--5)
scannedd with laser eneergy of 120 mJ in the range 3277 329 nm
m.
33
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200
180
160
140
Intensity (a.u.)
120
100
80
Samp
ple-5, 80mJ
60
Samp
ple-5, 120mJ
40
20
Samp
ple-5, 160mJ
0
0
20 40 60 8
80 100 120 140 160 180 200 220
Depth (µm)
FIGURE 2.
2 LIBS spectraa of the pressurrized chitosan
biomembraane (Sample-5) in
i the range 3277 - 329 nm for
laser energiies 80, 120, and
d 160 mJ. Contrrol (Sample-1)
spectrum iss presented (kep
pt at laser energgy of 120 mJ)
for the com
mparison.
FIGUR
RE 3. Intensityy of atomic em
mission of Ag (I) at
wavelength of 328 nm obtained by LIB
BS with laser ennergies
d
from the surface
80, 1200, and 160 mJ ass a variation of depth
for the pressurized chittosan biomembraane (Sample-5).
To study about thhe adsorption process
p
of Ag in the
chitosaan biomembrrane, four methods
m
mem
mbrane
treatment are introduuced. The resullts are shown inn Fig.
4. For natural (Sampple-2) after firstt shot (shot-1, depth
~ 20 μm)
μ by laser energy
e
of 120 mJ, the intensity of
Ag (I) obtained was ~ 6.67 a.u, whhile at a depth of 40
μm (ssecond shot) was null, indicating
i
thaat no
inclusiion process occcurred. To im
mprove the deteection
perform
mance of the
t
adsorptioon processes, an
adsorpption by heatiing method was
w introducedd, the
treatedd membrane with
w the same process
p
of Sam
mple-2
is heaated to 35°C (Sample-3) annd the intensiity is
increassed to ~ 8.75 a.u.
a This indicaates that the prrocess
was innfluenced by the
t temperaturre. Result from
m the
secondd shot was alsoo zero. Furtherrmore an adsorrption
after heating
h
methodd was used. Heating the mem
mbrane
before dripping it with 1000 ppm Ag sollution
(Sampple-4), gave inttensity as low
w as, ~ 5.5 a.uu. The
intensiity of Samplle-5 (adsorptiion with preessure
methodd) was the highhest at ~ 21.5 a.u.
a
Theese results desscribe Ag liquiid penetrate intto the
membrrane properly when
w
pressurizzed (adsorptionn with
pressuure method). This causes Ag interact both
chemiccally and phyysically with the
t
membranee and
producces strong covaalent bonds in the
t membrane. As a
result, providing a strong
s
reboundd momentum during
d
the lasser shot and prroduced plasmaa emission inteensity
Ag (I) at wavelengthh of 328 nm is high
h
comparedd with
other adsorption
a
methods.
Figure 2 shows LIB
BS spectra of the pressurizeed
b
(Sample-5)
(
in the range 327 chitosan biomembrane
329 nm foor varies of laseer energies 80 mJ,
m 120 mJ, annd
160 mJ. Control
C
(Samplle-1) spectrum
m at laser energgy
of 120 mJJ was also keptt for the comparison. It show
ws
that the intensity of Ag
A (I) peak increases witth
increasingg laser energy. This describees more numbeer
of electronns from the ato
oms and more ions have beeen
excited heence more em
mission of specctrum obtained.
The spectrrum also showss increasing in the backgrounnd
signal as laser
l
energy in
ncreases, whicch is due to thhe
continuum
m emission of the plasma foorm [14]. From
m
these resuults, further ex
xperiments weere focused annd
analyzed on laser energ
gy of 120 mJJ and stated as
a
membrane.
optimal coondition for thee chitosan biom
Figure 3 shows the in
ntensity of atom
mic emission of
o
Ag (I) at wavelength of
o 328 nm obttained by LIB
BS
(with laserr energies 80, 120,
1 and 160 mJ)
m as a functioon
of depth from
fr
the surfacce, of the presssurized chitosaan
biomembrrane (Sample-5
5). The graph shows that thhe
emission was
w observed for all depthss indicating thhat
Ag has beeen evenly disttributed withinn the sample. At
A
the higherr laser energy
y, 160 mJ shoows fluctuationn.
This meaans that the intensity
i
of the
t
backgrounnd
increase, the
t peak becom
mes broad andd self adsorptioon
process takke place.
For fuurther examinaation of Fig. 3, the standarrd
deviation of the LIBS intensity wass calculated by
b
measuringg the intensity from three ideentical series of
o
adjacent areas
a
on the sample surfacce. The overaall
standard deviation
d
in th
he intensities of
o Ag (I) was ~
2% for lasser energy 80 and
a 120 mJ, annd ~ 5% for 1660
mJ.
34
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ACKNOW
WLEDGME
ENTS
Intensity (a.u.)
25
w
to thankk the Facultty of
The authors wish
Mathematics and Natural Sciences, Udaayana
Univerrsity for the LIIBS facility.
20
15
REF
FERENCES
S
10
5
1.
0
2.
SampleS
SampleSample2
2;shot-1
Sample3;shot-1
Sample4;shot-1
Sample5;sshot-1
ampleSa
2;shot-2
3;shot-2
Sample4;sshot-2
5;shot-2
FIGURE 4.
4 Intensity of em
mission of Ag (I)) at wavelength of
328 nm for various membraane treatments.
3.
The addsorption proceesses occurredd in the chitosaan
biomembrrane can be deescribed as follows. The Agg+
ions whichh were chemicaally adsorbed through
t
bondinng
with N in [Ag (NH3)2]+ as a covalent bond
b
resulted in
i
only a paiir of electronss shared by attoms N. Such a
bond is called a coordinaation covalent bond.
b
Here, Agg+
ion is an electron acceeptor, while N is an electroon
ormed adsorption layer is noot
donor. Thherefore, the fo
sufficientlyy strong when the laser shot and hence gavve
relatively low emission (Sample-2). To
T enhance thhe
results off this adsorpttion, the reinnforcement waas
carried ouut by heatin
ng (Sample-3)) and producce
relatively higher emissions than without
w
heatinng
(Sample-22). The adsorrption after heating
h
methood
produced low emission
ns. In this casse, heating haad
caused a damage to th
he physical structure
s
of thhe
membranee and eliminatiing or reducingg the number of
o
N that acteed as Ag adsorrption media, thus
t
resulting in
i
a low intennsity.
4.
5.
6.
7.
8.
9.
10.
11.
CONCLUSION
12.
The present
p
study demonstrated laser induceed
breakdownn spectroscopy
y (LIBS) to prrobe the presennt
of Ag eleement in the pressurized treated
t
chitosaan
biomembrrane at variouss depths from
m the surface. It
was analyyzed by monittoring the em
mission of Ag I
(wavelenggth of 328 nm
m). The pressuurized filtratioon
process reesulted in a hom
mogenously distributed Ag in
i
the membrrane up to a deepth of 200 μm
m. The optimum
m
laser enerrgy was 120 mJ.
m The chem
mical adsorptioon
process occcurred only att the surface of the membranne
without innclusion. Impro
ovements can be
b done by heat
treatment at
a 35qC.
13.
14.
S. R. Popuri, Y. Vijaya,
V
V. M. Boddu
B
and K. Abburi,
A
Biioresour. Technool 100, 194-199 (2009).
K.. Zieliska, A. G. Chostenko and S. Truszkoowski,
”A
Adsorption of caadmium ions on chitosan membbranes:
Kiinetics and equuilibrium studies” in Progreess on
Chhemistry and Appplication of Chittin and Its Derivvatives
Voolume XV, editeed by M. M. Jaaworska et. al., Lodz:
Poolish Chitin Sociiety, 2010, pp. 733-78.
R.. Ahmed and M.. A. Baig, J. Apppl. Phys 106, 03333071-6 (2009).
R.. Noll, H. Bette, A. Brysch, M. Kraushaar,
K
I. M¨onch,
L. Peter and V. Sturm,
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Spectrochim. Acta B 566, 6376449 (2001).
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Biioanal Chem 3855, 225–233 (2006).
P. Maravelaki-Kallaitzaki, D. Angllos, V. Kilikogloou and
V.. Zafiropulos, Spectrochim. Acta
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B 56, 8887-903
(2001).
M A. Baig, IEEE
EE. Trans. Plasm
ma Sci
R.. Ahmed and M.
388, No. 8, August,, 2052-2055 (2010).
C..C. Garcia, J. M.
M Vadillo, S. Pallanco, J. Ruiz annd J.J.
Laaserna, Spectrochhim. Acta B 56,, 923-931 (2001)).
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W.-B.
Lee, J. Wuu, Y. –I. Lee andd J. Sneddon, J. Appl.
Sppectrosc. Rev 39,, No. 1, 27-97 (22004).
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2999-308 (2000).
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a
M. Sabsaabi, “Laser Innduced
Brreakdown Speectroscopy Stuudies for Material
Chharacterization”,, Ph.D. Thessis, Homi Bhabha
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Naational Institute, 2010.
M R. Leahy-Hoppa, J. Miragliiotta, R. Osiandder, J.
M.
Buurnett, Y. Dikm
melik, C. McEnnnis and J. B. Spicer,
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Seensors 10, 4342-4372 (2010).
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Marcel Dekker.
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Pllasma and Appllications, New York:
19989.
35
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Ni Nyoman Rupiasih, Hery Suyanto, Made Sumadiyasa, Christine Prita Purwanto, and Rendra Rustam Purnomo
Citation: AIP Conf. Proc. 1555, 32 (2013); doi: 10.1063/1.4820987
View online: http://dx.doi.org/10.1063/1.4820987
View Table of Contents: http://proceedings.aip.org/dbt/dbt.jsp?KEY=APCPCS&Volume=1555&Issue=1
Published by the AIP Publishing LLC.
Additional information on AIP Conf. Proc.
Journal Homepage: http://proceedings.aip.org/
Journal Information: http://proceedings.aip.org/about/about_the_proceedings
Top downloads: http://proceedings.aip.org/dbt/most_downloaded.jsp?KEY=APCPCS
Information for Authors: http://proceedings.aip.org/authors/information_for_authors
Downloaded 05 Sep 2013 to 114.79.59.195. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://proceedings.aip.org/about/rights_permissions
Study of Filtering Ag Liquid Sample by Chitosan
Biomembrane Using Laser-Induced Breakdown
Spectroscopy (LIBS)
Ni Nyoman Rupiasih1,*, Hery Suyanto2, Made Sumadiyasa2,
Christine Prita Purwanto1 and Rendra Rustam Purnomo1
1
Biophysics Laboratory, 2 Applied Physics Laboratory, Department of Physics,
Faculty of Mathematics and Natural Sciences, Udayana University, Denpasar, 80361, Indonesia
*Email: rupiasih69@yahoo.com
Abstract. The capability of Laser-Induced Breakdown Spectroscopy (LIBS) to resolve filtration process of Ag liquid
sample by chitosan biomembrane is demonstrated. The biomembrane was prepared by inversion method used to filter
Ag liquid using pressurized technique samples which were then analyzed by monitoring the emission corresponding to
Ag (I) at wavelength of 328 nm. The experiment was conducted by varying the laser energy i.e. 80, 120, and 160 mJ,
where, subsequently, and its effect on the depth-profile from 20 - 200 μm was characterized by LIBS. The results
showed that the physical processes of pressurized filtration led a homogeneous Ag in the membrane from the surface to
a depth of 200 μm. The optimum condition was obtained at laser energy of 120 mJ. The adsorption occurred only on
the surface of the membrane i.e. 20 μm depth, but there was no inclusion. Improvement of the detection performance of
adsorption process was done by heating the dripped membrane at 35 oC and was resulting in increase in emission
intensity as expected.
Keywords: Chitosan biomembrane; pressurized filtration; liquid Ag; Laser-Induced Breakdown Spectroscopy
PACS: 82.35Pq
one requires a pulsed laser for generating microplasma on the target surface and elemental analysis is
accomplished by studying the emission of the plasma
plume. The performance of LIBS depends on several
parameters including laser wavelength, pulse energy,
pulse duration, time interval of observation, and
geometrical configuration of collecting optics, target
features, and properties of ambient medium. Extensive
work has been devoted to optimize these parameters
for the best experimental and commercial realization
of this technique.
The main disadvantage of LIBS is the high limit of
detection, about 500 ppm but 1ppm can be reached for
some elements [4].
LIBS is a very versatile technique and have been
used in siderurgy, industrial process control [4-7],
environmental geochemistry, biohazard material
detection, forensic science, microbiology, odontology,
archaeology, cultural heritage and art conservation [812].
Several papers dealing with LIBS applications in
depth-resolved analysis have also reported [5, 9-13].
In their reports, the laser was focused to a different
extent resulting in high irradiances (typically in the
order of 109 - 1011 Wcm-2).
In this study, the main purpose is to explore the
capability of Laser-Induced Breakdown Spectroscopy
INTRODUCTION
Chitosan is the most abundant natural polymer
after cellulose. It is a partially deacetylated product of
chitin, which has many useful features such as nontoxic,
biocompatibility,
biodegradability,
and
antibacterial property. Due to its features, chitosan has
been widely applied in many industries including
weastewater treatment. Chitosan has the ability to
form complexes with metals. It exhibits higher
adsorption capacity for metal ion compared to that of
chitin owing to the amino group content. However, the
serious drawback of chitosan for metal ion adsorbent
from practical utilization is that it is soluble in acidic
media [1-2].
Laser induced breakdown spectroscopy (LIBS) or
laser induced plasma spectroscopy is a useful method
to determine the chemical composition of a wide
range of materials including metals, liquids, aerosols,
plastics, minerals, biological tissues, etc. [3]. As an
analytical technique, LIBS presents some advantages
to other techniques: no sample preparation, real time
analysis, contactless analysis, apparatus or
experimental simplicity, inexpensiveness, robustness,
and quickness are interesting properties which makes
LIBS an attractive analytical technique. In many cases
is a non destructive technique [1]. In this technique
International Conference on Theoretical and Applied Physics (lCTAP 2012)
AIP Conf. Proc. 1555, 32-35 (2013); doi: 10.1063/1.4820987
© 2013 AIP Publishing LLC 978-0-7354-1181-4/$30.00
32
Downloaded 05 Sep 2013 to 114.79.59.195. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://proceedings.aip.org/about/rights_permissions
(LIBS) too resolve filtrration processs of Ag liquiid
sample byy chitosan bio
omembrane ussing pressurizeed
technique. Depth profilee analysis was conducted by
b
varying laser energy from
m 80 to 160 mJ
m each for 20 to
t
200 μm depth.
d
Variouss methods off the adsorptioon
process off Ag solution in the membrranes were alsso
carried ouut i.e. control (w
without treatm
ment) is called as
a
Sample-1; natural adsorp
ption as Sampple-2; adsorptioon
by heatingg as Sample-3
3; adsorption after
a
heating as
a
Sample-4; and adsorption
n with pressuree as Sample-5.
d. Laser-In
nduced Breaakdown
Specttroscopy (LIIBS)
Lasser induced brreakdown specctroscopy was used
to probbe the present of Ag elemennt in the pressuurized
treatedd chitosan biom
membrane at various
v
depths from
the surrface. The LIB
BS 2500-7 pluss model was ussed. It
uses Nd-YAG
N
Laseer (1064 nm (wavelength), 7 ns
(pulse width), 200 mJ
m (max. energgy)) and echellle HR
2500 spectrometer
s
w specifications such as, range
with
of the spectrum 200--980 nm, with 7 channels, FW
WHM
n using 7 deetectors with 2048
resoluttion of 0,1 nm
elemennt linier siliconn CCD arrayss that given tootal of
14336 pixels. The ouutput of the speectrometer anaalyzed
OLIBS and OOIICOR softwarees that displeyyed on
by OO
the moonitor.
In the
t present stuudy, the delay time
t
used was 1 μs,
4 pulses of each scaan, and 0 pulsee cleaning (to avoid
unneceessary scan). The
T laser energgy density (fluuence)
employyed in the expperiments was in the range 600-180
mJ. Thhe pulse to pullse energy variation throughoout all
measurements perforrmed, was no > ± 5%. The saample
was pllaced approxim
mately 2 cm inn front of the focal
point and
a a relativelly wide spot (aapprox. 1 mm) was
used in the LIBS measurement
m
inn order to obttain a
represeentative averaage of the maaterial compossition.
Emissiion spectra were recorded separately for each
one off successive laaser pulses andd were subsequuently
analyzzed.
MAT
TERIALS AND
A
METH
HODS
a. Ma
aterials
The materials
m
used are
a Chitosan powder
p
with
characterisstics i.e. 87,9% deacetylateed and their
solubility in acetic acid is 99,4%; aceetic acid and
sodium hyydroxide p.a. All
A reagents weere analytical
grade and were used with
hout further puurification.
b. Prep
paration of Chitosan
C
M
Membrane
The chhitosan solution
n of 4% (w/v) was
w prepared
by dissolvving 10 g of chiitosan powder in 250 ml of
1% acetic acid solution
n. The mixturee was stirred
for 8 houurs at room teemperature to obtain dope
solution. The
T dope solutiion was pouredd into a glass
plate and dried
d
at room temperature
t
forr 6 days. The
membranee was in the NH
H3+ form. It was
w dipped in
1% sodiuum hydroxidee solution too reach the
unchargedd amino form, washed
w
with diistilled water
3 times to eliminate the excess of sodium
d.The thickneess of the
hydroxide, then dried
membranee was around 236 μm.
RESULTS
S AND DISC
CUSSION
Figgure 1 shows LIBS
L
spectra off control (Sampple-1)
and pressurized
p
t
treated
chitoosan biomem
mbrane
(Sampple-5) scanned with
w laser enerrgy of 120 mJ in the
range 327 - 329 nm. It shows a peak at wavelenggth of
328 nm
n in Samplee-5 which is known as attomic
emission line of Ag (I), whereas no
n peak observves in
the control membranne (Sample-1). This explains that
mple-5 that adm
mitted by presssure.
there is Ag in the Sam
c. Membrane Treatm
ments
In this study, the chiitosan biomem
mbranes have
been treatted in 5 diffeerent ways i.ee. Sample-1:
control (w
without treatm
ment), Sample-2: Ag 1000
ppm droppped on the meembrane and allow
a
to dry
naturally (natural
(
adsorp
ption), Samplee-3: Ag 1000
ppm droppped on the mem
mbrane and heeated to 35°C
(adsorptionn by heatin
ng), Sample-44: heat the
membranee to 35°C then dropped wiith Ag 1000
ppm (adssorption after heating), andd Sample-5:
membranee exposed to Ag
A 1000 ppm
m solution by
filtration method with
h pressure ~ 50 kPa
(adsorptionn with pressuree).
FIGUR
RE 1. LIBS sppectra of controol (Sample-1) and
a
pressurrized treated chhitosan biomem
mbrane (Sample--5)
scannedd with laser eneergy of 120 mJ in the range 3277 329 nm
m.
33
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200
180
160
140
Intensity (a.u.)
120
100
80
Samp
ple-5, 80mJ
60
Samp
ple-5, 120mJ
40
20
Samp
ple-5, 160mJ
0
0
20 40 60 8
80 100 120 140 160 180 200 220
Depth (µm)
FIGURE 2.
2 LIBS spectraa of the pressurrized chitosan
biomembraane (Sample-5) in
i the range 3277 - 329 nm for
laser energiies 80, 120, and
d 160 mJ. Contrrol (Sample-1)
spectrum iss presented (kep
pt at laser energgy of 120 mJ)
for the com
mparison.
FIGUR
RE 3. Intensityy of atomic em
mission of Ag (I) at
wavelength of 328 nm obtained by LIB
BS with laser ennergies
d
from the surface
80, 1200, and 160 mJ ass a variation of depth
for the pressurized chittosan biomembraane (Sample-5).
To study about thhe adsorption process
p
of Ag in the
chitosaan biomembrrane, four methods
m
mem
mbrane
treatment are introduuced. The resullts are shown inn Fig.
4. For natural (Sampple-2) after firstt shot (shot-1, depth
~ 20 μm)
μ by laser energy
e
of 120 mJ, the intensity of
Ag (I) obtained was ~ 6.67 a.u, whhile at a depth of 40
μm (ssecond shot) was null, indicating
i
thaat no
inclusiion process occcurred. To im
mprove the deteection
perform
mance of the
t
adsorptioon processes, an
adsorpption by heatiing method was
w introducedd, the
treatedd membrane with
w the same process
p
of Sam
mple-2
is heaated to 35°C (Sample-3) annd the intensiity is
increassed to ~ 8.75 a.u.
a This indicaates that the prrocess
was innfluenced by the
t temperaturre. Result from
m the
secondd shot was alsoo zero. Furtherrmore an adsorrption
after heating
h
methodd was used. Heating the mem
mbrane
before dripping it with 1000 ppm Ag sollution
(Sampple-4), gave inttensity as low
w as, ~ 5.5 a.uu. The
intensiity of Samplle-5 (adsorptiion with preessure
methodd) was the highhest at ~ 21.5 a.u.
a
Theese results desscribe Ag liquiid penetrate intto the
membrrane properly when
w
pressurizzed (adsorptionn with
pressuure method). This causes Ag interact both
chemiccally and phyysically with the
t
membranee and
producces strong covaalent bonds in the
t membrane. As a
result, providing a strong
s
reboundd momentum during
d
the lasser shot and prroduced plasmaa emission inteensity
Ag (I) at wavelengthh of 328 nm is high
h
comparedd with
other adsorption
a
methods.
Figure 2 shows LIB
BS spectra of the pressurizeed
b
(Sample-5)
(
in the range 327 chitosan biomembrane
329 nm foor varies of laseer energies 80 mJ,
m 120 mJ, annd
160 mJ. Control
C
(Samplle-1) spectrum
m at laser energgy
of 120 mJJ was also keptt for the comparison. It show
ws
that the intensity of Ag
A (I) peak increases witth
increasingg laser energy. This describees more numbeer
of electronns from the ato
oms and more ions have beeen
excited heence more em
mission of specctrum obtained.
The spectrrum also showss increasing in the backgrounnd
signal as laser
l
energy in
ncreases, whicch is due to thhe
continuum
m emission of the plasma foorm [14]. From
m
these resuults, further ex
xperiments weere focused annd
analyzed on laser energ
gy of 120 mJJ and stated as
a
membrane.
optimal coondition for thee chitosan biom
Figure 3 shows the in
ntensity of atom
mic emission of
o
Ag (I) at wavelength of
o 328 nm obttained by LIB
BS
(with laserr energies 80, 120,
1 and 160 mJ)
m as a functioon
of depth from
fr
the surfacce, of the presssurized chitosaan
biomembrrane (Sample-5
5). The graph shows that thhe
emission was
w observed for all depthss indicating thhat
Ag has beeen evenly disttributed withinn the sample. At
A
the higherr laser energy
y, 160 mJ shoows fluctuationn.
This meaans that the intensity
i
of the
t
backgrounnd
increase, the
t peak becom
mes broad andd self adsorptioon
process takke place.
For fuurther examinaation of Fig. 3, the standarrd
deviation of the LIBS intensity wass calculated by
b
measuringg the intensity from three ideentical series of
o
adjacent areas
a
on the sample surfacce. The overaall
standard deviation
d
in th
he intensities of
o Ag (I) was ~
2% for lasser energy 80 and
a 120 mJ, annd ~ 5% for 1660
mJ.
34
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ACKNOW
WLEDGME
ENTS
Intensity (a.u.)
25
w
to thankk the Facultty of
The authors wish
Mathematics and Natural Sciences, Udaayana
Univerrsity for the LIIBS facility.
20
15
REF
FERENCES
S
10
5
1.
0
2.
SampleS
SampleSample2
2;shot-1
Sample3;shot-1
Sample4;shot-1
Sample5;sshot-1
ampleSa
2;shot-2
3;shot-2
Sample4;sshot-2
5;shot-2
FIGURE 4.
4 Intensity of em
mission of Ag (I)) at wavelength of
328 nm for various membraane treatments.
3.
The addsorption proceesses occurredd in the chitosaan
biomembrrane can be deescribed as follows. The Agg+
ions whichh were chemicaally adsorbed through
t
bondinng
with N in [Ag (NH3)2]+ as a covalent bond
b
resulted in
i
only a paiir of electronss shared by attoms N. Such a
bond is called a coordinaation covalent bond.
b
Here, Agg+
ion is an electron acceeptor, while N is an electroon
ormed adsorption layer is noot
donor. Thherefore, the fo
sufficientlyy strong when the laser shot and hence gavve
relatively low emission (Sample-2). To
T enhance thhe
results off this adsorpttion, the reinnforcement waas
carried ouut by heatin
ng (Sample-3)) and producce
relatively higher emissions than without
w
heatinng
(Sample-22). The adsorrption after heating
h
methood
produced low emission
ns. In this casse, heating haad
caused a damage to th
he physical structure
s
of thhe
membranee and eliminatiing or reducingg the number of
o
N that acteed as Ag adsorrption media, thus
t
resulting in
i
a low intennsity.
4.
5.
6.
7.
8.
9.
10.
11.
CONCLUSION
12.
The present
p
study demonstrated laser induceed
breakdownn spectroscopy
y (LIBS) to prrobe the presennt
of Ag eleement in the pressurized treated
t
chitosaan
biomembrrane at variouss depths from
m the surface. It
was analyyzed by monittoring the em
mission of Ag I
(wavelenggth of 328 nm
m). The pressuurized filtratioon
process reesulted in a hom
mogenously distributed Ag in
i
the membrrane up to a deepth of 200 μm
m. The optimum
m
laser enerrgy was 120 mJ.
m The chem
mical adsorptioon
process occcurred only att the surface of the membranne
without innclusion. Impro
ovements can be
b done by heat
treatment at
a 35qC.
13.
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