Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
1
Iss. 2
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
2
Sankt Lorenzen 36, 8715, Sankt Lorenzen, Austria
By Magnolithe GmbH
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Mechanics, Materials Science & Engineering Journal
April 2017
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
3
Mechanics, Materials Sciences & Engineering Journal, Austria, Sankt Lorenzen, 2017
Volume 9, Issue 2
Mechanics, Materials Science & Engineering Journal (MMSE Journal) is journal that deals in peer-
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Editor-in-Chief Mr. Peter Zisser
Dr. Zheng Li, University of Bridgeport, USA
Prof. Kravets Victor, Ukraine
Ph.D., Shuming Chen, College of Automotive Engineering, China
Dr. Yang Yu, University of Technology Sydney, Australia
Prof. Amelia Carolina Sparavigna, Politecnico di Torino, Italy
ISSN 2412-5954
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Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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CONTENT
Studies on the Growth, Thermal and Optical Properties of p-methyl Anilinium Malate Single
Crystal. S. Kalaiyarasi, S. Suresh, R. Mohan Kumar ..................................................................... 8
An Analysis of Structural, Electronic and Reactivity Properties of MetforminChloride using
XRD and DFT Approach. R. Niranjana Devi, S. Israel, C. Ancline ............................................ 14
Structural, Spectroscopic, Thermal studies of Pure and DL-Methionine Doped ADP
Crystals. J.H. Joshi, H.O. Jethva, P.T. Bagda, K. Ashish Prasad, M.J. Joshi ................................ 20
Impedance Spectroscopy of Sodium Sulphide Added ADP Crystals. A.P. Kochuparampil,
J.H. Joshi, H.O. Jethva, M.J. Joshi. .............................................................................................. 25
Growth and Characterization of a Novel Nonlinear Optical Single Crystal of L- Isoleucinium
Hydrogen Maleate Hemihydrate. A. Hemalatha, K. Deepa, A. Venkatesan, S. Senthil ............. 31
Group 12-Metal Complexes derived from Donor Substituted Carboxylic Acids and 5-Nitro-
1,10-Phenanthroline: Spectroscopic and Biological Studies. Champaka Gurudevaru,
Nallasamy Palanisami ................................................................................................................. 37
Spectroscopic Properties of Sm3+Doped Lithium Zinc Borosilicate Glasses. N. Jaidass,
C. Krishna Moorthi, A. Mohan Babu, M. Reddi Babu .................................................................... 42
Spectral Analysis of Nd3+ Doped Lead Borosilicate Glasses for Efficient Broadband Laser
Amplification. M. Reddi Babu, N. Madhusudhana Rao, A. Mohan Babu .................................... 49
Growth and Characterization of a Nonlinear Optical Crystal a Complex Orthonitroaniline
with Picric Acid Single Crystal by Vertical Bridgman Technique. S. Noormohammad Shareef,
K. Chidambaram, S. Kalainathan ................................................................................................ 54
Studies of Crystal Growth, Structural and Optical Properties of Glycinium-3-Carboxy-4-
Hydroxybenzenesulfonate Single Crystal. A. Thirunavukkarsu, T. Sujatha, P.R. Umarani, A.
Chitra, R. Mohan Kumar .............................................................................................................. 60
Growth and Characterization of L-Glycinium Phosphate: A Promising Crystal for Opto
Electronics Applications. K. Rajesh, A. Mani, P. Praveen Kumar ............................................... 67
Growth and Characterization of Organo-metallic Single Crystals of (HCLPTM)
Heptachloro (L-Proline) TetraMercury (II). V. Revathi Ambika, D.Shalini, R. Usha, N. Hema, D.
Jayalakshmi ................................................................................................................................. 73
Comparative Study of Erbium Doped KDP Single Crystals Grown by Different Techniques.
V. Roopa, Dr. R. Ananda Kumari ................................................................................................. 78
Crystal Growth, Optical, Dielectric, Mechanical and Second Harmonic Generation
Characterization of 2,5-Dimethylanilinium Dihydrogen Phosphate Single Crystal. A. Mani, K.
Rajesh, P. Praveen Kumar .......................................................................................................... .93
Comparative Study of Properties of L-Histidine and L-Histidine Nickel Nitrate
Hexahydrate Crystals Grown by Slow Evaporation. R. Vinayagamoorthy, A. Albert Irudayaraj,
A. Dhayal Raj, S. Karthick, G. Jayakumar..................................................................................... 92
Growth and Characterization of Unidirectional Grown Imidazolium L-Tartrate (IMLT)
Single Crystal by SR Method. V. Thayanithi, P. Praveen Kumar ............................................... 98
Growth, Nonlinear, Dielectric Studies on Urea Phosphoric Acid (UP) Single Crystals.
N. Hema, R. Usha, D. Shalini, V. Revathi Ambika, D. Jayalakshmi ............................................ 103
Optical, Thermal and Electrical Studies on L-Malic Acid Doped ADP Single Crystals for
Non-Linear Optical Application. S. Arulmani, K. Deepa, N. Indumathi, M. Victor Antony Raj,
S. Senthil .................................................................................................................................... 108
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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Thermal and Dielectric Properties Of L-Malic Acid Doped KDP Single Crystals. A.
Venkatesan, S. Arulmani, E. Chinnasamy, S. Senthil, M.E. Rajasaravanan ................................. 114
Optical, Thermal and Electrical Characterization of Urea Sulphamic Acid Single Crystals.
E. Chinnasamy, A.Venkatesan, M.E. Rajasaravanan, S.Senthil ................................................... 120
Crystal Growth, Spectral and Optical Studies of 2-Aminoanilinium Benzoate Single Crystal.
I. Md. Zahid1, C. Amirtha Kumar1, R. Mohan Kumar ................................................................ 126
Synthesis, Vibrational Spectroscopy, Thermal Analysis, Non-Linear Optical Properties and
DFT Calculation of a Novel L-Phenylalanine Maleic Acid Single Crystals. K. Deepa, J.
Madhavan .................................................................................................................................. 131
Piezoelectric and Ferroelectric Properties of Lead-free 0.9(Na0.97K0.03NbO3)-0.1BaTiO3
Solid Solution. S. Sasikumar, R. Saravanan, S. Saravanakumar ................................................ 137
Synthesis and Physicochemical Investigation of THz Material: 4Ethoxy Benzaldehyde4'
N'Methyl Stilbazolium Hexafluorophosphate (EMBSHP). A. Karolin Martina1, J. Arul Martin
Mani1, N.S. Nirmala Jothi1, P. Sagayaraj .................................................................................. 145
Recycling Technology of Fiber-Reinforced Plastics Using Sodium Hydroxide. K. Baba,
T. Wajima .................................................................................................................................. 150
Synthesis, Growth and Optical, Electrical, Thermal Properties of L- Proline Adipate Single
Crystals for Nonlinear Optical Applications. N. Indumathi, K. Deepa, J. Madhavan,
S. Senthil .................................................................................................................................... 156
Synthesis, Growth, Spectral, Thermal and Mechanical Properties of Inorganic Organic
Hybrid NLO Crystal: NH4[Cd(NCS)3] C12H24O6. V. Ramesh, K. Rajarajan ....................... 162
Synthesis, Growth and Characterization Aspects of Non-linear Organometallic Single
Crystals of BCTZ. K.Showrilu, V.Naga Lakshmi, K.Rajarajan .................................................. 168
Crystal Growth, Spectral and Optical Properties of Quinolinium Single Crystal: 1-Ethyl-2-
[2-(4-Nitro-Phenyl)-Vinyl]-Quinolinium Iodide. S. Karthigha, C. Krishnamoorthi .................. 174
Synthesis, Growth, Spectral, Optical and Mechanical Properties of an Organic Single
Crystal: (E)-2-(4-Chlorostyryl)-1-Methylpyridin-1-Ium Iodide Hydrate. K. Nivetha,
W. Madhuri ................................................................................................................................. 179
Theoretical Investigation of Optical and Mechanical Properties of Sodium Hydrogen
Succinate Single Crystal: a Third Order NLO Material. P.S. Latha Mageshwari, R. Priya, R.
Subhashini, V. Joseph, S. Jerome Das ......................................................................................... 184
Crystal Structure, Dielectric Response and Thermal Analysis of Ammonium Pentaborate
(APB). Hiral Raval, Mitesh Solanki, Bharat Parekh, M.J. Joshi ................................................. 190
Investigation on Thermal, Optical, Second Order and Third Order NLO Properties of a
Nonlinear Optical Single Crystal of L-Leucinium Hydrogen Maleate (LLM). Hemalatha, S.
Senthil ........................................................................................................................................ 196
Growth and Dielectric Properties of 1,3-bis(4-methoxyphenyl)prop-2-en-1-one Organic
Single Crystal. K. Arunkumar, S. Kalainathan .......................................................................... 202
Effect of Hydrochloric Acid (HCl) on Synthesis and Anisotropic Phenomena of Triglycine
Phosphate (TGP) Single Crystals. M.R. Meera, S.L. Rayar, V. Bena Jothy .............................. 208
Structural Properties of Bioactive Molecule Naphthalene 2-Sulfonic Acid. R. Mini, T. Joselin
Beaula, I. Hubert Joe, V. Bena Jothy .......................................................................................... 215
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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Fluorescence Emission and Decay Time Studies on Doped 1, 3, 5-Triphenylbenzene
Scintillator Crystal Grown by Solution Growth Technique. N. Durairaj, S. Kalainathan,
R. Kumar ................................................................................................................................... 220
Bulk Crystal growth and Characterization of Organic Nonlinear Optical Crystal: 2-(2,4-
dimethoxybenzylidene) malononitrile (DMM). A. Priyadharshini, S.Kalainathan .................. 225
Growth and Etching Studies of Cadmium Mercury Thiocyanate Single Crystals Grown by
Gel Technique. P. Nisha Santhakumari, S. Kalainathan ............................................................ 230
Cadmium Dimethyl Sulfoxide Thiocyanate NLO Crystal: Structural, Optical and Thermal
Properties. S. Karthick, A. Albert Irudayaraj, A. Dhayal Raj, R. Vinayagamoorthy ................... 235
Laser Hardening and Pack Boriding of EN 8D Steel. K. Monisha, P. Selvamuthumari,
D. Narendran, Rasik Ahmad Parray, J. Senthilselvan ................................................................. 240
Synthesis, Growth and Characterisation of New Organic Crystal: L-Histidinium 5 Sulfo
Salicylate for Second Order Nonlinear Optical Applications. R. Usha, N. Hema, V. Revathi,
Ambika D. Shalini, D. Jayalakshmi ............................................................................................ 244
Investigation on Zn (II) Doped Lithium Sulphate Monohydrate Single Crystals. E. Glitta
Sumangali, Girish M. Joshi ........................................................................................................ 250
Gel Growth: A Brief Review. H.O. Jethva ......................................................................... 255
Importance of Impedance Spectroscopy Technique in Materials Characterization: A Brief
Review. M.J. Joshi ..................................................................................................................... 261
A Combined Experimental and Theoretical Investigations on N, N′-Diphenylguanidine
Based Single Crystals For Nonlinear Optical Applications. G. Saravana Kumar, R. Roop Kumar,
P. Murugakoothan. .................................................................................................................... 267
Facile Preparation and Characterization of Polyaniline-iron Oxide Ternary Polymer
Nanocomposites by Using Mechanical MixingApproach. N. Dhachanamoorthia, L. Chandra,
P. Suresh, K. Perumal ................................................................................................................ 273
Experimental Investigation of Static Mechanical Properties of Epoxy Based Glass, Carbon
& Sisal Woven Fabric Hybrid Composites. M. Arulkumar, K.S. Rajeshwaran, G. Sathish ...... 281
Structural and Complex Formation of PVC LiNO3 CdO. . Karthika, R. Karthigai Selvi,
P.S. Devi Prasadh. ..................................................................................................................... 287
Investigation of Surface Texture Generated by Friction Drilling on Al2024-T6. M. Boopathi,
S. Shankar, T.C. Kanish. ............................................................................................................ 291
Mechanical Properties of Natural Fiber Sandwich Composite: Effect of Core Layer.
M. Rajesh, T.C. Kanish .............................................................................................................. 296
Fabrication of Hybrid Metal Matrix Composite Reinforced With SiC/Al2O3/TiB2. S.
Johny James, A. Raja Annamalai, P. Kuppan, R. Oyyaravelu. .................................................... 301
Fabrication of Aluminium Metal Matrix Composite and Testing of Its Property. S.
JohnyJames, A. Raja Annamalai. ............................................................................................... 306
Determination of Activation Energies from Complex Impedance Parameters of Microwave
Sintered NiMgZn Ferrites. K. Chandra Babu Naidu, W. Madhuri. .......................................... 312
Structural and Dielectric Properties of CuO, PbO and Bi2O3 Doped SrTiO3
Ceramics. T. Sofi Sarmash, V. Narasimha Reddy, T. Vidya Sagar, M. Maddaiah,
T. Subbarao. ............................................................................................................................. 318
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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Multiwalled Carbon Nanotubes (MWCNT) / Poly O-Cresophthalein Complexone Film
(POCF) Modified Electrode for Determination of Cd (ll) Using Anodic Stripping
Voltammetry. J. Jayadevimanoranjitham, C. Lakshmi Devi, S. Sriman Narayanan. .................. 324
Spectroscopic Analysis of Gas Phase Astrophysical Molecule: Beryllium Monofluride.
R. Sindhan, P. Sriramachandran, R. Shanmugavel, S. Ramaswamy. ........................................... 329
Study of Charge Density and Crystal Structure of co-doped LaCrO3 System. N. Thenmozhi,
S.Sasikumar, R. Saravanan, Yen-Pei Fu. .................................................................................... 335
Electrical Properties of Ni0.4Mg0.6Fe2O4 Synthesized by Conventional Solid-State Reaction
Method. K.T. Veeranjaneaya, D. Ravinder. ............................................................................... 343
Synthesis and Characterization of PbZrTiO3 Ceramics. T. Vidya Sagar, T. Sofi Sarmash,
M. Maddaiah, T. Subbarao. ........................................................................................................ 348
Effect of Multiple Laser Shock Peening without Coating on Al-2024-O Alloy for Automotive
Applicatio. Yash Jain, Sandeep Varin, S. Prabhakaran, S. Kalainathan. ................................... 353
Influence of Multiple Laser Shock Peening without Coating on Ti-6Al-4V Alloy for Aircraft
Applications. Sandeep Varin, Yash Jain, S. Prabhakaran, S. Kalainathan. ................................ 358
Analytical Quality by Design A Legitimate Paradigm for Pharmaceutical Analytical Method
Development and Validation. Balaji Jayagopal1, Murugesh Shivashankar. ............................. 364
Effect of Laser Shock Peening Without Coating on Surface Morphology and Mechanical
Properties of Nickel-200. Aniket Kulkarni, Siddarth Chettri, S. Prabhakaran,
S. Kalainathan. .......................................................................................................................... 374
Characterization of Cr Doped CuGaS2 Thin Films Synthesized By Chemical Spray Pyrolysis.
N. Ahsan, S. Kalainathan, N. Miyashita, T. Hoshii, Y. Okada. .................................................... 380
Deposition and Characterisation of Zinc Telluride as a Back Surface Field Layer in
Photovoltaic Applications. Srimathy N., A. Ruban Kumar. ....................................................... 388
Phtotocatalytic Degradation of Methyelene Blue by Cu Doped TiO2 Thin Films under Visible
Light Irradiation. Vidhya Rajendran, Gandhimathi Rajendran,
Neyvasagam Karuppathevar. ..................................................................................................... 395
Highly Porous and Novel 1D-TiO2 Nanoarchitecture with Light Harvesting Morphology for
Photovoltaic Applications. K. Pugazhendhi, W. Jothi Jeyarani, Tenzin Tenkyong, P. Naveen Kumar,
B. Praveen,J. Merline Shyla. ...................................................................................................... 402
Application of Quaternionic Matrices for Finite Turns’ Sequence Representation in Space.
Victor Kravets, Tamila Kravets, Olexiy Burov. ........................................................................... 408
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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Studies on the Growth, Thermal and Optical Properties of p-methyl Anilinium
Malate Single Crystal
1
S. Kalaiyarasi
1
, S. Suresh
1
, R. Mohan Kumar
1
1 Department of Physics, Presidency College, Chennai, India
DOI 10.2412/mmse.83.31.489 provided by Seo4U.link
Keywords: organic compound, solution growth, photoluminescence, nonlinear optical studies.
ABSTRACT. Single crystal of a novel p-methyl anilinium malate (PTM) was grown by slow evaporation method. Single
crystal and powder X-ray diffraction studies confirm that PTM belongs to monoclinic system with centro-symmetric
space group P2
1
/c. FTIR spectral analysis showed the presence of functional groups in PTM compound. Thermal studies
exhibit that PTM crystals are stable up to 166C. UV-visible study showed the good transmission region, cut-off
wavelength (206 nm) and band gap energy (5.8 eV) and photoluminescence studies explored its efficacy towards device
fabrication. The third order nonlinear optical parameters such as the nonlinear refractive index (n
2
) = 3.41 × 10
8
cm
2
/W,
nonlinear absorption coefficient () =0.03 × 10
4
cm/W and third order nonlinear susceptibility (
(3)
) = 3.77 × 10
6
esu of
PTM crystal were estimated by using Z-scan measurement.
Introduction. Recently, much attention has been paid on the development of a novel nonlinear
optical (NLO) materials because of their optical applications, such as optical data storage, electro-
optical modulation, optical switching, optical frequency doubling and optical communication. The
organic compounds are having high nonlinear optical susceptibility (χ) than inorganic materials. The
organic materials contain proton acceptor and donor groups positioned at either end of a suitable
conjugation path. The efficient optical switching behaviour of third order nonlinear optical organic
materials was investigated in recent years. The aim for designing the molecules with high third-order
nonlinearity is to incorporate them into device applications. 4-methylaniline contains a proton
acceptor amino (NH
2
) group, which can creates a strong hydrogen bond with organic acids and forms
N-H--O, an anilinium group [1]. DL-malic acid one of the simplest chiral dicarboxylic acids, is a
suitable building block in crystal engineering and it is used to create two-dimensional anionic
networks held together by hydrogen bonds [2]. The structure of the p-methyl anilinium malate
compound has been reported [3]. The systematic investigation has been carried on the growth aspects
of PTM crystal. The spectral, optical, thermal properties of PTM crystal were studied by using various
characterization techniques and results are reported.
Material synthesis and crystal growth. p-methyl anilinium malate compound was synthesized
nfrom high pure p-toluidine (sigma-Aldrich 99.6%) and malic acid. Equimolar amounts of reactants
were fully dissolved in deionized water. The solution was continuously stirred for obtaining
homogeneous state and the solution was allowed for evaporation by using a constant temperature
bath. After the period of 30 days, a good quality of single crystal was harvested with dimension
14x3x2 mm
3
as shown in Fig. 1.
© 2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
9
Fig. 1. Photograph of PTM crystal.
Results and discussion
X-ray diffraction studies. The single crystal X-ray diffraction study was performed using MoK
α
radiation from X-ray diffractometer. The estimated cell parameters values of PTM crystal are
a = 7.4849 Å, b = 16.1306 Å, c = 10.4904 Å, α = γ = 90, β =109.23, V = 1195.9 Å
3
and Z=4.
It was found that the grown crystal belongs to monoclinic system with space group P2
1
/c.
The powder X-ray diffraction of the grown crystal was recorded from 10
to 50
by using CuK
α
radiation of wavelength 1.5406 Å (Fig.2). The hkl values of prominent planes were indexed.
Fig. 2. Powder X-ray diffraction pattern of PTM crystal.
FTIR spectral studies. Fourier transform infrared spectrum of PTM was recorded in the range
400-4000 cm
-1
by KBr pellet method (Fig.3). The presence of functional groups in the synthesized
compound was ascertained and corresponding frequency assignments are given in Table 1. FT-IR
spectrum of PTM crystal shows a band at 3432 cm
-1
which is assigned to N-H stretching vibrations.
The asymmetric and symmetric stretchings observed at 2990 and 2605 cm
-1
are due to C-H vibrations.
The presence of carboxylate ions confirmed through the asymmetric and symmetric stretching
vibrations of COO
-
at 1591 and 1422 cm
-1
respectively. The deformation and wagging vibrations of
N-H group yielded peaks at 1243 and 1084 cm
-1
. The infrared bands appeared at 878 and 803 cm
-1
is
attributed to C-C stretching vibrations. The absorption occurred at 597, 548 and 484 cm
-1
is
10 15 20 25 30 35 40 45 50
-100
0
100
200
300
400
500
600
700
800
Intensity (Cps)
2 (Degree)
(0 3 1)
(1 3 1)
(2 1 1)
( 1 2 3)
(1 5 1)
(0 0 4)
(2 0 0)
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
10
characteristics of COO
-
wagging mode and supports the protonation and the deprotonation of title
compound.
Fig. 3. Infrared spectrum of PTM.
TG-DSC analysis. From the TG-DSC curves (Fig.4), it was observed that, the title compound is
thermally stable upto 166C and the DSC thermal study confirms that the PTM crystal melts at
167°C.There was no major weight loss occured before 167° C. The weight loss started at 167°C due
to the liberation of volatile substances such as CO, CO
2
and hydrocarbons. The final stage of
decomposition started at 215
C and it prolonged upto 315
C. From these results, it was concluded that
the PTM crystal is capable to function at temperature upto 166C which could be useful in optical
applications.
Fig. 4. TG-DSC Thermogram of PTM.
UV-Visible transmission studies. From the UV-Visible optical studies, the transmission range,
transparency, absorption coefficient band gap energy were estimated which are the important
parameters for optical applications. UV-vis spectrum of PTM showed good transparency about 72%
with lower cut-off wavelength 206 nm. The optical band gap energy (E
g
) was estimated using
(Eqn.1), and it was found to be 5.8 eV as shown in Fig.5(a) and (b).
4000 3500 3000 2500 2000 1500 1000 500
20
30
40
50
60
70
80
90
100
Transmittance (%)
Wavenumber (cm
-1
)
3432
2605
2990
1695
1591
1516
1422
1347
1301
1234
1168
1084
1028
943
878
803
756
643
548
484
597
0 100 200 300 400 500 600 700
0
20
40
60
80
100
B
C
Temperature (C)
Weight (%)
-4
-3
-2
-1
0
1
2
3
DSC (mW/mg)
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
11
(αhυ)
2
= A (E
g
–hυ) (1)
Fig. 5. (a) UV-Visible transmission spectrum (b) Tauc’s plot of PTM crystal.
Photoluminescence spectral studies. Photoluminescence spectrum was recorded for PTM crystal at
room temperature with an excitation wavelength of 250 nm as shown in Fig.6. The sharp spectrum
showed a peak centered at 355 nm and no other visible emission peak has been observed. In the
present study, a very strong intense emission peak observed at 355 nm (E
g
= 3.4 eV) corresponds to
near band-edge exitons of as-gown crystal. It may be occurred due to the * transition.
Therefore, the PTM crystals might be suitable for UV filters and optoelectronic laser devices [4].
Fig. 6. PL spectrum of PTM crystal with an excitation wavelength of 250 nm.
Nonlinear optical studies. Third order nonlinear optical property of PTM crystal has been
investigated by Z scan technique and it is an exact method to find the sign and magnitude of nonlinear
refractive index (n
2
) and nonlinear absorption coefficient (β) of the sample. It is the single beam
250 300 350 400 450 500 550 600 650
-100000
0
100000
200000
300000
400000
500000
600000
700000
Intensity (a.u)
Wavelength (nm)
355 nm
a
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
12
method, which utilizes self focusing or self defocusing phenomena in optical nonlinear materials [5].
The Z-scan measurement traces in closed aperture mode and open aperture are shown in Fig. 7(a) and
Fig. 7(b) respectively.
The third order nonlinear optical susceptibility was calculated using the relation,
χ
(3)
=

 

(2)
The third-order nonlinear refractive index (n
2
) = 3.41 × 10
8
cm
2
/W, nonlinear absorption coefficient
() =0.03 × 10
4
cm/W and third order non-linear susceptibility (
(3)
) = 3.77 × 10
6
esu were estimated
by Z- scan technique.
Fig. 7 (a) Z-scan plot of PTM crystal in closed aperture (b) Z-scan plot of PTM crystal in open
aperture.
Summary. Third-order nonlinear optical PTM single crystal with 14x3x2 mm
3
dimension was grown
by slow evaporation technique. Single crystal X-ray diffraction studies reveal that the grown PTM
crystal belongs to monoclinic system with P2
1
/c space group. The functional groups present in PTM
were confirmed by FTIR spectral studies. TG-DSC thermogram revealed the thermal stability of PTM
crystal. UV-visible study showed the good transmission region and the cut-off wavelength, band gap
energy were found to be 206 nm and 5.8 eV respectively. Photoluminescence spectral analysis
suggests that PTM could be used in UV filters and optoelectronic devices.
Z-scan measurements revealed the values of third-order nonlinear refractive index, nonlinear
absorption coefficient and third order non-linear susceptibility.
References
[1] J.V. Jovita, K. Boopathi, P. Ramasamy, A. Ramanand, P. Sagayaraj, Synthesis, growth and
characterization of 4-methyl anilinium phenolsulfonate single crystal, J. Cryst. Growth, Vol. 380,
pp. 218-223, 2013, DOI: 10.1016/j.jcrysgro.2013.06.027.
[2] A. Senthil, P. Ramasamy, Synthesis, growth and characterization of strontium bis (hydrogen l-
malate) hexahydrate bulk single crystal: a promising semi-organic nonlinear optical material, J. Cryst.
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-15 -10 -5 0 5 10 15
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
Normalised transmittance
Z(mm)
closed aperture
-15 -10 -5 0 5 10 15
1.00
1.01
1.02
1.03
1.04
Normalised transmittance
Z(mm)
open aperture
a
b
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
13
[3] S. Kalaiyarasi, S. Reena Devi, R. Akilan, R. Mohan Kumar, G. Chakkaravarthi, 4-
Methylanilinium 3-carboxy-2-hydroxypropanoate, IUCrData, Vol.1(9), pp.1,x161525, 2016,
DOI:10.1107/S241431461601525X.
[4] S. Sudhahar, M. KrishnaKumar, A. Silambarasan, R. Muralidharan, R. Mohan Kumar, Studies
on structural, spectral, and optical properties of organic nonlinear optical single crystal: 2-Amino-
4,6-dimethylpyrimidinium p-Hydroxybenzoate, J. Mater., 2013, DOI: org/10.1155/2013/539312
[5] V. Subashini, S. Ponnusamy, C. Muthamizhchelvan, Synthesis, growth, spectral, thermal,
mechanical and optical properties of piperazinium (meso) tartrate crystal: A third order nonlinear
optical material, J. Cryst. Growth, Vol. 363, pp. 211-219, 2013, DOI: 10.1016/j.jcrysgro.2012.10.045.
Cite the paper
S. Kalaiyarasi, S. Suresh, R. Mohan Kumar, (2017). Studies on the Growth, Thermal and Optical Properties of
p-methyl Anilinium Malate Single Crystal. Mechanics, Materials Science & Engineering, Vol 9. Doi
10.2412/mmse.83.31.489
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14
An Analysis of Structural, Electronic and Reactivity Properties of
MetforminChloride using XRD and DFT Approach
2
R. Niranjana Devi
1
, S. Israel
1
, C. Ancline
1
1 Research and post graduate department of Physics, The American College, Madurai 625002, Tamilnadu, India
DOI 10.2412/mmse.19.50.462 provided by Seo4U.link
Keywords: charge, reactivity, electrophilicity index, electrophilic region, electrostatic potential
ABSTRACT. In this work, crystallization of first-line antidiabetic drug MetforminChloride has been done by slow
evaporation method and the structure has been re-determined at 100K and the most thermodynamically stable phase A
has been obtained. Experimentally and theoretically obtained structures and their parameters match well. With the goal
of understanding the nature and reactivity of the molecule, some reactivity descriptors such as ionization energy, electron
affinity, HOMO-LUMO energy gap, chemical potential, molecular softness, hardness and electrophilicity index has been
calculated using Density functional theory with the basis set B3LYP/6-311++G(d, p). In order to get insight into the
electronic charge distribution in a molecule, Mulliken, AIM and Natural charges have been calculated and electrostatic
potential has been visualized to identify the sites of electrophilic and nucleophilic regions where the molecular interactions
likely to happen. The dipole moment has been calculated to predict the shape and polarity of the molecule. The NBO
analysis has been carried out to obtain information about the hyper conjugative interaction and electron density transfer
from the filled lone pair electron to the bonding orbitals. The docking study of Metformin cation with the 1FM9 protein
has been carried out to better understand the drug-receptor interaction.
Introduction.
Metformin Chloride(MET/Cl) is known as potent drug in the treatment of type2 non-
insulin-dependent diabetes mellitus[1]. The mechanism of the drug is alleviating hepatic glucose
production as well as increasing insulin sensitivity. This is also known as anti-hyperglycemic drug as
it reduces the risk of cardiovascular mortality without inducing hypoglycemia[2]. The investigation
on the structural, electronic, nature and reactivity of the MET/Cl molecule leads us not only to obtain
better knowledge about the existing drug but also paves way for the design of new potential and
efficient drugs. In that sense this study throws light into the structure related things, charges,
HOMO(Highest occupied molecular orbital)-LUMO(Lowest unoccupied molecular orbital) analysis,
NBO analysis, electrostatic potential and dipole moment in order to obtain better interpretation on
the character and reactivity properties of the MET/Cl molecule.
Methodology
Experimental. Crystallization of MET/Cl has been done using slow evaporation technique and
needle shaped crystal have been harvested. The structure has been re-determined at 100K and the
most thermodynamically stable phase A has been obtained.
Theoretical details. Using GAUSSIAN09 [3] software, the optimization of structure of MET/Cl has
been done at B3LYP level with the basis set 6311G++(d, p) to obtain minimum energy structure. The
equilibrium structure has been achieved with the absence of imaginary frequency.
Results and discussion
Structural details. The optimization yields the results that MET/Cl molecule has 22 atoms and it has
60 degrees of freedom. The structure has one Metformin cation and one Chlorine anion. Especially
the metformin cation consists of three amine(-NH2) groups and two methyl(-CH3) groups linked
© 2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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15
through alternate C-N bonds. The optimized structure clearly shows the occurrence of delocalization
among the C-N bonds. The nuclear repulsion energy has been found to be 661.70 Hatrees. The
optimized structure of MET/Cl was shown in figure1.
Fig. 1. Optimized Structure of MET/Cl.
Atomic charges
Analysis on the atomic charges provides information on charge distribution in the molecule and this
describes the process of electronegativity equalization and charge transfer in chemical reactions. In
order to get better perspective on charge distribution the comparison of Mulliken charges[4], AIM[5]
and Natural population analysis[6] has been done and is given in Fig.2. Mulliken Population Analysis
[4] based on the linear combination of atomic orbitals is the study of charge distribution within
molecules, which partitions the total charge among the atoms in the molecule with its sign and
magnitude while AIM charges[5] are based on charge density distribution. According to the results
of the three analyses, all nitrogen N11, N12, N13, N14, N15 and Cl22 atoms carry negative charges.
Fig. 2. Plot of atoms and charges from AIM, MPA and NPA analysis.
Nature and chemical reactivity
Frontier molecular orbital theory is an application of Molecular Orbital theory which describes the
HOMO (Highest occupied molecular orbital) and LUMO (Lowest unoccupied molecular orbital)
interactions and the bonding nature in terms of wave characteristics of electrons. Notably the HOMO-
LUMO analysis has been carried out to explain the charge transfer within the molecule. The HOMO
and LUMO energies were calculated by the standard basis set B3LYP/6-311G++ (d, p) where HOMO
C1
H2
H3
H4
C5
H6
H7
H8
C9
C10
N11
N12
N13
N14
N15
H16
H17
H18
H19
H20
H21
Cl22
Atoms
-1.2
-0.7
-0.2
0.3
0.8
1.3
1.8
Charges
AIM
MPA
NPA
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16
state is found at -0.214a.u. and LUMO is found at -0.039a.u. The HOMO-LUMO isosurface maps
and energy level graph of the molecule is given in Fig.3.
DFT has become an efficient tool to provide theoretical insights into the chemical reactivity and site
selectivity in terms of popular qualitative chemical concepts like electronegativity (χ), chemical
hardness (η), softness(S), chemical potential (μ), and electrophilicity index (ω). By Koopmans’
theorem [7] ionization potential (I)[8], electron affinity(A)[9], electronegativity(χ)[10], hardness
()[11], softness(S)[12] which are based on the energy of the HOMO and the LUMO.
 


 


 
where 

 

Where I and A are the ionization potential and electron affinity of the molecules respectively.
The DFT method predicts that the HOMO LUMO energy gap of MET/Cl is 0.175a.u. which is
found to be very low and it leads to less stability of the molecule and it is more polarizable as the
frontier orbital gap is small and is associated with low kinetic stability, high chemical reactivity.
The low ionization energy 0.214a.u. of MET/Cl shows that the molecule is highly reactive.
Electronegativity measures the power of an atom to attract electrons to it. The target molecule has
electronegativity of 0.126a.u. and so it has low capacity of attracting electrons from the neighboring
molecules. Softness is used to measure the extent of chemical reactivity and is the measure of the
capacity of an atom or group of atoms to receive electrons [12]. It is the reciprocal of hardness.
S = 1/
The calculated softness value for this molecule is very high and is found to be 5.715a.u. and this states
that the molecule is very soft. Notably if the HOMO and the LUMO are close together, the absolute
hardness is low and the atoms or molecules are ready to share the electrons to create the covalent
bond. The title molecule has very low HOMO LUMO energy gap of 0.175a.u. which forms a strong
bond with other polarizable molecule. This is the most desirable property for any possible
intermolecular interaction between a pharmaceutical compound and a bio molecule and a tool to
forecast whether the molecule is a fast interacting drug or not. Moreover MET/Cl has very less
toxicity as the electrophilicity index [13] is very low (0.090a.u.).
Fig. 3. Plots of HOMO, LUMO and energy gap of MET/Cl.
EHOMO = -0.214a.u.
ΔE= -0.175a.u.
EHOMO = -0.039a.u.
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17
The reactivity descriptors have been listed in Table 1.
Table 1. Reactivity descriptors of MET/Cl molecule.
Reactivity descriptor
Energy(a.u.)
Reactivity descriptor
Energy(a.u.)
Electron affinity
A=[-E
LUMO
]
Ionization potential
I=[-E
HOMO
]
Global hardness
η=(I-A)/2
softness
S=1/2η
0.039
0.214
0.088
5.715
Electronegativity
χ=(I+A)/2
Electrophilicity index
ω=μ
2
/2η
HOMO energy
LUMO energy
0.126
0.090
-0.214
-0.039
Electrostatic potential and docking analysis
The electrostatic potential is very effective tool to predict the reactive sites of the molecule with the
target molecule[14]. The Fig.4a clearly shows the electrophilic and nucleophilic regions of the
MET/Cl molecule. The large electronegative region(red colour isosurface) is found in the vicinity of
the Cl anion which is susceptible to electrophilic attack and large positive region(blue colour
isosurface) is seen on the MET cation which is prone to nucleophilic attack.
The interaction of drug with protein(Fig.4b) can be understood through docking analysis. Interaction
of the Metformin drug with the amino acid residues present in the 1FM9 protein. The N atoms are
interacting with the amino acid residues such as Hn, Hg1, Hz2 present in the 1FM9.
a) b)
Fig. 4. a) View of electrostatic potential of MET/Cl b) Interaction of metformin cation with the amino
acid residues of 1FM9 protein.
NBO Analysis
The NBO analysis provides information on the intermolecular interactions of the molecule and it
plays vital role in interpreting the hyper conjugative interaction and electron density transfer from the
filled lone pair electron[15]. The condition for occurring intra-molecular charge transfer is the orbital
overlap between bonding(σ) and non-bonding(σ*) orbital which stabilizes the system. Table2 gives
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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18
the Second order perturbation theory analysis of Fock matrix in NBO basis corresponding to the
intramolecular of the MET/Cl compound. The interaction of σ(C1 - H2) with the σ*(C5 - N11) takes
the highest hyperconjugative energy and is found to be 3.72kcal/mol. The interaction between the
bonding σ(C5-H6) and anti-bonding σ*(N11) takes the lowest hyper conjugative energy,
0.51kcal/mol.
Table 2. Donor and acceptor NBO and energy details of MET/Cl.
Donor
NBO(i)
Acceptor
NBO(j)
E
(2)a
kcal/
mol
E(j)-
E(i)
b
a.u.
F(i,j)
c
a.u.
Donor
NBO(i)
Acceptor
NBO(j)
E
(2)a
kcal/
mol
E(j)-
E(i)
b
a.u.
F(i,j)
c
a.u.
σ(C1 - H2)
σ(C1 - H3)
σ(C1 - H4)
σ(C1 N11)
σ(C5 - H6)
σ(C5 - H7)
σ(C5 - H8)
σ(C5 - N11)
σ(C9 - N11)
σ(C9 - N12)
σ*(C5 - N11)
σ*(C9 - N11)
σ*(N11)
σ*(C5)
σ*(N11)
σ*(C9 - N11)
σ*(C1 - N11)
σ*(C1)
σ*(C1)
σ*(C1 - N11)
3.72
2.74
0.68
0.76
0.51
3.38
3.21
0.78
0.75
3.61
0.85
1.02
1.32
1.48
1.31
1.02
0.85
1.52
1.65
1.17
0.050
0.048
0.027
0.030
0.023
0.053
0.047
0.031
0.032
0.058
σ(C9 - N13)
σ(C10 - N1)
σ(C10 - N15)
σ(N12 - H16)
σ(N12 - H17)
σ(N14 - H18)
σ(N14 - H19)
σ(N15 - H20)
σ(N15 - H21)
σ*(C10)
σ*(N13)
σ*(N13)
σ*(C9)
σ*(C9)
σ*(C10)
σ*(C10)
σ*(C10)
σ*(C10)
2.59
0.82
0.53
0.55
1.95
0.84
1.43
1.78
0.93
1.95
1.61
1.62
1.86
1.87
2.25
1.80
1.75
1.77
0.064
0.033
0.026
0.029
0.054
0.039
0.045
0.050
0.036
E
(2)a
refers energy of hyperconjugative interaction;
E(j)-E(i)
b
refers energy difference between donor and acceptor i and j NBO orbitals;
F(i,j)
c
refers the Fock matrix element between i and j NBO orbitals.
Summary. This study gives clear picture about the structure, electronic properties, nature, chemical
reactivity and molecular electrostatic potential of the biguanide MET/Cl. The three analyses of
charges report that all the N atoms have negative charges and especially the Cl anion has the highest
negative charge. The molecule is very soft in nature and highly polar molecule, less toxic when
compared to the other biguanides, highly chemically reactive and a fast interacting drug. The Cl anion
is susceptible to electrophilic attack and the MET cation is susceptible to nucleophilic attack. The
NBO analysis lists out the highest and lowest interaction of hyperconjugative energy. The docking
analysis reveals the interaction of metformin cation with the amino acid residues present in the 1FM9
protein.
References
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Cite the paper
R. Niranjana Devi, S. Israel, C. Ancline, (2017). An Analysis of Structural, Electronic and Reactivity
Properties of MetforminChloride using XRD and DFT Approach. Mechanics, Materials Science &
Engineering, Vol 9. doi 10.2412/mmse.19.50.462
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
20
Structural, Spectroscopic, Thermal studies of Pure and DL-Methionine Doped
ADP Crystals
3
J.H. Joshi
1
, H.O. Jethva
1
, P.T. Bagda
1
, K. Ashish Prasad
1
, M.J. Joshi
1
1 Department of Physics, Saurashtra University, Rajkot 360 005, India
DOI 10.2412/mmse.42.48.140 provided by Seo4U.link
Keywords: ammonium dihydrogen phosphate, powder XRD, FT-IR, TGA/DTA.
ABSTRACT. The growth of Nonlinear Optical crystals retains great number of attention nowadays. Ammonium
Dihydrogen Phosphate (ADP) is an important NLO material used for electro-optical applications and LASER material
for Nd: YAG and Nd: YLF etc. Amino acids due to their properties like molecular chirality and zwitter ionic structure
attract many researchers to dope them in ADP for the improvement of its properties. The Pure and 0.1wt% DL-Methionine
doped ADP crystals were grown using slow solvent evaporation technique at room temperature. The Powder XRD shows
single phase nature of doped crystal with slight variation in unit cell parameters. The interaction of DL-Methionine with
functional groups of ADP crystal was studied using FT-IR spectroscopy. The TGA curve of pure ADP sample indicates
that it remain stable upto 200
o
C and then decompose slowly, while the doped sample slowly decomposes right from
beginning of the analysis. The DTA curves exhibits endothermic peaks at 209
o
C and 212
o
C for pure and doped sample,
respectively.
Introduction. Ammonium dihydrogen phosphate (ADP) is important isomorphs of the Potassium
dihydrogen phosphate (KDP) type crystal, which is used for several nonlinear optical applications
and higher SHG efficiency of fundamental laser with large NLO coefficients [1-2]. Amino acids
possess properties like molecular chirality, absence of strongly conjugated bond and Zwitter ionic
nature [3] attracted researcher to dope them in KDP [4] and ADP [5,6] crystals to improve the NLO
performance and other properties. DL-Methionine consists of a 4-carbon aliphatic straight chain, the
distal end of which is capped by a complex guanidinium group. The conjugation between the double
bond and the nitrogen lone pairs, the positive charge is de-localized, enabling the formation of
multiple H-bonds. In present context, the authors have doped amino acid DL-Methionine in ADP
crystals to investigate its effect on structural, spectroscopic and thermal properties.
Experimental Technique. The slow solvent evaporation technique was employed for the growth of
crystals. ADP was added to 200ml distilled water under constant stirring to achieve saturation. After
rigorous stirring for 4 hours the solution was filtered using Watmann filter paper no.1. Then the
solution was subdivided into two beakers; one beaker contains 100ml pure ADP solution and in the
other beaker 0.1wt% DL-Methionine was added in 100 ml solution of ADP and stirred well for 4
hours. All beakers were kept in a dust free atmosphere with a porous lid to control the evaporation.
After 20 days good quality, transparent, colourless crystals were harvested. Fig. 1show the harvested
crystals of pure ADP and 0.1wt %DL-Methionine doped ADP, respectively.
© 2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
21
Fig. 1. Grown crystal of Pure and 0.1wt% DL-Methionine doped ADP crystals.
Powder XRD was carried on PHILIPS X’PERT MPD system and the data were analyzed by software
powder-X. FTIR spectra were recorded in KBr media within the region of 4004000 cm-
1
employing
THERMO NICOLET 6700 spectrophotometer. The TGA/DTA/ was performed on Linseis STA PT
1600 setup from room temperature to 900
0
C at a heating rate of 15
0
C/min in air atmosphere.
Results and Discussion:
Fig. 2. Powder XRD Pattern.
Fig. 2 shows Powder XRD pattern of pure and 0.1wt% DL-Methionine doped ADP crystals. From
the Fig. it can be seen that due to doping of DL-Methionine in ADP no additional phase was observed
and both the samples retained single phase nature with characteristic diffraction peaks like (2 0 0), (1
1 2), (2 0 2), (3 0 1), (3 0 3), (2 0 4), (3 2 3) etc. But the variation in intensity is observed which
indicates the presence of dopant in ADP. Both the crystals belonged to tetragonal symmetry with
lattice parameter a=b=7.504 Å, c=7.552 Å for pure ADP and a=b=7.507 Å, c=7.557 Å for 0.1wt%
DL-Methionine doped ADP.
To estimate the lattice strain introduced by the dopin, the Williamson-Hall method was applied to
power XRD patters [7].
β cosθ = Kλ/L + ηsinθ
where β full width half maximum of high internsity diffraction peaks;
L crystallite size;
Pure ADP
DL-Methionine doped ADP
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22
η strain;
K 0.9;
λ 1.54178 Å.
Fig. 3. (a-b).W-H plots of pure and 0.1wt% DL-Methionine doped ADP crystals.
Fig. 3(a-b) shows Williamson Hall plots of pure and 0.1wt% DL-Methionine doped ADP crystals
respectively. The linear fitted plot of βcosθ vesus sinθ gives crystallite size and strain from intercept
and slope respectively.
The crystallite size is found to be 0.431 mm and 0.779 mm while the strain is found to be 0.03161
and 0.00515 for pure and 0.1wt% DL-Methionine doped ADP crystals respectively. Such plots revel
that the doping of DL-Methionine in ADP increses teh crystallite size of ADP and decrese the lattice
strain. These results confirmed presence of DL-Methionine in ADP.
Fig. 4. FT-IR spectra of pure and 0.1wt% DL-Methionine doped ADP crystals.
The doping of DL-Methionine in ADP was confirmed by FT-IR spectra of Fig. 4. The FT-IR spectrum
of pure ADP crystal shows the O-H stretching of water at 3229 cm
-1
, P-O-H stretching at 1084 cm
-1
,
N-H stretching of ammonium at 2825 cm
-1
and PO
4
vibration at 590 cm
-1
and 453 cm
-1
. The FT-IR
spectrum DL-Methionine doped ADP shows the peak shifting from higher to lower wavelength due
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
23
to presence of DL-Methionine in ADP, e.g., the PO
4
vibration of pure ADP is shifted from 590 cm
-1
to 565 cm
-1
in the doped ADP crystal. The FTIR spectrum of DL-Methionine doped ADP indicates
absorption occurring at 2828 cm
-1
and 1697 cm
-1
are due to C-H symmetric stretching and C=O
stretching of COOH group, respectively, indicating the presence of amino acid, which is absent in
pure ADP.
The relation between the absorption frequency and the force constant can be written as [8],
υ = 1330 [F (1/M
1
+ 1/M
2
)]
½
where υ absorption frequency (cm
-1
), 1330 = (N
A
10)
1/2
/ 2C;
N
A
Avogadro’s number;
F force constant (Nm
-1
);
M
1
and M
2
molecular masses of atoms (u).
Presently the force constant for O-H stretching vibration were calculated. It is found to be 558 N/m
and 552 N/m for pure and 0.1wt% DL-Methionine doped ADP respectively. It can be seen that the
force constant altered as the DL-Methionine interacts with the hydrogen bond of ADP.
Fig. 5. (a-b) TGA/DTA curves for pure and 0.1wt% DL-Methionine doped ADP crystals.
Figures 5 (a-b) shows the TGA/DTA curves of pure and 0.1wt% DL-methionine doped ADP crystals,
respectively. The pure ADP sample destabilizes above 200
o
C and starts decomposing and above
500
o
C it is decomposed more than 69% of the original mass by expelling various gases. From the
thermogram of 0.1 weight % DL-methionine doped ADP crystal, it is found that the crystal starts
decomposing very slowly right from the beginning of the analysis and at 200
o
C it is decomposed by
6 % of the original weight, thereafter, the thermal behaviour is almost the same that of the pure ADP.
The endothermic reaction peak can be assigned due to melting and decomposition of ADP, i.e.
decomposition to orthophosphoric acid H
3
PO
4
of the crystal [9]. It can be found that the stability of
the crystals is not appreciably affected by doping of amino acid DL-methionine in ADP.
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
24
Table 1. Thermodynamic parameters of pure and 0.1wt% DL-Methionine doped ADP crystals.
Sample
Reaction
Peak
Temperature
(
0
C)
ΔH
(J/kg)
ΔC
p
(J/kg.K)
Amount of
Heat change
(Vs/kg)
Pure ADP
Endothermic
209
0
-45.56 * 10
-4
648
-160.26
ADP + 0.1wt%
DLM
Endothermic
212
0
-50.75 * 10
-4
1351
-160.38
Summary. The pure and 0.1wt% DL-Methionine doped ADP crystals were successfully grown by
slow solvent evaporation technique at room temperature. The powder XRD exhibits single phase
nature of doped sample with slight variation in the unit cell parameters. The shifting of absorption
peaks in FT-IR and the occurrence of absorptions responsible to C-H and C=O indicated interaction
of amino acids with ADP. The Thermal study shows DL-methionine marginally reduced the thermal
stability of ADP.
Acknowledgement.
The authors are thankful to UGC for financial assistance under SAP DRS II and DST under FIST
and Prof. H.H.Joshi (Head, Department of Physics, Saurashtra University, Rajkot) for his
encouragement and support
References
[1] R.B.Adhav, Application of Nonlinear Crystals in LIA Handbook of Laser Material Processing,
Mognolia (2001).
[2] D.N.Nikogosyan, Nonlinear Optical Crystals A Complete Survey, Springer Heidelberg (2005).
[3] J.F.Nicoud, R.J.Twieg, Eds, D.S.Chemla and J.Zyss, Academic press, London, 277 (1987).
[4] K.D.Parikh, D.J.Dave, B.B.Parekh and M.J.Joshi, Bull.Mater.Scie, 30,105-112 (2007).
doi:10.1007/s12034-007-0019-4.
[5] J.H.Joshi, B.V.Jogiya, M.J.Joshi and K.D.Parikh, Int. J. Chemtch. Res.,6, 1555-1558 (2014).
[6] T.Josephine Rani, F.Loretta, P.Selvarajan, S.Ramalingom, S.Peruma, Rec.Res.Scie &
Tech.,3(7),69-72,2011.
[7] G.K.Williamson, W.H.Hall, X-ray line broadening from filed aluminium and wolfram,
1(1)(1953)22-31 doi:10.1016/0001-6161(53)90006-6.
[8] V.S.Joshi, M.J.Joshi, Ind.J.Phy., 75(2) (2001) 159-163.
[9] A.Abdul Kadar, A.A.Ammer, S.I.Saleh, Thermochimica Acta., 176(1991)293-304.
doi:10.1016/0040-6031(91)80285-Q.
Cite the paper
J.H. Joshi, H.O. Jethva, P.T. Bagda, K. Ashish Prasad, M.J. Joshi, (2017). Structural, Spectroscopic, Thermal
studies of Pure and DL-Methionine Doped ADP Crystals. Mechanics, Materials Science & Engineering, Vol 9.
doi 10.2412/mmse.42.48.140
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
25
Impedance Spectroscopy of Sodium Sulphide Added ADP Crystals
4
A.P. Kochuparampil
1
, J.H. Joshi
1
, H.O. Jethva
1
, M.J. Joshi
1
1 Department of Physics, Saurashtra University, Rajkot, Gujarat, India
DOI 10.2412/mmse.4.87.814 provided by Seo4U.link
Keywords: slow solvent evaporation, ADP, Chalcogenide, dielectric, complex impedance, complex modulus.
ABSTRACT. Ammonium dihydrogen phosphate (ADP) is popular nonlinear optical material with wide applications.
Chalcogenide compounds are very poorly soluble in water and hence difficult to add during growth of ADP from aqueous
solution to engineer and modify properties of ADP. Hence the solubility of chalcogenide compound Na
2
S was increased
by synthesizing its nano-particles with capping agents. The growth of pure and Na
2
S added crystal was achieved by the
slow solvent evaporation method. Complex impedance plots were recorded in the frequency range of 100 Hz to 1MHz at
room temperature. Dielectric constant and loss exhibited normal behaviour with respect to frequency. The complex
modulus spectra indicated effect of grain and grain boundary in pure ADP sample. From Jonscher’s plot various
parameters were calculated and found to decrease for doped samples compared to pure ADP. The non Debye type
relaxation was found from plots of Z'' and M'' versus frequency.
Introduction. Complex Impedance Spectroscopy is an effective experimental technique used to
characterize a.c. electrical properties of crystalline materials. It enables to resolve the relaxation
contributions, like, bulk effects, grain boundaries and electrode interface effects in the frequency
domain of materials [1]. Ammonium Dihydrogen Phosphate (ADP) is widely used in the area of
nonlinear optics, electric-optics, harmonic generation and optical mixing [2]. Na
2
S can be used as
thermo-chemical storage system [3]. In present paper authors studied dielectric, complex impedance
and modulus spectroscopic aspects of pure and Na
2
S doped ADP crystals. The authors aim is to add
Na
2
S in ADP crystal to engineer and modify its properties.
Experimental: Sodium sulphide (Na
2
S) was synthesised by co-precipitation method and then sample
was irradiated through microwave to increase the solubility of precipitate nanoparticles. 0.5M sodium
acetate (CH
3
COONa) and 1.5M thiourea (CH
4
N
2
S) were taken as starting materials. The solution of
sodium acetate was filled in burette. 10ml capping agent ethylene diammine was added in the thiourea
solution at 70
0
C. The solution of sodium acetate was added in drop-wise manner into the thiourea
solution, resulting towards light yellowish precipitate. After continuous stirring of 7 hours the
colloidal solution was subjected to the microwave irradiation in domestic microwave oven of Kenstar
having input power of 1450W and by adjusting microwave irradiation 10% of input power, 145W for
15 minutes till that the solution completely evaporated and only solid remained which was further
washed by distilled water and acetone. The dried irradiated sample was crushed using mortar pestle.
As the chalcogenide compound Na
2
S nanoparticles were very less soluble in water to increase its
solubility capping agent ethylene diammine was used. Its solubility was increased and found to be
0.18g in 100ml. Pure ADP and Na
2
S added ADP crystals were grown by using the slow solvent
evaporation method at room temperature. Required amount of ADP was added to 400ml distilled
water under constant stirring to achieve saturation. After rigorous stirring for 4 hours the solution was
filtered using Watmann filter paper no.1. Then the solution was subdivided into four beakers; one
beaker contains 100ml pure ADP solution and in the other three for 2ml, 5ml and 10ml Na
2
S solution
was added in ADP solution and stirred for 3 hours. After 15 days the highly transparent and good
© 2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
26
quality crystals have been grown, due to the doping of Na
2
S in ADP crystal there was no colour
change, but the change in morphology indicates the presence of dopants in ADP crystals as shown in
Fig. 1.
Fig. 1. a) pure ADP, b) 2NADP, c) 5NADP and d) 10NADP.
The AAS was carried on Shimazdu AA-6200 with sodium source was used to detect sodium in doped
crystals and the results were listed in table 1.The complex impedance spectra were recorded for
pelletized samples in a frequency range of 10Hz to 10MHz at room temperature using HIOKI 3532
LCR HITERSTER meter.
Result and discussion
Fig. 2. a) Dielectric constant versus logω and b) Dielectric loss versus logω.
Fig. 2 a) shows variations of dielectric constant with respect to applied angular frequency for pure
and different mole percentage Na
2
S added ADP crystals. High dielectric constant at lower frequency
for all samples which may due to the contribution of all kinds of polarization, Viz., electronic, ionic,
orientation and space charge polarizations. As frequency increases the dielectric constant decreases
because the dipoles can not comply with the variation of the external field and hence the polarization
decreases. The doped samples possessed low dielectric constant compared to pure. Fig.2 b) shows
variation in dielectric loss with respect to the angular frequency. From the Fig. it can be seen that the
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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27
doped sample exhibits less dielectric loss compared to pure ADP, which indicates that the doped
samples possessed minimum defect and good optical properties [4].
Fig. 3. Jonscher’s Plot.
Fig.3 shows Jonscher’s plot of both pure and Na
2
S added ADP crystals. Jonscher’s power law is:
σ
tot
= σ
dc
+ Aω
n
where A is dependent on temperature and indicates the strength of polarizibility and exponent n is
the degree of interaction of mobile ions with lattice.
The a.c. conductivity value is lower for all Na
2
S added ADP crystals as compared to pure ADP. The
a.c. conductivity decreases slightly with increases the doping concentration. The main reason for
conduction is due to L-defect in intra-bond jump of proton generates the vacancy and D-defect at
inter-bond jump to a double occupied bond [5]. The electric conduction in ADP is ionic and the
migrating charge carrier is proton, which moves in the three-dimensional hydrogen bond network,
affecting the motion of neighbouring protons. To occupy the Na
2
S molecule in site it creates a defect.
As the conduction in ADP is protonic and mainly due to the anion [(H
2
PO
4
)
-
ion] and not due to the
cation [(NH
4
)
+
ion], the additional hydrogen bonds created may reduce the L-defect and as a result
obstruct the movement of protons. This may be the reason for the decrease in a.c. conductivity value
in all Na
2
S added ADP crystals. Here the higher value of ‘n’ for pure ADP indicates large energy
stored in such collective motion [6].The values of ‘A’ and ‘n’ are listed in table 1.
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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28
Fig. 4. Nyquist plot a) Pure ADP and b) Na2S added ADP.
Fig.4. shows Nyquist plots of pure ADP and Na
2
S added ADP crystal. The small semi-circle near the
origin for pure ADP at higher frequency region indicates the grain effect and the large semi-circle at
lower frequency indicates the grain boundary effect, while same plots for the Na
2
S added ADP
samples shows single semi-circle indicates grain effect only. The equivalent R-C parallel circuits are
presented at inset of fig. 4.
Fig. 5. Complex modulus.
To discriminate the electrode polarization and grain boundary effect complex electric modulus is
used. Fig. 5 shows complex modulus plots for pure and Na
2
S added ADP. In pure ADP spectrum two
clear semi circles appear due to grain at higher frequency and grain boundary effect at lower
frequency, while for doped ADP crystals, single semicircles are observed confirming the presence of
grain effect only.
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
29
Fig. 6. M’’ and Z’’ versus logω a)Pure ADP, b) 2NADP, c) 5NADP and d) 10NADP.
Fig.6 shows the plots of M'' and Z'' versus applied angular frequency. The modulus spectra of pure
and Na
2
S added ADP crystals, exhibit broad and asymmetric nature indicating non-Debye type
relaxation process with distributed relaxation times about mean relaxation time. The non-Debye type
relaxation immediately indicates the stretched exponent parameter β, given as β = 1.196/W - 0.047,
where W is FWHM from M'' Vs logω plot. The smaller the value of β the greater is the deviation with
respect to Debye type relaxation. The β value is always less than unity for a system in which the
dipole-dipole interaction is significant [7]. From table no.1 it can be seen that the β parameter of
doped samples appropches to higher value compare with pure ADP indicates more debye type
relaxation behaviour in doped samples compare to pure.
Table 1. AAS data and parameters of complex impedance and complex modulus.
Sample
ppm
counts
of
Na
+
R
g
(MΩ)
C
g
(pF)
R
gb
(MΩ)
C
gb
(pF)
τ
g
(mS)
τ
gb
(mS)
n
A
(S.m
-1
.rad
-n
)
β
Pure
ADP
-
28.9
141.5
30.75
58.47
4.08
1.79
0.71
8.26x10
-6
0.145
2NADP
0.89
66.97
43.07
-
-
2.88
0.51
1.58x10
-8
0.517
5NADP
1.98
98.28
18.44
-
-
1.81
0.50
1.62x10
-8
0.520
10NADP
3.66
48.83
38.32
-
-
1.87
0.47
2.51x10
-8
0.4990
Summary. Pure and Na
2
S added ADP crystals have been sucessfully grown using slow solvent
evaporation method. The AAS data confirms the presence of sodium ion in Na
2
S added ADP crystals.
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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30
Dielectric constant and dielectric loss found to be lower in Na
2
S added ADP compared to pure ADP.
The Jonscher’s Plot is applied to the a.c. conductivity. The complex modulus spectra showing two
semi-circle for pureADP due to presence of grain and grain boundary and single semi circle for Na
2
S
added ADP due to effect of grain only. The streched exponent revels more debye type relaxation in
doped samples compare to pure one. The Impedance and Modulus spectroscopy found to be very
sensitive for small concentration of dopant in ADP.
Acknowledgement. Authors are thankful to Prof. H.H. Joshi (HOD, Department of Physics,
Saurashtra University, Rajkot, Gujarat, India) ,Prof. D.K. Kanchan (M.S. University, Baroda,
Gujarat, India) for their keen interest and also the authors acknowledge the financial assistance under
SAP DRS-II and DST FIST.
References
[1] J.R.Macdonald, Impedance Spectroscopy, (John Wiley and Sons, 1987)
[2] D.N. Nikogosyan, Nonlinear Optical Crystals, A complete Survey, Spinger, Heidelberg (2005)
[3] M. Roelands, R. Cuypers, K. D. Kruit, H. Oversloot, A. Jong, W. Duvalois, L. Vliet and C.
Hoegaerts, Energy Procedia 70 ( 2015 ) 257 266.
[4] D.Zion, S.Devarajan, T.Arunachalam, Journal of Crystallization Process & Technology, 3 (2013)
5-11. doi:10.4236/jcpt.2013.31002.
[5] M.Meena and C.K.Mahadevan, Crystal Research and Technology, 43(2) (2008) 166 172,
doi:10.1002/crat.200711064.
[6] J.H. Joshi, K.P.Dixit, M.J.Joshi and K.D. Parikh, AIP conference Proceeding, Bikaner, 2016,
(2016) pp.17281731, doi: 10.1063/1.4946270.
[7] M.P.Dasari, K.S.Rao, P.M.Krishna, G.Gopala Krishnan, Acta Physica Polonica A, 119(3) (2011)
387-394.
Cite the paper
A.P. Kochuparampil, J.H. Joshi, H.O. Jethva and M.J. Joshi, (2017). Impedance Spectroscopy of Sodium
Sulphide Added ADP Crystals. Mechanics, Materials Science & Engineering, Vol 9. Doi
10.2412/mmse.4.87.814
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
31
Growth and Characterization of a Novel Nonlinear Optical Single Crystal of L-
Isoleucinium Hydrogen Maleate Hemihydrate
5
A. Hemalatha
1,2
, K. Deepa
3
, A. Venkatesan
4
, S. Senthil
2, a
1 Department of Physics, Quaid-E-Millath Government College for women, Chennai, India
2 Department of Physics, Government Arts College (Men), Nandanam, Chennai, India
3 Department of Physics, Loyola College, Chennai, India
4 Department of Physics, Aringnar Anna Government Arts College, Villuppuram, India
a ssatoms@yahoo.co.in
DOI 10.2412/mmse.85.63.511 provided by Seo4U.link
Keywords: nonlinear optical single crystal, monoclinic system, XRD analysis, NIR spectroscopy.
Abstract: L Isoleucinium Hydrogen Maleate Hemihydrate (LIM), a nonlinear optical single crystal was grown from
aqueous medium by the slow evaporation method at room temperature. The powder XRD analysis reveals that the grown
crystal is belongs to monoclinic system with the space group P2
1
. The presence of various functional groups in the LIM
is confirmed by FT-IR and FT-RAMAN spectroscopy. The second harmonic generation (SHG) efficiency measurements
reveal that the LIM is suitable for nonlinear optical (NLO) applications. Thermo-gravimetric and differential thermo
gravimetric analysis reveal the thermal stability of the material. The optical transparency has been studied using UV-Vis-
NIR spectroscopy and the band gap energy were found out from the absorption studies. The third order nonlinear behavior
has been investigated using Z-Scan technique.
Intorduction. L- Isoleucine is organic amino acid which is the potential material with excellent
optical, thermal and mechanical properties. It is non-polar and aliphatic in nature. L-Isoluecine have
been studied and reported in the literature[1]. L-Malic acid is a organic component and it is basically
dicarboxilic acid with large π-conjucation has attracted much attention [2]. In the present work L-
Isoluecinium hydrogen maleate hemihydrates was grown from aqueous solution by slow evaporation
method. The material was characterised by powder XRD analysis, UV-Vis-NIR spectroscopic
studies, FT-IR and FT-RAMAN studies, TGA/DTA analysis and Nonlinear optical Studies were
discussed.
Crystal growth. LIM crystal was synthesized from L-Isoluecine and L-Maleic acid taken in
equimolar ratio. The required quantity of L-Isoleucine and L-Maleic acid was thoroughly dissolved
in 2D water and stired well for about six hours using a magnetic stirrer to obtain a homogenoes
mixture. Then the saturated solution of LIM was taken in a beaker and kept at room temperature for
crystallisation. Finnaly a well defined single crystal was obtained after 40 days by slow evaporation
method.
CHARACTERIZATION
Powder x-ray analysis. Powder x-ray differaction technique is used to show the inner arrangements
of atoms molecules in a crystalline material. The XRD study enumerates that the LIM belong to the
monoclinic crystal system with space group P2
1
and the lattice parameters are a=11.745 (Å),
© 2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
32
b=6.1011(Å),c=19.2198(Å), α= γ=90°, β=96.7329°. Further the diffraction pattern (Fig.1) of LIM is
perfectly matched with the reported literature [1,3].
Fig. 1. Powder XRD pattern of the LIM crystals.
Optical Analysis. Absorption spectroscopy is one of the best techniques to check the suitablity of the
grown crystal for optical device fabrication. The absorption spectrum of the grown LIM single crystal
is as shown in fig. 2(a). The crystals are transparent in the entire tested region with lower cut off
waveslength at 215nm. The highly tranparent is the essential requirment for optically active materials.
The recorded optical data was used to calculate the band gap of the grown crystal. The band gap of
the LIM crystal is shown in fig. 2(b) and found to be 4.75 eV. The grown LIM crystal can be a suitable
candidate for optoelectronic applications because of its large band gap [4].
250 300 350 400 450 500 550 600 650 700
1.0
1.5
2.0
2.5
3.0
Absorption(A) (%)
wavelength)nm
215
LIM
(a)
Fig. 2. (a). UV-Vis absorption spectrum of LIM.
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
33
0 1 2 3 4 5 6
0
2
4
6
8
10
12
14
h
x10
5
(eV)
2
m
2
heV
4.75eV
LIM
(b)
Fig. 2. (b). plot of (αhν)
2
versus hν of LIM crystal.
NLO Studies. In NLO material Second hormonic generation efficiency is most important [5]. A Q-
switched Nd: YAG laser emitting a fundamental wavelength of 1064 nm and a pulse width of 9 ns
with a repetetion rate of 10 Hz was used. The laser incident input energy of 0.7 mJ/s was illuminate
on the crystalline powder, which is filled in an air tight micro capilary tube. The emission of green
radiation of wavelength 532nm from the sample confirmed the frequency doubling of LIM. The KDP
was used as a reference material and the output energy was found to be 4.48 mW and 5.03mW from
grown crystal and reference materials respectively. Hence, from the above discussion second
hormonic generation efficincy of LIM crystal was 0.9 times that of standard KDP crystal. Thus LIM
is confirmed as a suitable NLO medium for laser generation.
Third Hormonic Generation. Third order NLO studies of LIM crystals were performed by a
versatile tool of Z scan technique. It is a acurate method to determine the nonlinear index of refraction
(n
2
), nonlinear absorption coefficient (β) and nonlinear susceptability (
(3)
) of the grown crystal. In
this technique a He-Ne laser (=632.8nm) is used as the light source and is by a lens of focal length
18.5cm. The open aperture mode helps us to calculate the nonlinear absorption coefficient and the
closed aperture mode shows the information about the third order nonlinear refractive index and the
open and closed aperture modes are shown in fig.4 (a) andfig.4 (b). The nonlinear refractive index
(n
2
), the nonlinear absorption coefficient (β) and the third order nonlinear optical susceptibility (
(3)
)
are calculated and are given in table 1.
-2 0 2 4 6 8 10 12 14 16 18 20 22 24 26
12.0
12.5
13.0
13.5
14.0
Normalized Transmittance
Z (mm)
LIM
(a)
Fig. 3. (a)Closed aperture z-scan spectrum of LIM crystal.
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
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34
3 6 9 12 15
13.0
13.2
13.4
13.6
13.8
14.0
14.2
14.4
14.6
14.8
15.0
15.2
Normalized Transmittance ( a.u.)
Z (mm)
LIM
(b)
Fig. 3. (b) open aperture z-scan spectrum of LIM crystal.
Table 1. Parameters in Z scan experiment.
Nonlinear refractive index (n
2
)
2.458x10
-11
cm
2
/W
Nonlinear absorption coefficient (β)
2.438x10
-5
cm/W
Third order nonlinear susceptibility (
(3)
)
5.5236x 10
-5
esu
Thermal Analysis. The thermal stability of LIM was studied by thermogravimetric analysis (TGA)
and differential thermal analysis (DTA) at a temperature range from room temprature to 650°C and
the thermogram is shown in fig.4. The TGA and DTA analysis is very important to understand the
thermal stability and various transaction of the sample. From TG curve, it has one stage of weight
loss. The compound start to decomposs at 144°C. The weight loss of approximately 82% occures
between the temperature 144°C - 570°C due to the elimination of a molecule such as CO
2,
H and O
and major weight loss due to decomposition of the crystal. The remaining weight loss occurs above
570°C and the sample is completely decomposed. DTA curve shows two endothermic peaks and three
exothermic peaks at 87.6°C, 128°C, 144°C, 489.6°C and 540°C respectively. The sharp peak
indicating the purity and crystallinity of the material. The endothermic peak observed at 87°C shows
the weight loss is about 7% due to the liberation of water molecules present in the crystal itself. The
first exothermic peak absorved at 144°C. It is equal to the decomposition point of the TGA curve.
The second exothermic peak observed at 489.6°C which is matched with the TGA curve. From the
DTA and TGA study, it is observed that the material has water molecules in its crystal lattice and it
has thermal stability till its 144°C.
Vibrational spectral Analysis. FTIR and FT Raman spectroscopy are very important to analysis the
various functional groups in the structure of a compound present in the grown crystal and are shown
in fig.5(a) and fig. 5(b). In the high energy region there is a broad band observed from 3600 cm
-1
-
2400 cm
-1
is assigned for O-H stretching vibration of carboxlic group.It is also over lap with the peaks
corresponding to NH assymetric stretching vibration due to the primary amines of NH
2
at 3346 cm
-
1. CH
3
assymetric stretching vibration modes at2964 cm
-
1. The peaks at 2946 cm
-1
is due to NH
3
assymetric stretching vibration which is also over lap on the OH stretching vibration and the
corresponding band in the Raman spectrum is observed at 2942 cm
-1
. Strong band observed at 1739
cm
-1
contributed of C=O symetric vibration of COOH group. The peak at 1578 cm
-1
is due to the
NH
3
deformation. The bands appeared in the region 1472 cm
-1
and 1395 cm
-1
are assigned to COO
-1
symmetric stretching vibration of COOH group and the corresponding band is observed at 1453 cm
-
1
in the Raman spectrum. The peaks at 1347 cm
-1
and 1004 cm
-1
occurs due to the CN vibration and
the corresponding band is observed at 1005 cm
-1
in the Raman spectrum. The peak observed at 1308
cm
-1
is due to CH
2
wagging vibration and the corresponding peak is also observed at 1302 cm
-1
in the
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
35
Raman spectrum. The NH
3
rocking vibration observed at 1174 cm
-1
. C-CN symetric stretching
vibtation observed at 926 cm
-1
. Very strong band observed at 871 cm
-1
due to the C-C stretching
vibration. The COO
-1
wagging and rocking vibrations are observed at 578 cm
-1
and 483 cm
-1
respectively and the corresponding band are observed at 540 cm
-1
and 479 cm
-1
in the Raman
spectrum. The vibrational study confirms the presence of COOH and NH
2
group in the LIM crystal.
0 100 200 300 400 500 600 700
-50
0
50
100
570°C
540°C
128°C
87.6°C
144°C
TEMP (°C)
DTA%/min
LIM
144°C
489.3°C
0
1000
2000
3000
4000
5000
6000
7000
DTA
TG%
TGA
Fig. 4. TG/DTA curve for LIM crystal.
4000 3500 3000 2500 2000 1500 1000 500
0
20
40
60
80
100
483
2646
1472
1891
1739
1578
1174
1004
926
871
713
578
1347
1308
2964
1249
1211
1395
3346
Wave Numbers cm-1
3515
%T
LIM
(a)
540
479
431
3055
1302
83
166
299
742
808
910
1005
1211
1398
1453
1619
1694
2744
2878
2942
2982
2913
3055
3000 2500 2000 1500 1000 500 0
0.0
0.1
0.2
0.3
0.4
RAMAN INTENSITY
Wave Numbers cm-1
LIM
(b)
Fig. 5. (a) FT-IR spectrum of the grown LIM crystal, (b)FT-RAMAN of the grown LIM crystal
Summary. Single crystals of LIM were grown by slow evaporation solution growth method at room
temperature. Powder x-ray diffraction analysis was carried out and the lattice parameters were
calculated. The Calculated values are good in agreement with the reported values. UV-Vis-NIR study
shows that the crystals are transperant in entire visible region and have minimum cut off wavelength
of 215nm. Thermal analysis was carried out and it confirms the crystal is stable upto 144°C. Its
Second Harmonic Generation efficiency was found to be 0.9 times that of standard KDP. The
functional groups present in the LIM crystal is identified by FTIR analysis and it is confirmed by the
FT-RAMAN. The nonlinear optical refractive index is (n
2
) 2.458x10
-11
cm
2
/W, nonlinear absorption
coefficient (β) is 2.438x10
-5
cm/W and third order nonlinear optical susceptibility (
(3)
) of 5.5236x
10
-5
esu are calculated by Z scan technique. Hence LIM single crystals are suitable material for
nonlinear optical device fabrication.
References
[1] Sergey G. Arkhipov, Denis A. Rychkov, Alexey M. Pugachevc and Elena V.Boldyrevaa,
Structural Chemistry (Research Paper), New hydrophobic L-amino acid salts: maleates of L-leucine,
L-isoleucine and L-norvaline, Journal of Acta Crystal C, 2015, C17, 1-9. DOI.
org/10.1107/S2053229615010888.
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
36
[2] C. Alosious Gonsago, Helen Merina Albert, S. Janarthanan, and A. Joseph Arul Pragasam, Crystal
Growth and Characterization of an Organic Nonlinear Optical Material: L-Histidinium
Maleate,(LHM), International Journal of Applied Physics and Mathematics, November 2012,Vol.2,
No. 6, DOI: 10.7763/IJAPM.2012.V2.150
[3] G. Ramasamy, Subbiah, Meenakshisundaram, Studies on amino acid picrates: Crystal growth,
structure and characterization of a new nonlinear optical material l-isoleucinium picrate, Journal of
optic communication, 2014, 125, 4422-4426. DOI. org /10.1016/j.ijleo.2014.02.036
[4] Mohd Shkir, Haider Abbas, Physico chemical properties of L-asparagine L-tartaric acid single
crystals: A new nonlinear optical material, Journal of Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy, (2014), 118, 172176, DOI. org / 10.1016/j.saa.2013.08.086.
[5] S. Masilamani, A. Mohamed Musthafa, P. Krishnamurthi, Synthesis, Growth and characterisation
of a semiorganic nonlinear optical material: L-threonine cadmium chloride single crystals, Arabian
Journal of Chemistry, 2014, DOI.org/10.1016/j.arabjc.2014.06.003.
Cite the paper
A. Hemalatha, K. Deepa, A. Venkatesan, S. Senthil (2017). Growth and Characterization of a Novel Nonlinear
Optical Single Crystal of l-Isoleucinium Hydrogen Maleate Hemihydrate. Mechanics, Materials Science &
Engineering, Vol 9. Doi 10.2412/mmse.85.63.511
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
37
Group 12-Metal Complexes derived from Donor Substituted Carboxylic Acids
and 5-Nitro-1,10-Phenanthroline: Spectroscopic and Biological Studies
6
Champaka Gurudevaru
1
, Nallasamy Palanisami
1
1 Department of Chemistry, School of Advanced Sciences, VIT University, Vellore 632 014, Tamil Nadu, India
DOI 10.2412/mmse.46.5.782 provided by Seo4U.link
Keywords: metal complexes, 5-Nitro-1,10-phenanthroline, Donor Carboxylic acid, Anti-fungal and Anti-Microbial
studies.
ABSTRACT. Momeric group 12 metal complexes [M(R-C
6
H
4
-COO)
2
(5-NO
2
-phen)] [M=Zn, R=NMe
2
(1) and M=Cd,
R=NH
2
(2)] have been synthesized from a reaction between the metal acetate, donor substituted carboxylic acid and 5-
nitro-1,10-phenathroline (5-NO
2
-Phen) at room temperature. Both complexes were characterized by elemental analysis,
FT-IR spectroscopy,
1
H NMR and UV-Vis spectroscopy studies. Compound 1 showed more potent anti-fungal activity
when compared to standard drug fluconazole and demonstrated MIC at concentration 1.6 µg/ml, 25 µg/ml, 0.4 µg/ml,
3.12 µg/ml against K. pneumonia, Pseudomonas, S. aureus, S. mutans respectively.
Introduction. In the past three decades, transition metal (TM) complexes research has been found
applications in the fields like catalysis, material science and biology [1-3]. In particular, group 12
complexes with chelating ligands show interesting biological activity, since zinc plays an importance
role in many biological processes
[4-6]
.The synthesis of derivatives of 1,10-phenanthroline and
investigations of their properties have become an attractive research area [9]. Furthermore,
carboxylate group can bind with metal ion in various modes, such as monodentate, bidentate and
bridging which are good source of ligands (O-donor) for the very generous strong bonds that they
form [10-12]. The metal complexes based on 5-nitro-1,10-phenanthroline carboxylates and further
exploiting the relationship between their structure and biological properties have constituted one of
the most attractive research fields in modern bioinorganic chemistry [13]. In particular, the zinc
complexes of different substituted carboxylic acids are important substances which have been found
to be useful as antimicrobial and antifungal agents and the antimicrobial and antifungal mode of
action of these molecules is still not fully understood while the few groups attempted to understand
the mechanism of antibacterial and antifungal activity of zinc compounds were done, but still it is
unclear [14-15]. The best of our knowledge, there is no report in the literature on antibacterial and
antifungal studies based on zinc derivative of aromaticcarboxylates using 5-nitro-1,10-phenanthroline
as a co-ligand. Inspired by the aforementioned considerations, we report here,the synthesis and
investigation of synthesis, spectral and antimicrobial and antifungal activity of group 12 metal
complexes with 5-nitro 1,10-phenanthroline as a co-ligand.
Experimental
Instruments and Methods. Elemental analysis (C, H and N) was performed using LECO-932 CHNS
Analyser, IR spectra was recorded using Perkin Elmer Spectrum 100 and recorded from the range
4000 to 650 cm
-1
, UV-Visible spectra were recorded on a Perkin Elmer Lambda 35
spectrophotometer. Molar extinction coefficients (ɛ max, M
-1
cm
-1
) were determined from absorption
maxima obtained in the range 200800 nm, using a 1 cm quartz cuvette. Samples were prepared in
methanol and analysed at room temperature. Melting Point was recorded using Buchi M-565
© 2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
38
Instrument, One dimensional NMR spectra was obtained using 400 MHz Bruker spectrometer in d
6
-
DMSO as solvent.All chemical shifts are reported in parts per million (ppm). d = doublet, dd = doublet
of doublets, t = triplet,s = singlet, bs = broad singlet, bd = broad doublet, bt = broad triplet.
Solvents and starting material. Analytical grade solvents were used for the synthesis of the
compounds.Zinc acetate, cadmium acetate, 4-aminobenzoic acid and 4-(dimethylamino) benzoicacid
were purchased from Sigma Aldrich.The precursor 5-NO
2
-phen was synthesized based on already
reported synthetic procedure [16].
Antifungal and Antibacterial studies. Antifungal activities of compound 1 were studied against C
albicans. Results of anti-fungal activity when compared to standard drug Fluconazole. Antibacterial
activity for compound 1 were performed towards different microorganisms which was carried out
using MIC determination method. Different microorganisms such as, Gram Positive Staphylococcus
aureus (S. aureus), Staphylococcus mutans (S. mutans), and Gram Negative Klebsiella pneumoniae
(K.Pneumoniae), Pseudomonas aeruginosa (P.aeruginosa) bacterial strains were used for
antibacterial activity of compound 1 and compared with the standard drug Ciprofloxacin.
Synthesis
Compound 1. Sodium methoxide solution (10 mL) is added to 4-(dimethylamino) benzoic acid
(0.1651g,1 mmol) and stirred for 30 minutes. To which zinc (II) acetate dihydrate (0.2195g,1 mmol)
was dissolved in methanol (10 mL) and clear methanolic solution (20 mL) of 5-NO
2
-phen (0.2250g,1
mmol) was added. The resulting solution was stirred for 30 minutes and filtered. The filtrate was kept
at room temperature for crystallization. Dark red color crystals were isolated after a few days. Yield:
60 %. mp. 185˚C . Anal. Calcd for C
30
H
27
N
5
O
6
Zn: C 58.2; H 4.4; N 11.3. Found: C57.9; H 4.2; N
10.9. IR (KBr, cm
-1
): 3452(s), 1737(m), 1597(s),1516(s), 1354(broad s), 1193(s), 837(s),783(s), UV-
Vis (CH
3
OH, nm) 206, 225, 299.
1
H NMR (400 MHz, DMSO-d
6
) 2.9 (s, 4CH
3
), 6.6 (d, aromatic
4CH), 7.7 (d, aromatic 4H), 8.2 (t, phen 2H), 9.0 (d, phen1H), 9.2 (d, phen 2H), 9.4 (d, phen 2H).
Compound 2. The compound 2 was synthesized in the similar method of Compound 1.Dark Rediish
Brown color crystals were isolated after a few days. Yield: 55 %. MP. 198˚C . Anal. Calcd for
C
26
H
19
N
5
O
6
Cd: C 51.2; H 3.1; N 11.48. Found: C 50.8; H 3.2; N 11.1. IR: 3466(w), 3176(s), 1593(s),
1514(s), 1365(s), 1178(m), 785 (s). UV-Vis (CH
3
OH, nm) 206,273.
1
H NMR (400 MHz, DMSO-d
6
)
5.4 (s, aromatic 2NH
2
), 6.5 (d,aromatic 4CH), 7.6 (d,aromatic 4CH), 8.1 (t, phen 2H), 9.0 (d, phen
1H), 9.1 (d, phen,1H,), 9.2 (s, phen,1H), 9.3 (d, phen,1H), 9.4 (d, phen, 1H).
Results and Discussion
Synthesis. The synthesis of the compound 1and 2 has been achieved by reaction between zinc acetate
and sodium methoxide solution is added to 4-(dimethylamino) benzoicacid in the presence of 5-NO
2
-
phen ligand (Fig. 1). Both are air stable, soluble in common organic solvents like MeOH, DMF and
DMSO and the crystalline products was purified by the recrystallization technique by the slow
evaporation method. The results of compound 1 and 2 in elemental analysis shows that the products
consistentswith the calculated values in the molecular formula of [Zn(Me
2
N-C
6
H
4
-COO)
2
(5-NO
2
-
phen)] (1) and [Cd(NH
2
-C
6
H
4
-COO)
2
(5-NO
2
-Phen)] (2).
Fig. 1. Scheme of Synthesis.
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
39
Spectral Characterization. Compound 1and 2 was characterized by FT-IR spectroscopy. It revealed
that monodentate binding mode of aromatic COO
in compound 1 displays asymmetric stretching
vibration band ν
a
(COO
) at 1597 cm
-1
and wheras for the compound 2 at 1593 cm
-1
, and symmetric
stretching vibration band ν
s
(COO
) at 1365 cm
-1
for compound 1 and 1354 cm
-1
for compound
2
[17]
.Addtionally, the C-H bending vibration of Phenanthroline ring occurs at 783 cm
-1
for compound
1 and 785 cm
-1
for compound 2.
The
1
H NMR spectrum for the compound 1 and compound 2 in DMSO-d
6
, compound 1 shows the
presence of resonances at δ = 2.9 ppm which can be assigned to the protons of the CH
3
group in
aromatic rings. The resonance appearing at δ = 6.6 and 7.7 ppm can be assigned to the proton attached
to aromatic rings, δ = 8.2 ppm can be assigned to –CH proton attached to aromatic rings, δ = 9.0, 9.2
and 9.4 ppm can be assigned to the proton attached to phen ring, whereas compound 2 shows the
presence of resonances at δ = 5.4 ppm can be assigned to the NH
2
attached to aromatic rings and
δ=6.5 and 7.6 ppm can be assigned to the proton attached to aromatic rings, δ = 8.1 ppm can be
assigned to CH proton attached to aromatic rings, δ = 9.1, 9.2, 9.3 and 9.4 ppm can be assigned to
the proton attached to phen ring.
The UV-Vis spectrum of compound 1 and 2 in CH
3
OH shows absorption maximum band in the region
200-300 nm for high energy π–π* and n π* transitions (Fig. 2). Compound 1 has absorption
maximum at 299, 225 and 206 nm whereas Compound 2 has absorption maximum at 273 and 206
nm [18].
Fig. 2. UV Vis spectra of compound 1 and 2.
Antimicrobial and Antibacterial activity of compound 1. The tested bacterial and fungal strains
were prepared in the BHI broth and incubated at 37˚C and 200 rpm in an orbital incubator for
overnight.Sample solutions were prepared in DMSO for concentration 100, 50, 25, 12.5, 6.25, 3.12,
1.6, 0.8, 0.4 and 0.2 µg/ml. The standard drug solution of Ciprofloxacin (antibacterial drug) and
Fluconazole (antifungal drug) were prepared in DMSO. Serial broth micro dilution was adopted as a
reference method. 10 µl solution of test compound was inoculated in 5 ml BHI broth for each
concentration respectively and additionally one test tubes was kept as control. Each of the test tubes
was inoculated with a suspension of standard microorganism to be tested and incubated at 35˚C for
24 hrs. At the end of the incubation period, the tubes were examined for the turbidity.Turbidity in the
test tubes indicated that microorganism growth has not inhibited by the antibiotic contained in the
medium at the test concentration
Compound 1 demonstrated MIC at concentration 1.6 µg/ml, 25 µg/ml, 0.4 µg/ml, 3.12 µg/ml against
K. pneumonia, Pseudomonas, S. aureus, S. mutans respectively and was compared with the standard
drug Ciprofloxacin. The results indicate that compound 1 shows moderate antibacterial activity
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
40
against K. pneumonia, Pseudomonas, S. aureus, S. mutans respectively compound 1 was having good
activity in S. aureus, bacterium due to the role of zinc in complex system, coordination and chelating
tends are acting as more powerful and influential bacteriostatic agents, thus inhibiting the growth of
the microorganisms.
The compound 1 were exhibited the growth of C. albicans at concentration 1.6 µg/ml, whereas the
standard anti-fungal drug Fluconazole executed antifungal activity at 16 µg/ml. It can be concluded
from this study that the tested compound 1 showed more potent anti-fungal activity when compared
to standard drug Fluconazole, whereas antibacterial activity is moderate when compared to standard
drug Ciprofloxacin.
Table 1. Antibacterial and Antifungal activity of compound 1.
Drug
Organism
Concentration of compound 1 (µg/ml)
100
50
25
12.5
6.25
3.12
1.6
0.8
0.4
0.2
K. pneumoniae
S
R
R
R
Pseudomonas
S
R
R
R
R
R
R
R
R
S. aureus
S
R
S. mutans
S
R
R
R
R
Candida
albicans
S
R
R
R
Summary. Monomeric group 12 metal complexes have been synthesized and characterized by
analytical and spectroscopic studies. Compound 1 possesses showed more potent anti-fungal activity
when compared to standard drug fluconazole. Compound 1 demonstrated MIC at concentration 1.6
µg/ml, 25 µg/ml, 0.4 µg/ml, 3.12 µg/ml against K. pneumonia, Pseudomonas, S. aureus, S. mutans
respectively against Ciprofloxacin, Hence compound 1 to exhibit more potent anti-bacterial and
Antifungal activity.
Acknowledgement. The authors thank the management of VIT University for providing the excellent
research facilities (VIT-SAIF). CG acknowledges Sigma Aldrich, subsidiary of Merck Life Sciences
for sponsoring my Ph.D. program. Also, the authors are very much thankful to Maratha Mandal
Dental College, Belgaum for performing the antibacterial and antifungal activity.
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1049. DOI: 10.1002/syn.20683.
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MMSE Journal. Open Access www.mmse.xyz
41
[6] A. Mastrolorenzo, A. Scozzafava, C.T, Supuran, Antifungal activity of silver and zinc complexes
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Wright, Dalton Transaction, 2007. DOI: 10.1039/b704973k
[10] G. Prabusankar, R. Murugavel, Organometallics, 2004, 5644-5647. DOI:10.1021/om049584u.
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Cite the paper
Champaka Gurudevaru, Nallasamy Palanisami, (2017). Group 12-Metal Complexes derived from Donor
Substituted Carboxylic Acids and 5-Nitro-1,10-Phenanthroline: Spectroscopic and Biological
Studies. Mechanics, Materials Science & Engineering, Vol 9. doi 10.2412/mmse.46.5.782
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
42
Spectroscopic Properties of Sm
3+
Doped Lithium Zinc Borosilicate Glasses
7
N. Jaidass
1, 2
, C. Krishna Moorthi
1
, A. Mohan Babu
1, 2
,
M. Reddi Babu
1, 2
1 School of Advanced Sciences, V I T University, Vellore - 632 014, India
2 Dept. of Physics, Chadalawada Ramanamma Engineering College, Tirupati - 517 506, India
DOI 10.2412/mmse.4.50.890 provided by Seo4U.link
Keywords: LZBS Glasses, quenching technique, photonic devices, optical amplifiers.
ABSTRACT. For spectroscopic analysis, the Sm
3+
ions doped with lithium zinc borosilicate (LZBS) glasses were
prepared by the conventional melt quenching technique. The prepared glasses were characterized by the XRD, SEM,
optical absorption, luminescence and decay measurements. The XRD spectrum clearly revealed that the LZBS glass is
amorphous in nature and the SEM spectrum conformed the same. The UV-VIS-NIR absorption spectra revealed seventeen
peaks at 360, 374, 389, 402, 416, 437, 462, 476,526, 562, 943, 1076, 1224, 1369, 1471, 1521 and 1584 nm corresponding
to the
6
H
5/2
4
D
3/2
,
6
P
7/2
,
4
L
15/2 ,
6
P
3/2
,
6
P
5/2
,
4
G
9/2
,
4
I
13/2
,
4
I
11/2
,
4
F
3/2
,
4
G
5/2
,
6
F
11/2
,
6
F
9/2
,
6
F
7/2
,
6
F
5/2
,
6
F
3/2,
6
H
15/2
and
6
F
1/2
transitions, respectively. The Judd -Ofelt intensity parameters (Ω
2
, Ω
4
and Ω
6
) have been determined from the absorption
data and these parameters are found to follow the trend as
4
6
6
. Photoluminescence spectra recorded by the
excitation wavelength of 402 nm, revealed four emission peaks at 562, 598, 645 and 713 nm corresponding to
4
G
5/2
6
H
5/2
,
6
H
7/2
,
6
H
9/2
and
6
H
11/2
transitions, respectively. Radiatiive transition probabilities (A
R
) peak stimulated emission
cross-sections (σ
e
), experimental
exp
) and calculated
R
) branching ratios were determined for different emission
transitions. The nature of decay curves of
4
G
5/2
level for different Sm
3+
ions concentrations in the LZBS Smx glasses has
been analyzed using Inokuti-Hirayama (I-M) model and the lifetimes (τ
exp
) are found to decrease with increase of Sm
3+
ions concentrations.
Introduction. Rare earth doped glasses are more useful materials, in the development of fiber
amplifiers, sensors, high optical data storage, laser media and quantum electronic devices [1-4]. For
the design of optical devices, host glasses with low phonon energies are essential. Among rare earth
ion doped glasses, borosilicate glasses are popular host materials due to their good transparency and
easy to draw into fibers for different laser applications. Borosilicate glasses possess excellent optical
properties like fluoride glasses with higher chemical durability and better mechanical properties [5-
7]. Moreover, the Sm
3+
, Dy
3+
and Tb
3+
ions emit orange, blue and green light, while the Pr
3+
ions emit
different colors depending on the concentration of dopant ions as well as surrounding environment.
In the present work, the emission characteristics of Sm
3+
ions in LZBS glasses are determined from
the absorption, luminescence and decay measurements. J-O intensity parameters
λ
(λ= 2, 4 and 6)
are determined from the experimental oscillator strengths. The radiatiive transition probabilities (A
R
),
experimental branching ratio
R
), stimulated emission cross-section (σ
e
), gain bandwidth
e
x∆λ
p
)
and optical gain
e
R
) are evaluated. The concentration quenching phenomenon with concentration
variation of Sm
3+
ions and the mechanism involved has been discussed.
Experimental. LZBS glasses with chemical compositions of (30-x) H
3
BO
3
: 25SiO
2
:
10Al
2
O
3
:
30LiF:5ZnO:xSm
2
O
3
were prepared with different Sm
2
O
3
concentrations of 0.1, 0.5, 1.0 and 2.0 mol
% by the conventional melt quench technique and are labeled as LZBS Sm01, LZBS Sm05, LZBS
Sm10, and LZBS Sm20. About 10g of the batch chemicals were thoroughly mixed and grinded to get
homogeneous mixture and heated at 1200
0
C in an electric furnace for 3 hours and then the melt was
poured onto a pre-heated brass plate. After casting, the glasses were annealed at 350
0
C for 7 hours to
remove thermal strains and stress. To determine the amorphous nature of the host glass, the XRD
© 2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
43
spectrum was recorded using the Philips X’Pert - MPD X-ray diffractometer using Cu radiation.
The optical absorption spectra were recorded in the region 200 - 2200 nm using JASCO V- 770 UV-
VIS-NIR spectrophotometer and the photoluminescence excitation and decay measurements were
recorded using the FLS-980 spectrofluorimeter.
Results and discussion. The XRD spectrum of undoped LZBS glass is shown in the Fig.1. It revealed
the absence of sharp peaks in the host LZBS glass and SEM image is shown in the Fig. 2 conformed
the amorphous nature of LZBS glass.
20 30 40 50 60 70 80
0
10
20
30
40
Intensity (counts)
Angle (
Fig. 1. (a) XRD pattern of LZBS Sm0.0 glass. Fig. 1. (b) SEM image of LZBS Sm0.0 glass.
Optical analysis.To study the optical absorption properties of LZBSSm10 glass, the absorption
spectra were recorded in the UV-VIS and NIR regions are shown Figs. 2(a) & (b). The intensities of
absorption bands are determined by their oscillation strengths (f), which are directly proportional to
the area to the absorption bands. The assignment absorption bands are made by comparing the band
positions with those reported by Carnall et al. [8].
350 400 450 500 550 600 650
0.5
1.0
1.5
4
G
9/2
Absorbance(arb.units)
Wavelength(nm)
6
P
3/2
6
P
7/2
4
D
3/2
4
I
13/2
6
P
5/2
4
L
15/2
4
G
5/2
4
F
3/2
4
I
11/2
6
H
5/2
1000 1200 1400 1600 1800
0.5
6
F
1/2
6
H
15/2
6
F
3/2
6
F
5/2
6
F
7/2
6
F
9/2
Absorbance(arb.units)
Wavelength(nm)
sm 1.0 abs
850
0.85
0.25
6
H
5/2
6
F
11/2
Fig. 2. Optical absorption spectrum of LZBSSm10 glass in the (a) UV-VIS regions (b) NIR region.
The observed
6
H
5/2
6
P
3/2
hypersensitivity transition at 402 nm exhibited highest intensity compared
to other transitions. The Judd-Ofelt theory [9, 10] has been adopted for the analysis of oscillator
strengths of the absorption bands in order to know the nature of bonding between the rare earth ions
Mechanics, Materials Science & Engineering, April 2017 ISSN 2412-5954
MMSE Journal. Open Access www.mmse.xyz
44
and the surrounding ligands as well as the symmetry around rare earth ions. The experimental (f
exp
)
and calculated (f
cal
) oscillator strength are determined by finding the relative areas of absorption bands
and also using the equations given in previous reports by Reddi Babu et al. [11] . The evaluated J-O
intensity parameters of LZBSSm10 glass are compared with those of other Sm
3+
doped glasses [12-
19] in the Table 1. All the J-O parameters follow the trend as
642
.
In the present
investigation, the considerably higher magnitude of
2
indicates lower degree of symmetry around
the Sm
3+
ion and relatively weaker covalence of active ion-oxygen bond.
Table 1. Comparison of Judd-Ofelt intensity parameters (in 10
-20
cm
2
) of Sm
3+
ions in LZBSSm10
glass along with other reported glasses.
System
Ω
2
Ω
4
Ω
6
Trend
Reference
LZBS Sm10
2.94
9.9
6.89
Ω
4
6
> Ω
2
Present work
NSBaP
0.33
8.60
3.92
Ω
4
6
> Ω
2
[12]
L5BS10
6.21
9.68
7.16
Ω
4
6
> Ω
2
[13]
Bismuth borate
2.10
5.54
4.58
Ω
4
6
> Ω
2
[14]
Fluorozincate
0.68
3.77
2.15
Ω
4
6
> Ω
2
[15]
Phosphate
1.50
3.75
1.89
Ω
4
6
> Ω
2
[16]
LBTAF
0.27
2.52
2.47
Ω
4
6
> Ω
2
[17]
LCZSFB
3.29
9.16
5.28
Ω
4
6
> Ω
2
[18]
ZNBS
0.30
3.82
3.65
Ω
4
6
> Ω
2
[19]
Photoluminescence and radiative analysis.The emission spectra recorded in the range 500800 nm
for the LZBSSmx (x = 0.1, 0.5, 1.0 and 2.0 mol %) glasses are shown in the Fig. 3. These spectra
revealed four emission bands at 562, 598, 645 and 767 nm from the excited
4
G
5/2
level to the
6
H
5/2
,
6
H
7/2
,
6
H
9/2
and
6
H
11/2
lower transition levels of Sm
3+
ion. Among these emissions, the band located
at 598 nm corresponding to
4
G
5/2
6
H
7/2
is the most intense one. In addition, the emission bands at
598, 647 and 709 nm are important because they are located at the longer wavelength region. The
transitions
4
G
5/2
6
H
5/2
(562 nm) and
4
G
5/2
6
H
7/2
(592 nm) contain both electric and magnetic dipole
contributions, obeying the selection rules, i.e ∆J = 0, +1, while the other two emission transitions
4
G
5/2
6
H
9/2
and
4
G
5/2
6
H
11/2
are purely electric dipole transitions [20, 21]. It is observed from the
Fig. 3, that the emission intensities are increased upto 0.5 mol% of Sm
3+
ions concentrations and then
decreased at higher concentrations. The luminescence efficiency of Sm
3+
ions doped LZBS emission
transitions are found by evaluating the radiative parameters such as transition probabilities (A
R
),
branching ratios (β
R
), radiative lifetimes
R
) and peak stimulated emission cross sections (σ
e
) for the
JJ
emission transitions by using the equations given in previous reports [11]. The efficiency
of laser transition mainly depends on the stimulated emission cross-section (σ
e
), gain bandwidth
(σ
e
×Δλ
eff
) and optical gain parameters (σ
e
×τ
exp
) [22, 23]. The laser characteristic parameters for the
4
G
5/2
6
H
7/2
and