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ARTICLE IN PRESSG ModelIJLEO-51946; No. of Pages 4Optik xxx (2012) xxxxxx

Contents lists available at SciVerse ScienceDirect

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Synthe ofThiosem

J. Chandr BalK. Sathisa Department o 641 0b Research andc Department o India

a r t i c l

Article history:Received 1 JunAccepted 3 NoAvailable onlin

Keywords:ThiosemicarbaInfrared spectOptical transmThermal analy

e (K(Ns. Thion wformctiondied. stanted. Ter. Th

linear optical properties using UVvis spectrophotometer. 2011 Elsevier GmbH. All rights reserved.

1. Introdu

The devent sourcesetc. These fbasis of nonmedium as materials hattractive pindices andtuted by we-electronIn view of from organithan the VamechanicalIn semiorgachiometricafamily cryseral researcproperties ofor NLO app

CorresponE-mail add

0030-4026/$ doi:10.1016/j.e this article in press as: J. Chandrasekaran, et al., Synthesis, crystal growth and characterization of a semiorganic material:arbazide potassium chloride, Optik - Int. J. Light Electron Opt. (2012), doi:10.1016/j.ijleo.2011.11.023

ction

elopment of optoelectronic functions includes coher- for emission, optical ampliers, modulators, switchesunctions and related devices can be operated on thelinear optical phenomena whereby the optical responsedriven by the optical elds [1]. In particular the organicave motivated several investigations because of theirroperties in high damage threshold, low refractive

easy growth, but in which the molecules are consti-ak Van der waals and hydrogen bond with conjugateds and it is difcult to cut and polish such crystals.this, a new type of NLO materials have been builtcinorganic complexes which form stronger ionic bondn der Waals and hydrogen bonds, which increases the

strength of material namely, semiorganic crystals [2,3].nics materials, polarizable organic molecules are stoi-lly bound within an inorganic host [4,5]. Organic acidtals have subjected to extensive investigation by sev-hers for their excellent characteristics. The physicalf organic acids properties made them ideal candidateslications. In the recent years, efforts have been made

ding author. Tel.: +91 422 2692461; fax: +91 422 2693812.ress: jchandaravind@yahoo.com (J. Chandrasekaran).

on the organic acid mixed with inorganic crystals, in order toimprove their properties. Thiosemicarbazone moiety helps the freethiosemicarbazone ligands and their metal complexes to improvesecond harmonic generation (SHG) efciency [6]. In this respectacetophenone thiosemicarbazone (APTSC), thiosemicarbazide cad-mium chloride monohydrate (TSCCCM) and thiosemicarbazidelithium chlorides [TSLC] have been identied as good semiorganicnonlinear optical materials [7,8]. In the present work potas-sium chloride is combined with thiosemicarbazide to form a newsemiorganic (metalorganic) material in this series. Systematicinvestigation has been carried out on the growth of TSCPC subjectedto Fourier transform infrared spectroscopy, optical transmission,thermal study, dielectric constant and microhardness measure-ment.

2. Synthesis and growth technique

The starting materials were highly pure and the synthesis andgrowth process were carried out in aqueous solution. Thiosemicar-bazide potassium chloride (TSCPC) has been synthesized by takingpotassium chloride and thiosemicarbazide in a 1:1 stoichiometricratio. The reaction responsible for synthesis and crystallization is.

KCl + NH2NHCSNH2 K(NH2NHCSNH2)ClThe calculated amount of potassium chloride was rst dissolved indeionized water. Then thiosemicarbazide was added to the solution

see front matter 2011 Elsevier GmbH. All rights reserved.ijleo.2011.11.023sis, crystal growth and characterizationicarbazide potassium chloride

asekarana,, P. Ilayabarathib, P. Maadeswaranc, S.hkumara, B. Babua

f Physics, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore Development Center, Bharathiyar University, Coimbatore 641 046, Tamil Nadu, Indiaf Physics, K. S. Rangasamy College of Technology, Tiruchengode 637215, Tamil Nadu,

e i n f o

e 2011vember 2011e xxx

zide potassium chloriderumission spectrumsis and microhardness

a b s t r a c t

Thiosemicarbazide potassium chloridganic materials for many applicationambient temperature and its dimenswhere characterized by Fourier transmodes of vibration due to various funtern of the grown crystal has been stuby using TGA/DTA. The dielectric confrequency and the results are discussied using Vickers microhardness tester .de / i j leo

a semiorganic material:

aprabhakarana,

20, Tamil Nadu, India

H2NHCSNH2)ClH2O) (TSCPC) is one of the potential semior-e crystal growth of TSCPC by slow evaporation method atas found to be (5 mm 3 mm 2 mm). The grown crystals

infrared spectroscopic (FT IR) analysis to nd the differental groups present in TSCPC. The powder X-ray diffraction pat-Thermal stability of the grown crystal was identied at 185 C

of the crystal was studied as a function of temperature withhe mechanical property of the grown crystal has been stud-e optical transmission spectrum was investigated to study its

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ARTICLE IN PRESSG ModelIJLEO-51946; No. of Pages 42 J. Chandrasekaran et al. / Optik xxx (2012) xxxxxx

Fig. 1. As shown in TSCPC crystals.

slowly. The solution was agitated with a magnetic stirring devicefor 8 h continuously and ltered after complete dissolution of thestarting materials. The prepared solution was left standby for sev-eral days acolorless cr

3. Result a

3.1. FT IR a

The FT thermo Nicof 400400shown in Fi3176 cm1

stretching m2969 cm1

bending moand 1644 cmto asymme(CNH2) m1000 cm1

600 cm1 rvarious funlated in Tab

3.2. Powde

Powder strate the employing ations of wspeed of 2

played in tcrystallinitydiffraction,

-10

0

10

20

30

40

50

60

70

80

90

100

%T

4000

Table 1FT-IR data of TSCPC crystal.

Wave number (cm1) Assignments

3368 NH asymmetric stretching vibration of NH23369 NH asymmetric stretching vibration of NH23370 (CH) stretching1644 NH3+ asymmetric bending mode1620 NH2 deformation1483 C S Asymmetric Stretching1316 (CNH2) mode of vibration1001 CCl Stretching mode800 C S Symmetric Stretching mode503 NCS Stretching

) 6000

7000

8000

2-Theta - Scale10 20 30 40 50 60 70 80

Fig. 3. X-ray powder diffraction of TSCPC.

wder diffraction data of TSCPC.

Experimental d value

5.82220 4.97569 4.40672 4.10541 3.59933 3.24516 2.92044 2.52292 2.22680 1.81069 1.75744 1.56869 1.40460 1.28869

near optical properties

optical transmission range of TSCPC crystal was observedeen wavelength 200 and 800 nm with scanning speed of/min using Varian, Cary 5000 instrument and thickness of

was 2 mm used. From the Fig. 4, it is evident that TSCPC has UV cut-off below 260 nm, which is sufcient for SHGt room temperature. After 2530 days a good qualityystals were obtained which is shown in (Fig. 1).

nd discussion

nalysis

IR spectrum of TSCPC crystal was recorded using aolet, Avatar 370 spectrometer in the wave length range0 cm1. The resulting spectrum of TSCPC crystal isg. 2. The broad envelope positioned between 3368 andwhich corresponds to the symmetric and asymmetricodes of NH2 group. A weak absorption is observed at

due to (CH) stretching mode. The asymmetrical NH3+

de and NH2 deformation was observed at 1620 cm11 respectively [9]. A sharp peak at 1483 cm1 is due

tric C S stretching. The band at 1316 cm1 is due toode of vibration and symmetric NCN stretching at

[10]. The CCl stretching band was observed at 647 andespectively. The assignments conrm the presence ofctional groups are present in the material and is tabu-le 1.

r X-ray diffraction analysis

X-ray diffraction studies were carried out to demon-crystallinity using Rich-Seifert X-ray diffractometerBruker AXS D8 Advance with Ni ltered Cu-K radi-avelength (1.5406 A) in the range 1080 with a scan/min. The powder X-ray diffraction spectrum is dis-he Fig. 3 and the spectrum shows a high degree of

of the synthesized compound. From the powder X-raythe 2 and d are given in Table 2.

Lin

(Cou

nts

0

1000

2000

3000

4000

5000

3

Table 2X-ray po

2 ()

15.20517.81220.13421.62924.71527.46330.58735.55540.47650.35451.99258.81966.51673.817

3.3. Li

Thein betw200 nmcrystalcrystale this article in press as: J. Chandrasekaran, et al., Synthesis, crystal grarbazide potassium chloride, Optik - Int. J. Light Electron Opt. (2012), d

500 1000 1500 2000 2500 3000 3500

Wavenumbers (cm-1)

Fig. 2. FT-IR spectrum of TSCPC crystals. Fowth and characterization of a semiorganic material:oi:10.1016/j.ijleo.2011.11.023

ig. 4. Optical transmission spectrum of TSCPC crystals.

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ARTICLE IN PRESSG ModelIJLEO-51946; No. of Pages 4J. Chandrasekaran et al. / Optik xxx (2012) xxxxxx 3

Fig. 5. TGA/DTA curve of TSCPC crystal.

properties aentire visib

3.4. Therma

The thergravimetricThe thermamodel Q60was used fin an atmostemperaturwas taken fthe materiabegins to apose. The shdegree of crweight percobserved atThis weightetc. Thus, tbetween 20

3.5. Dielect

The dieleatures usinwas found bis used to caranging betfrequencies150 C and iincreasing twith tempe1 MHz is sh

0

10

20

30

40

50

60

70

Har

dnes

s nu

mbe

r(H

v) K

g/m

m2

101214161820

Die

lect

ric

Con

stan

t (r

)

3.6. Microh

The mecT, Viationom 2umbindicing ting o, whi

the crysad o

clus

otenhloriationd peamallyire ve-le

gh mny aperstalectrcrea

wled

of pporh prnalyent

instrnd the transmittance of the crystal is about 90% in thele region [12].

l analysis

mal stability of TSCPC was identied by the thermo- analysis (TGA), and differential thermal analysis (DTA).l analyses were carried out using the instrument of0 SDT and Q20 which is shown in Fig. 5. A crucibleor heating the sample and analyses were carried outphere of nitrogen at a heating rate of 20 K/min in thee range 20800 C. The TSCPC sample weighing 25.9 mgor the analysis. From the DTA curve it is observed thatl is stable up to 185 C and above which the materialttain an endothermic transition and begins to decom-arpness of this endothermic peak at 205 C shows goodystallinity of the sample [13]. The TGA curve shows theentage of about 98.72% observed at 185 C and 59.86%

385 C which may attribute to the loss of lattice water. loss is due to release of gaseous product like CO2, NH3,he compound undergoes endothermic decomposition5 C and 385 C.

ric constant (r)

ctric property of TSCPC was studied at various temper-g Agilent A 2484. The dielectric constant (r) of crystaly measuring the capacitance and dielectric loss, whichlculate the dielectric constant at various temperaturesween room temperature to 150 C for three different. The maximum dielectric constant was observed att indicates that the dielectric constant is increased withhe temperature [14]. The variation of dielectric constant

HMV 2indentload frness ngraph increashardenoccursated byTSCPC for a lo

4. Con

A psium cevapordeneis therthe entoff wavand hifor mato undthe diewith in

Ackno

Onecial suresearccated aInstrumlytical e this article in press as: J. Chandrasekaran, et al., Synthesis, crystal grarbazide potassium chloride, Optik - Int. J. Light Electron Opt. (2012), d

rature at three different frequencies 100 Hz, 10 KHz andown in Fig. 7.

10050353025

Load (P)

Fig. 6. Microhardness of TSCPC crystals.

References

[1] J. Zyss, MPress, Bo

[2] J. WilliamAm. Chem1983.

[3] T. Pal, T. Kand charof L-argin

[4] S. Moitrbis(thiou

[5] J. Mary Lcharactercrystals, C

[6] R. SanthaNarayana02468

150140130120110100908070605040

TemperatureC

100Hz 10KHz 1MHz

Fig. 7. Dielectric constant of TSCPC crystals.

ardness measurement

hanical strength of the TSCPC crystal was found usingckers microhardness tester shown in Fig. 6. The statics were made on the surface of crystal by varying the5 to 100 g at room temperature. Vickers microhard-er was calculated using Hv = 1.8544 P/d2 kg/mm2. Theates at lower load, there is an increase in hardness withhe load up to 50 g, which can be attributed to the workf the surface and above 50 g load signicant crackingch may be due to the release of internal stresses gener-indentation. Finally the maximum value of hardness fortal at room temperature was found to be 63.2 kg/mm2

f 50 g [15].

ion

tial semiorganic crystals of thiosemicarbazide potas-de (K(NH2NHCSNH2)ClH2O) have been grown by slow

in mixed solvent of deionized water. The sharp well-ks conrm the crystalline nature of the materials. TSCPC

stable up to 185 C. TSCPC is optically transparent inisible region with 90% transparency level. The lower cutngth (260 nm) shows a good optical transparency levelelting point makes TSCPC as a new promising materialplications. Microhardness value was calculated in ordernd the mechanical stability of the grown crystals. Fromic studies it is seen that the dielectric constant decreasessed frequency.

gments

the authors (J.C) gratefully acknowledges the nan-t from the DST, Government of India for the majoroject (SR/S2/LOP-07/2008). The authors thank sophisti-tical Instrumentation facility (STIC), Cochin and Centralation Facility (CIF) Pondichery University, for their ana-ument facilities.

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[15] K. Selvaraju, R. Valluvan, S. Kumararaman, A new metalorganic crystal: potas-sium thiourea chloride, Mater. Lett. 61 (2007) 751753.e this article in press as: J. Chandrasekaran, et al., Synthesis, crystarbazide potassium chloride, Optik - Int. J. Light Electron Opt. (20owth and characterization of a semiorganic material:oi:10.1016/j.ijleo.2011.11.023

Synthesis, crystal growth and characterization of a semiorganic material: Thiosemicarbazide potassium chloride1 Introduction2 Synthesis and growth technique3 Result and discussion3.1 FT IR analysis3.2 Powder X-ray diffraction analysis3.3 Linear optical properties3.4 Thermal analysis3.5 Dielectric constant (r)3.6 Microhardness measurement

4 ConclusionAcknowledgmentsReferences