Investigations on Growth, Optical and Thermal Properties of Sulphamic Acid Single Crystals
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Hindawi Publishing Corporation Advances in Condensed Matter Physics Volume 2014, Article ID 950467, 5 pages http://dx.doi.org/10.1155/2014/950467 Research Article Investigations on Growth, Optical and Thermal Properties of Sulphamic Acid Single Crystals D. Jaishree,1 G. Kanchana,2 and R. Kesavasamy3 1 Department of Physics, Sri Ramakrishna Institute of Technology, Coimbatore, Tamil Nadu 641010, India 2 Department of Physics, Government Arts College, Coimbatore, Tamil Nadu 641018, India 3 Department of Physics, Sri Ramakrishna Engineering College, Coimbatore, Tamil Nadu 641022, India Correspondence should be addressed to D. Jaishree; [email protected] Received 10 April 2014; Accepted 21 October 2014; Published 25 November 2014 Academic Editor: Ram N. P. Choudhary Copyright © 2014 D. Jaishree et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. 3 Single crystals of sulphamic acid of 11 × 7 × 3mm dimension were successfully grown by slow evaporation technique. The crystal structure of grown crystals was confirmed by single crystal X-ray diffraction analysis. The presence of functional groups inthe crystal lattice has been qualitatively determined by FT-IR and FT-Raman analyses. Theoretical group factor analysis predicts the possible modes of vibrations. The optical transmission spectroscopy (UV-Vis) clearly evidences the suitability of this material for optical application. The thermal behaviour of the crystal was studied by thermogravimetric (TG) and differential scanning calorimetric (DSC) studies. The nonlinear optical (NLO) characteristic of this material was explored by the second harmonic generation (SHG) conversion efficiency. 1. Introduction highly stable and it can be kept for years without any change in properties. It is a strong inorganic acid; while Nonlinear optical (NLO) materials exhibiting second har- mixing it with water it exhibits Zwitterionic form [1]. Owing monic generation have been in great demand over the last few to these advantages, JIS (Japanese Industrial Standard) has decades due to technological importance in the fields of opti- established this reagent as a standard substance for titrimetric cal communication, signal processing, and instrumentation analysis and the British Analytical Methods Committee as [1–3]. Most of the organic NLO crystals usually have poor well as IUPAC has also recommended the acid [2]. Mainly, mechanical and thermal properties and are susceptible to solution growth techniques have been applied for growing damage during processing even though they have large NLO good quality crystals. The limited thermal stability of many efficiency. Also it is difficult to grow larger size optical-quality of the compounds examined makes particularly exploratory crystals of these materials for device applications. Most of solution growth as the first technique to be considered3 [ ]. the recent work has demonstrated that organic crystals can Crystal growth from solution is an important process that is have very large nonlinear susceptibilities compared with used in many applications from laboratory to industrial scale. inorganic crystals, but their use is impeded by their low The number of organic and inorganic crystals is grown in this optical transparencies, poor mechanical properties, low laser fashion [6]. damage thresholds, and inability to produce and process In the present investigation, sulphamic acid (SA) single large crystals [4]. The inorganic materials are widely used in crystals have been grown successfully by slow evaporation these applications because of their high melting point, high technique. The modes of vibrations were analysed for the mechanical strength, and high degree of chemical inertness first time by the factor group analysis. The grown crystals [5]. were characterized by powder X-ray diffraction and single Sulphamic acid (H2NSO3H) is the monoamide of sul- crystal X-ray diffraction analysis, FT-IR, FT RAMAN, and phuric acid and is formed as orthorhombic crystal. It is optical transmittance studies. TGA and DSC analysis show 2 Advances in Condensed Matter Physics 100 90 80 70 60 2133.82 50 2338.63 2019.24 40 2567.87 (%) 30 T Figure 1: Photograph of as-grown SA single crystals. 20 10 2455.62 2874.01 1002.73 0 1541.64 −10 544.51 690.67 the thermal behavior of the crystals. The SHG studies for 1450.78 −20 3152.54 1305.95 the sulphamic acid single crystal showed it is SHG active as 1069.44 −30 reported in the literature [4]. 3500 3000 2500 2000 1500 1000 500 −1 Wavenumbers (cm ) 2. Growth Procedure Figure 2: FT-IR spectrum. Saturated solution of SA was prepared using double dis- tilled water at room temperature. The solution is stirred continuously to get homogeneous mixture. It is filtered using 1.6 27 Whatman filter paper. The filtered solution was poured in BRUKER: RFS variousbeakersandwascoveredbyfilterpaper.Goodtrans- 1.4 SAIF, IITM 1057.04 CHENNAI parent single crystals were obtained after 12 days. The crystals 1.2 were purified by the process of repeated recrystallization (see Figure 1). 1.0 0.8 3. Characterization Studies 0.6 Raman intensity 536.38 0.4 1303.67 680.04 Single crystal X-ray diffraction was carried out using Enraf 1537.52 81.29 555.57 Nonius-CAD 4 diffractometer to determine the cell parame- 0.2 361.32 1277.99 698.95 1340.52 1019.07 154.27 1569.53 3040.55 ters and crystal structure. The FT-IR and FT-Raman spectra 2869.48 were recorded using BRUKER: RFS spectrometer in fre- 0.0 −1 5000 4000 3000 2000 1000 quency range 400–4000 cm to analyze the presence of −1 Wavenumber (cm ) functional groups. The optical transmission spectrum was recorded by double beam UV-Vis spectrophotometer in Figure 3: FT-RAMAN spectrum. the range 200–800 nm covering the entire near ultraviolet, visible, and NIR regions. The NLO property was tested using Kurtz and Perry powder test. crystal. The vibrational assignments for SA single crystal are 4. Results and Discussion given in Table 2. 4.1. Single Crystal X-Ray Diffraction Analysis. The titled 4.3.FactorGroupAnalysis.A group theoretical analysis material has been subjected to single crystal XRD employing predicts the possible modes of vibrations of the materials. Enraf Nonius-CAD 4 diffractometer. The single crystal XRD The unit cell has 8 atoms which gives rise to 192 (3 × 8 study reveals that the grown crystal belongs to orthorhombic × 8) fundamental modes of vibrations. The factor group crystal system and the obtained lattice parameters are = analysis of the compound gives rise to 192 normal modes 8.05 A,˚ =8.17A,˚ and =9.23A.˚ These values are compared of vibrations distributed as 144 internal and 18 (A +B1 + with already reported value of SA [7]crystalsandare g g B2g +B3g +Au +B1u +B2u +B3u) along with 3 acoustical tabulated in Table 1. (1A +2A) and 45 external modes. The A species are FromtheXRDanalysis,itisconfirmedthatthegrown g u g only RAMAN active and B1g,B2g,andB3g species are both crystal crystallizes to orthorhombic crystal structure with IR and RAMAN active. Group theoretical analysis carried ˚ Pbca space group. The unit cell volume is 596 A. The density outbytheprocedureoutlinedbyRosseauetal.[8]shows 3 is found to be 2.141 mg/m and the number is 8. 3 acoustical, 21 translational, and 24 rotational modes. The summaryoffactorgroupanalysisisgiveninTable 3. Each 4.2. FT-IR and FT RAMAN Analysis. Figures 2 and 3 show internal mode splits into B1g( ), B2g( ), B3g( ), B1u( ), , , therecordedspectrumofFT-IRandFT-RAMAN.The B2u( ), and B3u( )whichareIRactiveandAg( ), spectrum reveals the presence of all functional groups in the B1g( ), B2g( ), and B3g( )areRAMANactive.Table 4 Advances in Condensed Matter Physics 3 Table 1: Cell parameters of sulphamic acid single crystals. ∘ ∘ ∘ Sample (A)˚ (A)˚ (A)˚ ( ) ( ) ( ) Volume (A3) Crystal system Sulphamic acid 8.07 8.11 9.26 90 90 90 607.619 Orthorhombic Sulphamic acid 8.05 8.17 9.23 90 90 90 596.6 Orthorhombic Table 2: Vibrational assignments. 103.854 Wavenumber Wavenumber −1 − 88.574 (cm ) (cm 1) Assignment FTIR FT RAMAN 73.294 + 3152 — NH3 stretching vibration + (%) 2874 2869 Symmetric NH3 stretching T 58.014 2600–2200 — N–H stretching + 1541 1537 Degen. NH3 deformation 42.734 + 1450 — Symmetric NH3 deformation − 27.454 1305 1303 Asymmetric SO3 stretching − 200.00 320.00 440.00 560.00 680.00 800.00 1069 1057 Symmetric SO3 deformation + Wavelength (nm) 1002 1019 Degen. NH3 rocking 690 680 N–S stretching Figure 4: Transmittance spectra. − 544 555 Degen. SO3 deformation Exo 140 Mass change: −2.63% 50 120 40 100 Mass change: 23.83% 80 Mass change: −16.99% shows the correlation scheme obtained by the procedure of −8.74 30 60 Complex peak: Mass change: % Area: 500.7 J/g Mass change: −10.42% Fateley et al. [9]. ∘ 40 Peak: 267.3 C 20 251.8∘ −31.87 The polarizability tensors are of the forms (%) TG Onset: ∘ C Mass change: % 20 End: 280.0 C ∘ 366.2∘ Residual mass: 5.52% (772.9 C) 10 Peak: C ∘ ∘ 0 Peak: 401.2 C Peak: 548.2 C DSC (mW/mg) −20 ∘ 0 ∘ Peak: 601.7 C Peak: 343.9 C ∘ 00 −40 Peak: 617.5 C =( 0 0 ), 100 200 300 400 500 600 700 Ag ∘ 00 Temperature ( C) TG 0 0 =(000), DSC B1g 000 Figure 5: TGA and DSC thermograms. (1) 00 0 =(00 ), B3g 00 0 4.5. Thermogravimetric and Differential Scanning Calorimet- ric Studies. TGA and DSC thermograms are recorded using 00 NETZSCH STA 409C instrument between room temperature ∘ =(00 0). and 700 C in nitrogen atmosphere. Simultaneously recorded B2g 00 0 TGA and DSC thermograms are shown in Figure 5. The recorded thermogram gives information about the phase transition, water of crystallization, and different stages 4.4. UV-VIS-NIR Studies. Molecules containing -electrons of decomposition of the crystal.