- Email: [email protected]
Growth and investigation on structural optical, thermal and magnetic behavior of ammonium bisulphate nonlinear single crystals
Materials Chemistry and Physics 229 (2019) 149–155
Contents lists available at ScienceDirect
Materials Chemistry and Physics journal homepage: www.elsevier.com/locate/matchemphys
Materials science communication
Growth and investigation on structural optical, thermal and magnetic behavior of ammonium bisulphate nonlinear single crystals
T
S. Chidambarama, A. David Kalaimani Rajb, R. Manimekalaia,∗ a b
Department of Physics, A.V.V.M. Sri Pushpam College (Autonomous), Poondi, 613 503, Tamilnadu, India Department of Physics, BDUMC, Aranthangi, Tamilnadu, India
HIGHLIGHTS
novel inorganic NLO crystal namely Ammonium bisulphate has been grown by slow evaporation method. • AMelting point of ABS single crystal is 588 °C and it is found suitable for optical device fabrication. • The grown crystal exhibits paramagnetic nature. • From mechanical analysis the ABS crystal belongs to soft material. • From the results, the grown crystal is more suitable for opto-electronic applications. • ARTICLE INFO
ABSTRACT
Keywords: Crystal growth Single crystal XRD SHG analysis Magnetic property
The new inorganic NLO ammonium bisulphate single crystal was synthesized by the slow evaporation method. The structure of the grown crystal was analyzed by X-RAY diffraction studies. The FT-IR spectrum confirms the presence of different functional groups of the grown crystal. Its optical transmittance is understood by UV-Vis-NIR spectrophotometer. The presence of SHG efficiency of the grown crystal was confirmed by Kurtz powder technique. The dissever nature of the crystal was analyzed by thermal studies. The mechanical behavior of the grown crystal is carried out at room temperature using Vicker's micro hardness tester, whenever the load increased, its hardness also increased. The elemental composition of the grown crystal was studied by EDAX analysis. The paramagnetic behavior of the grown crystal is confirmed by vibrating sample magnetometer.
1. Introduction In recent years, the new materials are needed for the wide range of applications in various fields, namely optoelectronics, photonics, optical data storage and telecommunication etc. Now numerous inorganic NLO materials are produced. The inorganic materials have high thermal stability. They also have high refractive index and good magnetic properties. There is good literature on piezoelectric, dielectric inorganic materials with good optical and mechanical properties [1–3]. The materials like ADP, L-tartaric acid and triglycine sulphate crystals have already been reported [4] to be NLO active materials. Sagadevan suresh et al. has reported on microhardness and dielectric characterization of lithium potassium sulphate crystal [5–7]. In this work we have chosen ADP and potassium sulphate grow a new crystal using double distil water in slow evaporation method at room temperature. When potassium sulphate is ∗
added with ADP it yields ammonium bisulphate (NH4 H SO4) single crystal and the dipotassium phosphate (K2 H PO4) is evaporated. The grown crystals are obtained with good transparency [8–11]. They crystallize in orthorhombic structure. From the literature [12], it is known that the ammonium bisulphate is soluble in water and methanol, insoluble in acetone. Our grown sample also does the same. Hence it is confirmed that the grown crystals are ammonium bisulphate. The ammonium bisulphate crystals got excellent outcome of thermal properties and mechanical strength. The structural optical, thermal and magnetic properties of the grown crystals have been studied by single crystal XRD, FTIR, UV, TGA/DSC, EDAX, NLO and VSM studies [13–18]. 2. Experimental procedure The single crystals of ammonium bisulphate [ABS] have been grown
Corresponding author. E-mail address: [email protected] (R. Manimekalai).
https://doi.org/10.1016/j.matchemphys.2019.02.092 Received 31 October 2018; Received in revised form 25 February 2019; Accepted 27 February 2019 Available online 03 March 2019 0254-0584/ © 2019 Published by Elsevier B.V.
Materials Chemistry and Physics 229 (2019) 149–155
S. Chidambaram, et al.
3.3. UV-vis spectral studies The UV-Visible NIR spectrum of the grown crystal with dimension (12x3x3 mm3) is recorded using Bruker UV-Vis-NIR spectrometer, and is shown in Fig. 3. In general, the study is mainly used for optical analysis. The optical absorption spectrum for the grown crystal was recorded in the range from 190 to 1100 nm. The resultant spectrum has very low absorption in the entire visible and IR region. The ammonium bisulphate single crystal has a good transmittance as shown in Fig. 4. The lower cut-off wavelength is nearly at 390 nm. The large transmittance in the entire visible region enables it to be a good prospect for optical applications. Absorption in the near ultraviolet region arises from the electronic transitions associated within the crystal. Using the formula αhν = A (hν-Eg)1/2 the optical band gap energy was found, where h is the planck's constant and c is the velocity of light. From tauc's plot the calculated band gap energy is 3.6 eV and is shown in Fig. 5.
Fig. 1. Photograph of Ammonium bisulphate crystal.
by the slow evaporation of the solvent. The (Analar grade) ammonium dihydrogen phosphate (NH4 H2 PO4) and Potassium sulphate (K2SO4) are dissolved in deionized water in the molar ratio 1:1 at room temperature. The saturated solution of ammonium bisulphate was prepared and kept in the dust free atmosphere. The good quality transparent ammonium bisulphate crystals are harvested after 20 days with dimension (16x5x4 mm3) as delineate in Fig. 1. The chemical reaction is as follows:
3.4. Nonlinear optical study The nonlinear optical behaviour of ammonium bisulphate crystal was confirmed by Kurtz and Perry powder technique. The Nd:YAG laser (QUANTA RAY Model LAB-170-10) emitting a fundamental wavelength of wavelength 1064 nm; pulse width 6ns and input energy 0.70J was allowed to focus on the powder sample. The output energy was detected by a photomultiplier tube. The second harmonic generation in the crystalline sample was confirmed by the emission of green radiation at 532 nm from the sample. The measured output energy of ammonium bisulphate crystal was 3.54 mJ against 8.94 mJ for the KDP crystal. From this, it is clear that the SHG conversion efficiency of ABS is 0.39 times that of KDP. This confirms the nonlinear optical behavior of ABS crystals.
NH4 H2 PO4 + K2 SO4 → NH4 H SO4 + K2 H PO4 ↑ The compound K2HPO4 is evaporated; hence the resultant compound is ammonium bisulphate [8,21]. 3. Results and discussion 3.1. Single XRD To determine the unit cell parameters of the grown ABS single crystals, the APEX2 diffractometer is used. The good quality crystal was selected for the X-ray diffraction studies. They crystalize is orthorhombic system with non-centro symmetric space group as Pna21 [19,20]. The unit cell dimension is shown in Table 1.
3.5. Thermal studies Thermo gravimetric analysis (TGA) and Differential Scanning Calorimetric (DSC) analyses of ammonium bisulphate single crystals are shown in Fig. 6. The sample was heated at the rate of 20 °C/min in an inert nitrogen atmosphere between 20 °C and 1400 °C using Perkin Elmer Diamond TGA/DSC analyzer. In TGA thermogram, there is gradual weight loss up to 100 °C; it is due to the liberation of water molecules from the sample. There is also another exothermic peak nearly at 588 °C; this temperature corresponds to melting point of the compound. The sharp exothermic peak occurring nearly at 1050 °C may be the decomposition compound of the grown ABS crystal. At this temperature the volatile substances are likely to decompose into residues. The sharpness of peak indicates the purity and crystallinty of the sample [24–26].
3.2. Fourier transform infrared (FTIR) analysis FTIR Spectrum of the grown ammonium bisulphate crystal is recorded using Perkin Elmer RX1 spectrometer as shown in Fig. 2. From the interpretation of the FTIR spectrum, the functional groups present in the grown crystal can be confirmed. The broad peak at 3364 cm−1 is attributed to OH stretching frequency. The sharp peak observed at 2923 cm−1 is due to NH2 bending. The broad peak appearing at 1620 cm−1 is due to NH2 symmetric stretching. The strong peak at 1382 cm−1 is assigned to NH2 asymmetric stretching frequency. The week peak at 1248 cm−1 is due to S-O-H plane bending. The peak at 829 cm−1 and 614 cm−1 are due to SO4 symmetric stretching and asymmetric stretching [21–23]. The presence of various functional groups are identified and presented in Table 2.
3.6. Micro hardness studies The hardness test provides useful information about the strength and deformation characteristics of the ammonium bisulphate single crystal [4]. The microhardness study is done by using Vickers microhardness tester fitted with a diamond indenter. The load is applied to
Table 1 Single crystal XRD data of ammonium bisulphate. Sample
Cell parameters (Å)
ABS
a = 5.80
b = 7.55
c = 10.13
α=β=γ
Volume (Å)3
System
Space group
90
444
Orthorhombic
Pna21
150
Materials Chemistry and Physics 229 (2019) 149–155
S. Chidambaram, et al.
Fig. 2. FTIR Spectrum of ABS crystal.
the grown single crystal in the order of 25, 50 and 100 g at room temperature. The drawn graph clearly indicates that, if the load value increases then hardness value of the crystal also increases as shown in Fig. 7. In order to find the work hardening coefficient (n) by Mayer's law, a graph was plotted for log P and log d as shown in Fig. 8. The work harding coefficient (n) of the grown ABS crystal is found to be 3.1. Generally, it lies between 1 and 1.6 for hard materials and is more than 1.6 for soft materials. From the observed n value, it is concluded that the grown ABS crystal belongs to soft material category [27,28,30].
Table 2 FTIR spectral assignments of ABS crystal. Wave number for grown crystal in (cm−1)
Frequency assignments
3364 2923 1620 1382 1248 829 614
OH stretching NH2 bending NH2 symmetric stretching NH2 asymmetric stretching S-O-H in plane bending SO4 symmetric stretching SO4 asymmetric stretching
Fig. 3. Absorbance curve of ABS.
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S. Chidambaram, et al.
Fig. 4. Optical transmittance of ABS.
Fig. 5. Optical band gap of ABS crystal.
3.7. EDAX analysis
given in Table 3.
The energy dispersive X-ray analysis (EDAX) is the useful tool for the elemental analysis and it is carried out by Geon 5610 LV Model. The presence of various components of the grown sample is analyzed. The recorded EDAX spectrum of the ABS crystal is shown in Fig. 9. The weight percentages of the various elements present in the sample are
3.8. Vibration sample magnetometer The magnetic properties of a variety of materials have been investigated. In the present case, the magnetic study was carried out using a vibrating sample magnetometer CR155 quantum design. The mass of
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Fig. 6. TGA/DSC of ABS crystal.
Fig. 7. Variation of Vicker's hardness number with load.
the sample taken at room temperature was 3g and the hysteresis path is traced for moment Vs field as shown in Fig. 10. When the magnetic field is applied, the dipole will align with the externally applied magnetic field, resulting in the magnetic moment in the direction of the applied field. From the plot it is clear that the grown ABS crystal have a positive susceptibility. This confirms the paramagnetic nature of the grown ABS single crystal [29–31]. The paramagnetic ABS crystals are used to store
data on hard drive and read them out. 4. Conclusion The single crystal of ammonium bisulphate, a new inorganic NLO material, has been grown by slow evaporation technique. The single crystal XRD analysis confirms the structure of the crystal as
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Fig. 8. Plot of Log d vs Log P for ABS crystal.
Fig. 9. EDAX pattern of ABS crystal. Table 3 Elemental composition of ABS crystal. Element
O
N
S
Totals
Weight % Atomic %
57.80 60.50
19.04 23.20
23.16 16.30
100.00 100.00
orthorhombic system. The functional groups of ABS crystal were identified using FTIR. The optical behavior and lower cut off wavelength of the grown crystal are measured. The presence of various compounds in the grown sample is confirmed by elemental analysis. The thermal stability and NLO property of the grown crystal are
studied by TGA/DSC and SHG respectively. Mechanical properties are clarified by Vickers hardness test. The VSM graph confirms the paramagnetic nature of the grown crystal. These properties make ABS crystal a suitable candidate for optoelectronic device applications.
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Fig. 10. VSM plot of grown ABS crystal.
Acknowledgements
[10] K. Srinivasan, P. Ramasamy, A. Cantoni, G. Bocelli, Mater. Sci. Eng., B 52 (2–3) (1998) 129–133. [11] R. Ramesh, C. Mahadevan, Bull. Mater. Sci. 21 (4) (1998) 287–290. [12] David R. Lide (Ed.), CRC Handbook of Chemistry and Physics, 87th ed., CRC Press, Boca Raton, FL, 2006ISBN 0-8493-0487-3. [13] S. Nagalingam, S. Vasudevan, P. Ramasamy, Cryst. Res. Technol. 16 (6) (1981) 647–650. [14] R.J. Davey, J.W. Mullin, J. Cryst. Growth 26 (1974) 45. [15] Shyamala Devarajan Delcizion, Thayumanavan Arunachalam, J. of Cryz. Prod. Technol. 3 (2013) 5–11. [16] N. Bhuvaneshwari, K. Baskar, R. Dhansekaran, Optik 126 (2015) 3731–3736. [17] P. Rajesh, P. Ramasamy, Opt. Mater. 42 (2015) 87–93. [18] A. Kumaresh, R. Arunkumar, Optik 127 (2016) 1922–1925. [19] Y. Okaya, K. Vedam, R. Pepinsky, Acta Crystallogr. 11 (4) (1958) 307 307. [20] Kazuo Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds: Part B, fifth ed., John Wiley & Sons, New York, 1997. [21] G. Pasupathi, P. Philominathan, J. Min Matt. Charact. Eng. 11 (2012) 904–907. [22] Kazuo Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds: Part A, fifth ed., John Wiley & sons, NewYork, 1997. [23] Azha Periasamy, S. Muruganand, M. Palanisamy, Ra. J. Chem. 2 (4) (2009) 981–989. [24] S. Meenakshisundaram, S. Parthiban, G. Madhurambal, S.C. Mojumdar, J. Therm. Anal. Calorim. 96 (1) (2009) 77–80. [25] R. Manimekalai, A. Antony Joseph, C. Ramachandra Raja, Spectrochim. Acta Mol. Biomol. Spectrosc. 122 (2014) 232–237. [26] A.A. El-Fadl, M.A. Gaffar, M.H. Omar, Physa. B 269 (3–4) (1999) 403–408. [27] R. Punniyamoorthy, R. Manimekalai, G. Pasupathi, Crst. Res. Technol. 53 (10) (2018) 1800114. [28] R. Punniyamoorthy, R. suganthi, R. Manimekalai, G. Pasupathi, Asian J. Chem. 30 (2018) 12 0000-0000. [29] A.V. Baryshev, T. Kodama, K. Nishimura, H. Uchida, M. Inoue Citation, J. Appl. Phys. 95 (2004) 7336. [30] M.P. Binitha, P.P. Pradyumnan, J. Therm. Anal. Calorim. (2013), https://doi.org/ 10.1007/s10973-013-2998- 2. [31] G. Pasupathi, K. Uma, C. Ramachandra Raja, R. Manimekalai, Mater. Lett. 161 (2015) 224–226.
We are also full heartedly acknowledging the support rendered by St. Josephs College, Trichy, India and Indian Institute of Science, Bangalore, India. We also thank Alagappa University, Karaikudi, India and Indian institute of Technology (IIT) madras, India for their assistance to do our research work. Appendix A. Supplementary data Supplementary data to this article can be found online at https:// doi.org/10.1016/j.matchemphys.2019.02.092. References [1] Sunil chaki, M.P. Deslpande, Jiten P. Tailor, D. Chaudhary Mahesh, Amer. J. Cond. Mater. Phy. 2 (1) (2012) 22–26. [2] A. Jegatheesan, B. Neelakantaprasad, J. Murugan, G. Rajarajan, Int. J. Com. App. 53 (2012) 0975–8887. [3] G. Bhagavannarayan, S. Parthiban, S. Meenakshisundaram, Cry. Growth 8 (2) (2008) 446–451. [4] M. Krishna mohan, S. Ponnusamy, C. Muthamizhchelvan, Optic Laser. Technol. 97 (2017) 321–326. [5] Sagadevan Suresh, The Afri. Rev. Phy. 8 (2013) 0006. [6] Genbo Su, Xinxin Zhuang, Youping He, Guozong Zheng, Sci. Direct, Optic Mater. 30 (2008) 916–919. [7] Genbo Su, Xinxin Zhuang, Youping He, Zhengdong Li, Guofu Wang, J. Phys. D Appl. Phys. 35 (2002) 2652–2655. [8] M. Iyanar, J. Thomas, Joseph prakash, C. Muthamizhchelvan, S. Ekadevasena, Dhavud Shek, Mater. Sci. Res.: India 2 (1) (2015) 22–27. [9] K. Murugadoss, K. Gayathiridevi, G. Pasupathi, J. Opt. (2016), https://doi.org/10. 1007/s 12596-015- 0301- 6.
155
Contents lists available at ScienceDirect
Materials Chemistry and Physics journal homepage: www.elsevier.com/locate/matchemphys
Materials science communication
Growth and investigation on structural optical, thermal and magnetic behavior of ammonium bisulphate nonlinear single crystals
T
S. Chidambarama, A. David Kalaimani Rajb, R. Manimekalaia,∗ a b
Department of Physics, A.V.V.M. Sri Pushpam College (Autonomous), Poondi, 613 503, Tamilnadu, India Department of Physics, BDUMC, Aranthangi, Tamilnadu, India
HIGHLIGHTS
novel inorganic NLO crystal namely Ammonium bisulphate has been grown by slow evaporation method. • AMelting point of ABS single crystal is 588 °C and it is found suitable for optical device fabrication. • The grown crystal exhibits paramagnetic nature. • From mechanical analysis the ABS crystal belongs to soft material. • From the results, the grown crystal is more suitable for opto-electronic applications. • ARTICLE INFO
ABSTRACT
Keywords: Crystal growth Single crystal XRD SHG analysis Magnetic property
The new inorganic NLO ammonium bisulphate single crystal was synthesized by the slow evaporation method. The structure of the grown crystal was analyzed by X-RAY diffraction studies. The FT-IR spectrum confirms the presence of different functional groups of the grown crystal. Its optical transmittance is understood by UV-Vis-NIR spectrophotometer. The presence of SHG efficiency of the grown crystal was confirmed by Kurtz powder technique. The dissever nature of the crystal was analyzed by thermal studies. The mechanical behavior of the grown crystal is carried out at room temperature using Vicker's micro hardness tester, whenever the load increased, its hardness also increased. The elemental composition of the grown crystal was studied by EDAX analysis. The paramagnetic behavior of the grown crystal is confirmed by vibrating sample magnetometer.
1. Introduction In recent years, the new materials are needed for the wide range of applications in various fields, namely optoelectronics, photonics, optical data storage and telecommunication etc. Now numerous inorganic NLO materials are produced. The inorganic materials have high thermal stability. They also have high refractive index and good magnetic properties. There is good literature on piezoelectric, dielectric inorganic materials with good optical and mechanical properties [1–3]. The materials like ADP, L-tartaric acid and triglycine sulphate crystals have already been reported [4] to be NLO active materials. Sagadevan suresh et al. has reported on microhardness and dielectric characterization of lithium potassium sulphate crystal [5–7]. In this work we have chosen ADP and potassium sulphate grow a new crystal using double distil water in slow evaporation method at room temperature. When potassium sulphate is ∗
added with ADP it yields ammonium bisulphate (NH4 H SO4) single crystal and the dipotassium phosphate (K2 H PO4) is evaporated. The grown crystals are obtained with good transparency [8–11]. They crystallize in orthorhombic structure. From the literature [12], it is known that the ammonium bisulphate is soluble in water and methanol, insoluble in acetone. Our grown sample also does the same. Hence it is confirmed that the grown crystals are ammonium bisulphate. The ammonium bisulphate crystals got excellent outcome of thermal properties and mechanical strength. The structural optical, thermal and magnetic properties of the grown crystals have been studied by single crystal XRD, FTIR, UV, TGA/DSC, EDAX, NLO and VSM studies [13–18]. 2. Experimental procedure The single crystals of ammonium bisulphate [ABS] have been grown
Corresponding author. E-mail address: [email protected] (R. Manimekalai).
https://doi.org/10.1016/j.matchemphys.2019.02.092 Received 31 October 2018; Received in revised form 25 February 2019; Accepted 27 February 2019 Available online 03 March 2019 0254-0584/ © 2019 Published by Elsevier B.V.
Materials Chemistry and Physics 229 (2019) 149–155
S. Chidambaram, et al.
3.3. UV-vis spectral studies The UV-Visible NIR spectrum of the grown crystal with dimension (12x3x3 mm3) is recorded using Bruker UV-Vis-NIR spectrometer, and is shown in Fig. 3. In general, the study is mainly used for optical analysis. The optical absorption spectrum for the grown crystal was recorded in the range from 190 to 1100 nm. The resultant spectrum has very low absorption in the entire visible and IR region. The ammonium bisulphate single crystal has a good transmittance as shown in Fig. 4. The lower cut-off wavelength is nearly at 390 nm. The large transmittance in the entire visible region enables it to be a good prospect for optical applications. Absorption in the near ultraviolet region arises from the electronic transitions associated within the crystal. Using the formula αhν = A (hν-Eg)1/2 the optical band gap energy was found, where h is the planck's constant and c is the velocity of light. From tauc's plot the calculated band gap energy is 3.6 eV and is shown in Fig. 5.
Fig. 1. Photograph of Ammonium bisulphate crystal.
by the slow evaporation of the solvent. The (Analar grade) ammonium dihydrogen phosphate (NH4 H2 PO4) and Potassium sulphate (K2SO4) are dissolved in deionized water in the molar ratio 1:1 at room temperature. The saturated solution of ammonium bisulphate was prepared and kept in the dust free atmosphere. The good quality transparent ammonium bisulphate crystals are harvested after 20 days with dimension (16x5x4 mm3) as delineate in Fig. 1. The chemical reaction is as follows:
3.4. Nonlinear optical study The nonlinear optical behaviour of ammonium bisulphate crystal was confirmed by Kurtz and Perry powder technique. The Nd:YAG laser (QUANTA RAY Model LAB-170-10) emitting a fundamental wavelength of wavelength 1064 nm; pulse width 6ns and input energy 0.70J was allowed to focus on the powder sample. The output energy was detected by a photomultiplier tube. The second harmonic generation in the crystalline sample was confirmed by the emission of green radiation at 532 nm from the sample. The measured output energy of ammonium bisulphate crystal was 3.54 mJ against 8.94 mJ for the KDP crystal. From this, it is clear that the SHG conversion efficiency of ABS is 0.39 times that of KDP. This confirms the nonlinear optical behavior of ABS crystals.
NH4 H2 PO4 + K2 SO4 → NH4 H SO4 + K2 H PO4 ↑ The compound K2HPO4 is evaporated; hence the resultant compound is ammonium bisulphate [8,21]. 3. Results and discussion 3.1. Single XRD To determine the unit cell parameters of the grown ABS single crystals, the APEX2 diffractometer is used. The good quality crystal was selected for the X-ray diffraction studies. They crystalize is orthorhombic system with non-centro symmetric space group as Pna21 [19,20]. The unit cell dimension is shown in Table 1.
3.5. Thermal studies Thermo gravimetric analysis (TGA) and Differential Scanning Calorimetric (DSC) analyses of ammonium bisulphate single crystals are shown in Fig. 6. The sample was heated at the rate of 20 °C/min in an inert nitrogen atmosphere between 20 °C and 1400 °C using Perkin Elmer Diamond TGA/DSC analyzer. In TGA thermogram, there is gradual weight loss up to 100 °C; it is due to the liberation of water molecules from the sample. There is also another exothermic peak nearly at 588 °C; this temperature corresponds to melting point of the compound. The sharp exothermic peak occurring nearly at 1050 °C may be the decomposition compound of the grown ABS crystal. At this temperature the volatile substances are likely to decompose into residues. The sharpness of peak indicates the purity and crystallinty of the sample [24–26].
3.2. Fourier transform infrared (FTIR) analysis FTIR Spectrum of the grown ammonium bisulphate crystal is recorded using Perkin Elmer RX1 spectrometer as shown in Fig. 2. From the interpretation of the FTIR spectrum, the functional groups present in the grown crystal can be confirmed. The broad peak at 3364 cm−1 is attributed to OH stretching frequency. The sharp peak observed at 2923 cm−1 is due to NH2 bending. The broad peak appearing at 1620 cm−1 is due to NH2 symmetric stretching. The strong peak at 1382 cm−1 is assigned to NH2 asymmetric stretching frequency. The week peak at 1248 cm−1 is due to S-O-H plane bending. The peak at 829 cm−1 and 614 cm−1 are due to SO4 symmetric stretching and asymmetric stretching [21–23]. The presence of various functional groups are identified and presented in Table 2.
3.6. Micro hardness studies The hardness test provides useful information about the strength and deformation characteristics of the ammonium bisulphate single crystal [4]. The microhardness study is done by using Vickers microhardness tester fitted with a diamond indenter. The load is applied to
Table 1 Single crystal XRD data of ammonium bisulphate. Sample
Cell parameters (Å)
ABS
a = 5.80
b = 7.55
c = 10.13
α=β=γ
Volume (Å)3
System
Space group
90
444
Orthorhombic
Pna21
150
Materials Chemistry and Physics 229 (2019) 149–155
S. Chidambaram, et al.
Fig. 2. FTIR Spectrum of ABS crystal.
the grown single crystal in the order of 25, 50 and 100 g at room temperature. The drawn graph clearly indicates that, if the load value increases then hardness value of the crystal also increases as shown in Fig. 7. In order to find the work hardening coefficient (n) by Mayer's law, a graph was plotted for log P and log d as shown in Fig. 8. The work harding coefficient (n) of the grown ABS crystal is found to be 3.1. Generally, it lies between 1 and 1.6 for hard materials and is more than 1.6 for soft materials. From the observed n value, it is concluded that the grown ABS crystal belongs to soft material category [27,28,30].
Table 2 FTIR spectral assignments of ABS crystal. Wave number for grown crystal in (cm−1)
Frequency assignments
3364 2923 1620 1382 1248 829 614
OH stretching NH2 bending NH2 symmetric stretching NH2 asymmetric stretching S-O-H in plane bending SO4 symmetric stretching SO4 asymmetric stretching
Fig. 3. Absorbance curve of ABS.
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S. Chidambaram, et al.
Fig. 4. Optical transmittance of ABS.
Fig. 5. Optical band gap of ABS crystal.
3.7. EDAX analysis
given in Table 3.
The energy dispersive X-ray analysis (EDAX) is the useful tool for the elemental analysis and it is carried out by Geon 5610 LV Model. The presence of various components of the grown sample is analyzed. The recorded EDAX spectrum of the ABS crystal is shown in Fig. 9. The weight percentages of the various elements present in the sample are
3.8. Vibration sample magnetometer The magnetic properties of a variety of materials have been investigated. In the present case, the magnetic study was carried out using a vibrating sample magnetometer CR155 quantum design. The mass of
152
Materials Chemistry and Physics 229 (2019) 149–155
S. Chidambaram, et al.
Fig. 6. TGA/DSC of ABS crystal.
Fig. 7. Variation of Vicker's hardness number with load.
the sample taken at room temperature was 3g and the hysteresis path is traced for moment Vs field as shown in Fig. 10. When the magnetic field is applied, the dipole will align with the externally applied magnetic field, resulting in the magnetic moment in the direction of the applied field. From the plot it is clear that the grown ABS crystal have a positive susceptibility. This confirms the paramagnetic nature of the grown ABS single crystal [29–31]. The paramagnetic ABS crystals are used to store
data on hard drive and read them out. 4. Conclusion The single crystal of ammonium bisulphate, a new inorganic NLO material, has been grown by slow evaporation technique. The single crystal XRD analysis confirms the structure of the crystal as
153
Materials Chemistry and Physics 229 (2019) 149–155
S. Chidambaram, et al.
Fig. 8. Plot of Log d vs Log P for ABS crystal.
Fig. 9. EDAX pattern of ABS crystal. Table 3 Elemental composition of ABS crystal. Element
O
N
S
Totals
Weight % Atomic %
57.80 60.50
19.04 23.20
23.16 16.30
100.00 100.00
orthorhombic system. The functional groups of ABS crystal were identified using FTIR. The optical behavior and lower cut off wavelength of the grown crystal are measured. The presence of various compounds in the grown sample is confirmed by elemental analysis. The thermal stability and NLO property of the grown crystal are
studied by TGA/DSC and SHG respectively. Mechanical properties are clarified by Vickers hardness test. The VSM graph confirms the paramagnetic nature of the grown crystal. These properties make ABS crystal a suitable candidate for optoelectronic device applications.
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Fig. 10. VSM plot of grown ABS crystal.
Acknowledgements
[10] K. Srinivasan, P. Ramasamy, A. Cantoni, G. Bocelli, Mater. Sci. Eng., B 52 (2–3) (1998) 129–133. [11] R. Ramesh, C. Mahadevan, Bull. Mater. Sci. 21 (4) (1998) 287–290. [12] David R. Lide (Ed.), CRC Handbook of Chemistry and Physics, 87th ed., CRC Press, Boca Raton, FL, 2006ISBN 0-8493-0487-3. [13] S. Nagalingam, S. Vasudevan, P. Ramasamy, Cryst. Res. Technol. 16 (6) (1981) 647–650. [14] R.J. Davey, J.W. Mullin, J. Cryst. Growth 26 (1974) 45. [15] Shyamala Devarajan Delcizion, Thayumanavan Arunachalam, J. of Cryz. Prod. Technol. 3 (2013) 5–11. [16] N. Bhuvaneshwari, K. Baskar, R. Dhansekaran, Optik 126 (2015) 3731–3736. [17] P. Rajesh, P. Ramasamy, Opt. Mater. 42 (2015) 87–93. [18] A. Kumaresh, R. Arunkumar, Optik 127 (2016) 1922–1925. [19] Y. Okaya, K. Vedam, R. Pepinsky, Acta Crystallogr. 11 (4) (1958) 307 307. [20] Kazuo Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds: Part B, fifth ed., John Wiley & Sons, New York, 1997. [21] G. Pasupathi, P. Philominathan, J. Min Matt. Charact. Eng. 11 (2012) 904–907. [22] Kazuo Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds: Part A, fifth ed., John Wiley & sons, NewYork, 1997. [23] Azha Periasamy, S. Muruganand, M. Palanisamy, Ra. J. Chem. 2 (4) (2009) 981–989. [24] S. Meenakshisundaram, S. Parthiban, G. Madhurambal, S.C. Mojumdar, J. Therm. Anal. Calorim. 96 (1) (2009) 77–80. [25] R. Manimekalai, A. Antony Joseph, C. Ramachandra Raja, Spectrochim. Acta Mol. Biomol. Spectrosc. 122 (2014) 232–237. [26] A.A. El-Fadl, M.A. Gaffar, M.H. Omar, Physa. B 269 (3–4) (1999) 403–408. [27] R. Punniyamoorthy, R. Manimekalai, G. Pasupathi, Crst. Res. Technol. 53 (10) (2018) 1800114. [28] R. Punniyamoorthy, R. suganthi, R. Manimekalai, G. Pasupathi, Asian J. Chem. 30 (2018) 12 0000-0000. [29] A.V. Baryshev, T. Kodama, K. Nishimura, H. Uchida, M. Inoue Citation, J. Appl. Phys. 95 (2004) 7336. [30] M.P. Binitha, P.P. Pradyumnan, J. Therm. Anal. Calorim. (2013), https://doi.org/ 10.1007/s10973-013-2998- 2. [31] G. Pasupathi, K. Uma, C. Ramachandra Raja, R. Manimekalai, Mater. Lett. 161 (2015) 224–226.
We are also full heartedly acknowledging the support rendered by St. Josephs College, Trichy, India and Indian Institute of Science, Bangalore, India. We also thank Alagappa University, Karaikudi, India and Indian institute of Technology (IIT) madras, India for their assistance to do our research work. Appendix A. Supplementary data Supplementary data to this article can be found online at https:// doi.org/10.1016/j.matchemphys.2019.02.092. References [1] Sunil chaki, M.P. Deslpande, Jiten P. Tailor, D. Chaudhary Mahesh, Amer. J. Cond. Mater. Phy. 2 (1) (2012) 22–26. [2] A. Jegatheesan, B. Neelakantaprasad, J. Murugan, G. Rajarajan, Int. J. Com. App. 53 (2012) 0975–8887. [3] G. Bhagavannarayan, S. Parthiban, S. Meenakshisundaram, Cry. Growth 8 (2) (2008) 446–451. [4] M. Krishna mohan, S. Ponnusamy, C. Muthamizhchelvan, Optic Laser. Technol. 97 (2017) 321–326. [5] Sagadevan Suresh, The Afri. Rev. Phy. 8 (2013) 0006. [6] Genbo Su, Xinxin Zhuang, Youping He, Guozong Zheng, Sci. Direct, Optic Mater. 30 (2008) 916–919. [7] Genbo Su, Xinxin Zhuang, Youping He, Zhengdong Li, Guofu Wang, J. Phys. D Appl. Phys. 35 (2002) 2652–2655. [8] M. Iyanar, J. Thomas, Joseph prakash, C. Muthamizhchelvan, S. Ekadevasena, Dhavud Shek, Mater. Sci. Res.: India 2 (1) (2015) 22–27. [9] K. Murugadoss, K. Gayathiridevi, G. Pasupathi, J. Opt. (2016), https://doi.org/10. 1007/s 12596-015- 0301- 6.
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