Dosimetric applications of CdSiO₃ nanoparticles prepared via Solution Combustion Technique

 

Kamala Soppin¹, H.R. Venkatesha², B. M. Manohara^{3, *}

¹Department of Physics, DRM Science College, Davangere - 577004, India.

²Department of Physics, Government First Grade College, Hosadurga-577527, Chitradurga-Dist. India.

³Department of Physics, Government First Grade College, Davangere - 577004, India.

 

ABSTRACT:

Pure CdSiO₃ nanoparticles have been prepared by a solution combustion technique. The powders were well characterized by powder X-ray diffraction, Field Emission scanning electron microscopy and Ultra Violet-visible spectroscopy. The powder X-ray diffraction peaks of as-formed sample are broad and amorphous in nature; therefore it is further calcined at 800 ^oC for 2 h and its powder X-ray diffraction results shows that the sample had a good crystallization with Single phase. Debye- Scherer’s formula and Williamson–Hall plots are used to calculate the average crystallite size and found to 32-43 nm. The Scanning electron microscope and Transition electron microscope results reveal that the pure CdSiO₃ nanoparticles were porous and agglomerated with irregular nanopowder. The absorption peaks for pure CdSiO₃ nanoparticles were found to about 256 nm as observed in Ultra Violet-Visible spectra. The structural defects present in the material band gap (E_g) value were 5.6 eV. A well resolved thermoluminescence glow peaks in the range of (110-160) ^oC are observed in UV-irradiated pure CdSiO₃ nanoparticles. Glow peak at 160 ºC was seen and Thermoluminescece intensity increases linearly with Ultra Violet dose in the samples. The kinetic parameters were determined by Halperin – Braner, Luschik and Chen’s methods. De-convolution of pure CdSiO₃ nanoparticles exposed to Ultra Violet dose (UV dose: 30 min) was used for the estimation of kinetic parameters. Hence in pure CdSiO₃ nanoparticles presence of deep traps recommends that the prepared sample may be used as a radiation dosimeter.

 

 

INTRODUCTION:

Silicate hosts is found to be multi-color phosphorescent and is inactive with alkali, oxygen and acid environment^1,2. Various silicate hosts, exhibit a remarkable optical and luminescent property in their pure and doped form, however in CdSiO₃ nanoparticles due to the presence of Cd²⁺ ions and strong interaction between Si-O present in the SiO₃ group³. The crystal structure of CdSiO₃ nanoparticles shows one dimensional chain of edge-sharing SiO₄ tetrahedron and as a result dopants can be easily embedded into the host by replacing the Cd²⁺ site.

 

Synthesis of silicate nanoparticles has variety of routes such as Sol-Gel, solid state reactions, hydrothermal, microwave techniques etc^{4, 5}.

 

Pure CdSiO₃ nanoparticles have been synthesized by solution combustion technique (SC) using fumed silica and ODH as a fuel. SC technique offers a unique synthesis route via a highly exothermic redox reaction, results in homogeneous, crystalline, fine powders with porous morphology^{6, 7}. The synthesis samples were characterized by Powder X-ray diffraction (PXRD), Field emission scanning electron microscopy (FESEM) and UV-Visible Spectroscopy. Thermoluminescence (TL) studies were made at RT and discussed in detail.

 

SYNTHESIS Of PURE CdSiO₃ NANOPARTICLES:

The pure CdSiO₃ nanoparticles were synthesis by solution combustion technique (SC). The stoichiometric amounts of AR grade Cadmium nitrate (Cd (NO₃)₂·4H₂O), fumed silica, oxaly dihydrazine (ODH:C₂H₆N₄O₂) as a fuel were used for the synthesis of pure CdSiO₃ nanoparticles^{8, 9}. The final product was calcined at 600 ⁰C, 700 ⁰C, 800 ⁰C and 900 ⁰C for 2 h. The flow chart of complete process and the steps involved in the synthesis of pure CdSiO₃ nanoparticles was shown in Fig.1. and combustion reaction is, 5Cd (NO₃)₂ 4H₂O + 71C₂H₆N₄O₂ + 5SiO_{2 →} 5CdSiO₃ + 202N₂ + 218H₂O + 142CO₂                                          (1)

 

Fig.1. Flow chart showing low temperature solution combustion technique of pureCdSiO₃ nanoparticles

 

Powder X-ray diffraction (PXRD) analysis was performed using Shimadzu X-ray diffractometer (operating at 50 KV and 20 mA by means of CuK_ (1.541Å) radiation with a nickel filter at a scan rate of 2^o min^-1). Morphology of the samples was analyzed by using a field emission scanning electron microscope (FESEM) (ULTRA55, FESEM (Carl Zeiss) with EDS). The Elico SL-150 spectrophotometer was used for optical absorption studies in the range 200-800 nm. The samples are 0.03 g weights and irradiated for 5 to 40 min to a UV lamp at 254 nm with a 15 W with heating rate of 5^oCs^-1 a model Nucleonix TL Reader, Thermoluminescence (TL) measurements were made.

 

RESULTS AND DISCUSSION:

POWDER X-RAY DIFFRACTION ANALYSIS (PXRD):

PXRD patterns of SC synthesized pure CdSiO₃ nanoparticles shown in Fig.2. The samples calcined up to 700 ^oC show amorphous nature, single monoclinic phase was obtained after calcined at 800 ^oC for 2 h and all the Powder X-ray diffraction peaks of the sample were well matched with JCPDS card No. 35-0810, which is better than the results obtained by other synthesis methods. The line broadening in PXRD, average crystallite size of the sample was estimated using Scherrer’s formula^{10, 11}.

where, ‘K’ is the Scherrer’s constant 0.9, ‘λ’ is the wavelength of X-ray (1.5418 A), ‘β’ is the full width at half maximum of the diffraction peak, ‘θ’ is the Bragg’s angle. The pure CdSiO₃ nanoparticles average crystallite size is found to be 32 nm and W-H equation is used for estimated of strain present in the sample¹².

 

where ‘ε’ is the strain associated with the nanoparticles. The equation (3) represents a straight line between ‘4sinθ’ (x-axis) and ‘βcosθ’ (y-axis). The effective particle size for which the lattice strain has been taken into account can be estimated from the extrapolation of the plot as shown in Fig. 3. From the W-H plots the lattice strain is extracted from the slope and the crystalline size was extracted from the y-intercept of the linear fit. The average crystallite size was found to be 43 nm and lattice strain was 1.07× 10^-3.

 

Fig.2. PXRD of pure CdSiO₃ nanoparticles a) As formed and

calcined for 2 h, at b) 600 ^oC c) 700 ^oC d) 800 ^oC e) 900 ^oC.

 

Fig.3. Williamson-Hall plots of pure CdSiO₃ nanoparticles calcined at 800 ⁰C for 2 h.

 

MORPHOLOGICAL ANALYSIS:

Fig 4 (a-e) show the Field effect electron scanning microscopes (FESEM) pictures of prepared pure CdSiO₃ nanoparticles reveal that foamy, porous, large agglomerates with very fine particles having polycrystalline in nature. Depending upon the type of fuel and metal ions used reaction is influenced by metal–ligand complex formation. Flaming reactions involves liberation of large quantity of gases. The nature of combustion differs from flaming (gas phase) to non-flaming (smoldering and heterogeneous) type. The pores and voids to the large amount of gases escaping out of the reaction during combustion¹³.

 

UV-VISIBLE ABSORPTION STUDIES:

Fig.5. shows optical energy gap (E_g) of pure CdSiO₃ nanoparticles was calculated using Wood and Tauc relation was found to be 5.6 eV¹⁴. The inset Fig.5 shows optical absorption spectra of pure CdSiO₃ nanoparticles¹⁵ and the absorption bands at ~ 256 nm may be due to surface oxygen vacancies. Hence a pure CdSiO₃ nanoparticle is an insulating material.

 

Fig.4. FESEM images of pure CdSiO₃ nanoparticles, a) As formed and calcined for 2 h. at b) 600 ^oC c)700 ^oC d) 800 ^oC e) 900 ^oC.

 

Fig.5. Energy band gap of pure CdSiO₃ nanoparticles calcined at 800 ⁰C for 2h.

(Inset: UV-Vis absorption spectrum of pure CdSiO₃ nanoparticles)

 

THERMOLUMINESCENCE (TL) STUDIES:

Thermoluminescence (TL) of the samples irradiated under UV source for the time 5 to 40 min was studied at RT shown in Fig.6 and Fig.7. shows disparities of UV dose (5-40 min) verses intensity. TL glow curve shows well resolved glow peak at ~ 160 ^oC and the intensity increases with UV irradiation time¹⁶. The impurity-trapped exactions and annihilation will be a major dissipation of energy absorbed by a material with self-trapped exaction. The observed TL peaks may be attributed to recombination of trapped electrons with different holes produced during irradiation^{17, 18}.

 

Fig.6. TL glow curves of UV irradiated pure CdSiO₃ nanoparticles.

 

The kinetic parameters are responsible for dosimetric characteristic properties of a material. The trap depth (E) or activation energy, order of kinetics (b) and frequency factor (s) will give information about the stability of the traps. The glow peak occurs at a relatively lower temperature for lower activation energy and corresponding trap is unstable. If it is high then the trap is relatively stable. The order of kinetics revels about whether the trapped charge carriers will be re-trapped on heating or not. There are three standard methods to determination of these parameters namely Luschik, Halperin – Braner and Chen’s method¹⁹. Fig.8 shows the sample (UV dose: 15 min) estimation of kinetic parameters TL Glow curves de-convolution of pure CdSiO₃ particles exposed to 40 min UV dose at heating rate of 5 ^oCs^-1. The order of kinetics (b) or symmetry factor ‘μ_g’ is determine by the equation,

 

where, T₁ and T₂ are the temperature corresponding to the half of the maximum intensities on either side of the glow peak maximum - T_m. Theoretically, the value of ‘μ_g’ ranges between 0.42 and 0.52. It is close to 0.42 for first order kinetics and 0.52 for second order kinetics. The form factor ‘μ_g’ is found to be practically independent of the activation energy ‘E’ and strongly depends on the order of kinetics.

 

Fig.7.Variation of TL intensity as a function of UV irradiation dose (5-40 min)

 

Fig.8. Glow curve de-convolution of pure CdSiO₃ nanoparticles (UV dose: 15 min)

 

In the Luschik method²⁰, the descending part of the glow peak was used where the area of the half peak, resembled the area of the triangle having identical height and half width. The equation is given by

                                                                                                 

The ascending part of the glow peak whose area was assumed to be equal to the area of the triangle given in Halperin - Braner method ²¹ is,

 

where,

The activation energy in modified Chen’s method²² is,

 

According to Randall and Wilkinson^{23, 24} the estimation of frequency factor (s) is,

 

where, k is Boltzmann constant and

where, (k: Boltzmann constant = 8.6 x 10^-5 eV K^-1),

All the calculated parameters were tabulated in table 1. The presence of deep traps in pure CdSiO₃ nanoparticles suggests that it can be used as a radiation dosimeter for animated monitoring.

 

Table. 1. Estimated kinetic parameters using glow peak shape method in UV irradiated (5- 40 min) pure CdSiO₃ nanoparticles.

UV-Exposure (min	Peak	Tm (°C)	Balarin Parameter (ϒ)	Order of kinetics b (µg)	Activation Energy (eV)			Frequency factor ‘s’ (s-1)
					Lushchik method	Halperin- braner method	Chen’s method
	1	88.49	1.09	2(0.51)	0.7638	0.8376	0.6491	1.27E+09
	2	132.18	1.02	2(0.52)	0.8628	0.8885	0.6747	2.09E+08
5	3	170.0	1.03	2(0.51)	0.06042	0.6247	0.4479	5.50E+04
	1	113.17	0.98	2(0.49)	0.7179	0.7094	0.5220	5.205+E06
	2	154.95	0.99	2(0.49)	1.1218	1.1139	0.8507	1.01E+10
10	3	192.69	0.93	2(0.48)	0.8759	0.8166	0.5863	1.20+E06
	1	106.89	0.82	2(0.48)	0.8987	0.7426	0.5145	5.46+E06
	2	148.67	0.91	2(0.48)	1.2023	1.1044	0.8227	6.59E+09
	3	180.15	1.07	2(0.51)	0.6988	0.7492	0.5553	8.15+E05
20	1	125.02	1.03	2(0.50)	0.6324	0.6528	0.4789	804000.6
	2	168.2	0.95	2(0.48)	1.2604	1.2035	0.9115	2.54E+10
	3	211	0.82	2(0.48)	1.5394	1.2711	0.9063	2.2E+09
25	1	106.07	1.04	2(0.51)	0.7151	0.7459	0.5616	2.61+E07
	2	106.07	0.91	2(0.48)	1.1574	1.0552	0.7807	1.84E+09
	3	178.41	1.09	2(0.52)	0.6571	0.7176	0.5311	4.43+E07
30	1	94.92	0.93	2(0.48)	0.8765	0.8233	0.6093	2.28E+08
	2	134.59	1.01	2(0.50)	0.9322	0.9464	0.7198	7.16E+08
	3	171.54	1.01	2(0.50)	0.6611	0.6723	0.4855	1.55+E05
35	1	114.36	0.88	2(0.48)	0.7927	0.7003	0.4947	2.06E+E06
	2	140.07	0.94	2(0.48)	2.1405	2.0145	1.5719	2.97E+19
	3	170.42	0.91	2(0.48)	0.6823	0.6264	0.4334	3.62E+04
40	1	102.92	1.02	2(0.450)	0.6905	0.7104	0.5305	1.11+E07
	2	141.79	1.02	2(0.50)	0.7834	0.8045	0.6022	1.48+E07
	3	184.69	0.96	2(0.49)	0.6731	0.6515	0.4593	4.91+E04

 

CONCLUSIONS:

Pure CdSiO₃ nanoparticles have been successfully synthesized by using the SC technique. Monoclinic phase at low temperature of 800 ^oC for 2 h confirms by PXRD and nano in size. FESEM show that the powder is agglomeration, foamy, highly porous and polycrystalline nature. The energy band gap of the sample was found to be 5.6 eV confirms the synthesized Pure CdSiO₃ nanoparticles is an insulator, which well matches with the literature. The pure CdSiO₃ nanoparticles system shows grain boundary contributions and the high resistance attributed to both grain respectively. TL response of the sample show that its possible application in radiation dosimetry. Hence, pure CdSiO₃ nanoparticles prepared by this facile SC technique can be the better material for radiation dosimetry applications.

 

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Accepted on 24.09.2020           © RJPT All right reserved

Research J. Pharm. and Tech 2021; 14(10):5330-5334.