Science International  Volume 5 Issue 4, 2017

Research Article

Effect of Gamma Radiation on the Crystallographic Features and Applications of Stannic Antimonate and Its Dopants
Mamdouh Mohamed Abou-Mesalam
Atomic Energy Authority, Hot Labs. Centre, P. Code 13759, Cairo, Egypt

Asmaa Bendary Ibrahim
Atomic Energy Authority, Hot Labs. Centre, P. Code 13759, Cairo, Egypt

ABSTRACT:
Objective: Doping of inorganic ion-exchange material stannic antimonates with cobalt and strontium ions by sol-gel technique was conducted for a novel ion-exchangers. Methodology: Undoped and doped stannic antimonates has been characterized by elemental analysis (X-ray fluorescence), fourier transform infrared spectroscopy (FT-IR), thermal analysis and X-ray diffraction studies. X-ray peak broadening analysis was used to evaluate the crystallite size and lattice strain by Scherrer’s formula and Williamson-Hall (W.H) analysis. Results: The structures of three ion-exchangers were identified and the empirical formulas found as (SnSb.O(1.59).3.34H2O), (CoSnSb.O(1.51).4.18H2O) and (SrSnSb.O(1.5).H2O) for stannic antimonate, cobalt stannic antimonate and strontium stannic antimonate, respectively. Undoped and doped stannic antimonates as inorganic ion-exchangers were subjected to gamma doses of 10, 50 and 100 kGy to study the radiation stabilities of these compounds. The total capacity for Co2+ and Cd2+ ions were studied for stannic antimonates, cobalt and strontium doped stannic antimonates. Conclusion: There were no practically significant changes between the control and irradiated samples, showing that these exchangers are stable up to the levels of irradiation under investigation.
 
    How to Cite:
Mamdouh Mohamed Abou-Mesalam and Asmaa Bendary Ibrahim , 2017. Effect of Gamma Radiation on the Crystallographic Features and Applications of Stannic Antimonate and Its Dopants. Science International, 5: 155-163
DOI: 10.17311/sciintl.2017.155.163
 


INTRODUCTION
Antimonate salts are one of the most important classes of synthetic inorganic ion exchange materials as they are temperature resistant and stable under chemical attacks1-3. Some inorganic and organic materials show bad effect on the crystallographic features when exposed to high radiation doses. The main problem was shown in laboratory, prepared some salts of poly basic acids with tetravalent metal ions such as cerium (IV)-, tin (IV)-, titanium (IV)- and silicon (IV) antimonates3-7 under different conditions and study their possible use in the treatment of low and intermediate-level radioactive liquid wastes3-7. X- ray profile analysis is a simple and tool to estimate the crystallite size and lattice strain8. Among the available methods to estimate the crystallite size and lattice strain are the pseudo-Voigt function, riveted refinement and Warren-Averbach analysis9-11. Williamson Hall (W.H) analysis is a simplified integral breadth method where both size-induced and strain–induced broadening is deconvoluted by considering the peak width as a function of 2θ peak width Arora and Vashali12. The two main properties extracted from peak width analysis are (a) crystallite size and (b) lattice strain. Crystallite size is a measure of the size of a coherently diffracting domain. The crystallite size of the particles is not generally the same as the particle size due to the presence of polycrystalline aggregates13. Lattice strain is a measure of the distribution of lattice constants arising from crystal imperfections, such as lattice dislocation. The other sources of strain are the grain boundary triple junction, contact or sinter stresses, stacking faults, coherency stresses, etc.14-15. The aim of this study was to prepare and characterize stannic antimonate, cobalt and strontium doped stannic antimonates as inorganic ion exchangers. The crystallite size and lattice strain due to dopping of cobalt and strontium with stannic antimonate was investigated. The empirical formulas, structures and the ion-exchange capacities of the product materials were conducted.


MATERIALS AND METHODS
Synthesis of stannic antimonate (SnSb) ion exchanger: Stannic antimonate was synthesized by the reaction of 0.1M stannic tetra chloride (dissolved in distilled water) with 0.1 M antimony metal (dissolved in aqua regia) with molar ratio Sn to Sb equal 1:1. During the addition process, yellow gelatinous precipitate formed. After complete addition, few drops of diluted ammonia solution were added for complete precipitation, the precipitate left overnight standing and the mixture was hydrolyzed in distilled water and left for 2 days at room temperature. The precipitate formed was separated by centrifugation at 3000 rpm for 5 min. The precipitate was washed by 0.5M HNO3 to be free from Cl ions and rewashed by distilled water to remove NO3. The precipitate was dried at 60°C in a drying oven and washed with hot water (70°C) to remove the air traps in the solid and then redried at 60°C. The solid was ground, sieved to mesh size and stored at room temperature.

Synthesis of cobalt and/or strontium stannic antimonates (CoSnSb or SrSnSb) ion exchangers: Cobalt and/or strontium chloride solutions with concentration 0.1 M were used for doped cobalt and/or strontium in-situ stannic-antimonates. Cobalt and/or strontium stannic-antimonate solid samples were prepared by the reaction of 0.1 M cobalt and/or strontium chloride solutions with a mixture of 0.1 M stannic tetra chloride (dissolved in distilled water) and 0.1 M antimony metal ( dissolved in aqua regia) with volumetric molar ratio Co and/or Sr :Sn to Sb equal 1:1:1. The reaction carried out in water bath at 60°C with continuous stirring for 4 h. Gelatinous precipitates formed during the addition process of cobalt and/or strontium chloride solutions to the mixture. After an overnight standing the precipitates separated by centrifugation at 3000 rpm. The solids treated by 0.1 M HNO3 to remove impurities and Cl ions. Solids rewashed with distilled water to remove NO3 ions. After drying in drying oven at 60°C, the granules solids poured in near boiling water at 70-80°C to remove the trapped air. Dry, grand, sieve and store solids at room temperature.

Characterization of synthesized stannic antimonate and doping stannic antimonates: Fourier transform infrared spectra (FT-IR) for synthesized materials were measured using Bomem FTIR spectrometer model BOMEM, MBSeries. The measurement carried out by KBr disc method technique from 400-4000 cm–1. X-ray diffraction patterns (XRD) of the synthesized materials were recorded using Shimadzu XD-D1 spectrometer with CuKα radiation tube (λ = 1.5418 Å) and 30 Kv, 30 mA. The patterns and the intensity width- spacing value tables printed out for calculation of the crystallite size and strain of the samples. The crystal system for the structure was determined. Thermal analysis was measured using a Shimadzu DT-60 thermal analyzer, Japan, at a heating rate of 15 min. under a nitrogen atmosphere. An elemental analysis for the synthesized materials investigated by X-ray fluorescence technique, Philips-ray fluorescence PW-2400 sequential spectrometer. Samples were prepared for measurement process as reported earlier by El-Naggar et al.13 grained 1.0 g of the solid sample to very fine particles and mixed with poly vinyl metha-acrylate as a binder to facilitate the pressing process. The mixture pressed in pressing machine to 20 psi for 30 sec. The measurement carried out using super quantitative analysis program.

Capacity measurements: The capacity of synthesized stannic antimonate and doping stannic antimonate for Co2+ and Cd2+ ions were determined by the repeated batch technique, by equilibrating nearly 0.7 g of stannic antimonate and doping stannic antimonate with 70 mL of (30 ppm) Co2+ and Cd2+ ions solutions on a shaker thermostat adjusted at 25±1°C. After an equilibrium, the solution was separated and repeated until no further sorption occurs. The capacity was calculated using the following Eq:

(1)

(2)
Where:
Ao and A = Initial and final concentrations of solution
Co = Initial concentration of solution
V = Solution volume (mL)
m = Weight of the exchanger (g)

Irradiation of the ion exchanger: The samples were irradiated with gamma rays by using Egypt Mega I irradiation facility (type J -6300 Atomic Energy Canada). It was conducted for variable time periods in order to cover a range of absorbed doses 10, 50 and 100 kGy. The experiments described later were performed before and immediately after irradiation of the samples.


RESULTS AND DISCUSSION
Fourier transforms infrared spectroscopy: The effect of γ-radiation on the structure of synthesized stannic antimonate and doping stannic antimonate are shown in Fig. 1a-c. Figure 1(a-c) showed the IR spectra of unirrdiated and irradiated stannic antimonite and doping stannic antimonate. The data in Fig. (1a-c) showed partially there is very little difference between original and irradiated stannic antimonate and doping stannic antimonate. In case of stannic antimonit (Fig. 1a) the investigated bands at ~(3600-2800) may be due to the free water molecules present in the texture of stannic-antimonate16-18 are decreased by exbosing the sample of stannic antimonate and doping stannic antimonite to γ-radiation with dose 10, 50 and 100 kGy. The peaks at ~2455 and ~1652 cm–1 may be due to CO2 in the atmosphere and interstitial water(bonded water), respectively16-18. The peaks at ~1110, 754 cm–1 shown in (Fig. 1a-c) may be due to Sn-O bonds19. The peaks at 500 and 400 cm–1 are due to Sb-O bond19 and characterized to antimonate groups. These peaks not affected by γ-radiation. Figure (1a-c) show the IR spectra of original and irradiated stannic antimonate and doping stannic antimonite samples. These figures indicated that there is no notified difference between the original and irradiated stannic antimonate and doping stannic antimonite samples.

Figgure. 1(a-c): (a) IR spectra of original and irradiated stannic antimonate (SnSb), (b) IR spectra of original and irradiated cobalt stannic antimonate (CoSnSb) and (c) IR spectra of original and irradiated strontium stannic antimonate (SrSnSb)

Table 1: Total weight loss occurred from room temperature to 1000°C amounts for stannic antimonate and doping stannic antimonate

Thermal analysis: DTA and TGA thermograms of stannic antimonate and doping stannic antimonate are represented in Fig. (2a-c and 3a-c). DTA of stannic antimonate indicated a prominent endothermic peak at ~283.35°C that may be due to free adsorbed water. The broad exothermic peak at ~/337.07°C may be due to the decomposition of residual -OH groups and condensation of non-bonded oxygen. The broad endothermic peak at ~431.69°C corresponds to crystallization of metal oxides16. From TG curve it is evident that stannic antimonate was thermally stable up to the temperature of 1000°C. The total weight loss occurred from room temperature to 1000°C amounts are indicated in Table 1.

The loss of ignition that means the water content was calculated from the calcination of an ion exchange material at 1000°C. The data in Table 1 indicated that the weight loss due to ignition were equal 20.02, 20.09 and 21.44 for SnSb, CoSnSb and SrSnSb, respectively. This value was used in calculation of the number of water molecules in the material using the Eq. 117:

(3)
Where:
X = Percent weight loss of ignition
M = Molecular weight of the material

The elemental analysis of the material for Co, Sr, Sn and Sb elements was carried out by X-ray fluorescence technique.

Fig. 2(a-c): (a) Differential thermal and thermogravimetric spectra of original stannic antimonate, (b) Differential thermal and thermogravimetric spectra of original cobalt stannic antimonate and (c) Differential thermal and thermogravimetric spectra of original strontium stannic antimonate

From all results obtained from IR, DTA, XRD and XRF, the tentative formula of stannic antimonate, cobalt stannic antimonate and strontium stannic antimonate material was assigned to (SnSb.O(1.59).nH2O) ,(CoSnSb.O(1.51).nH2O) and (SrSnSb.O(1.5).nH2O), respectively. From the loss of ignition, the number of water molecules (n) per mole of the material was calculated and the above formulas then rewritten as (SnSb.O(1.59).3.34H2O),(CoSnSb.O(1.51).4.18H2O) and (SrSnSb.O(1.5).4.97H2O), respectively, for the structure modeling and the arrangement.

X-effect of gamma radiation on crystallographic feature of SnSb and M-SnSb: Figure 4a-c show the XRD patterns of stannic antimonate and doping stannic antimonate. These figures show different peaks at different 2θ with variable intensities indicating the crystalline nature of these materials. The brage angle 2θ and the full width at half maximum β(FWHM) were determined to evaluate the crystallite size and lattice strain of these materials.

From Debye-Scherrer’s formula:

(4)
Where:
D = Effective average crystalline size
K = Shape factor (0.89)
λ = Wavelength of CuKα radiation in nanometer
θ = Bragg diffraction angle
β = Measured full width at half maximum (FWHM)

Figure. 3(a-c): (a) Differential thermal and thermogravimetric spectra of irradiated stannic antimonate at 100 kGy, (b) Differential thermal and thermogravimetric spectra of irradiated cobalt stannic antimonate at 100 kGy and (c) Differential thermal and thermogravimetric spectra of irradiated strontium stannic antimonate at 100 kGy

The lattice strain induced in powders due to crystal imperfection and distortion was calculated using Hall equation with the formula20,21:

(5)
Where:
ε = Effective strain

By substitution in Eq. 3 from equation 1 about the value of (ε) Eq. 5 becomes:

(6)

By multiplying both sides of Eq. 6 in constant value {λ/(β.Cos θ)} and rearrangement we get on:

(7)

From Eq. 3 and 6, it was confirmed that the peak width from crystallite size varies as 1/Cos θ strain varies as tan θ.

Fig. 4(a-c): (a) X-ray diffraction patterns of stannic antimonate at 0 radiation, (b) X-ray diffraction patterns of cobalt stannic antimonate at 0 radiation and (c) X-ray diffraction patterns of Strontium stannic antimonate at 0 radiation

Assuming that the particle size and strain contributions to line broadening are independent to each other and both have a Cauchy-like profile, the observed line breadth is simply the sum of Eq. 4 and 7:

(8)

By rearranging the above equation, we get:

(9)

The above equations are Williamson-Hall’s (W-H) equations.

Table 2: Crystallite size and lattice strain for stannic antimonate and doping stannic antimonate

Table 3: Effect of gamma radiation on capacity of SnSb and M-SnSb at 25±1°C

Figure 5: Plots of β cos θ against 4 sinθ for SnSb and dopping SnSb ion exchangers

By plots the relation between (4 Sin θ) along the x-axis and (β.Cos θ) along the y-axis as shown in Fig. 5 and from the linear fit of the data, the crystallite size was estimated from the y-intercept and the lattice strain (ε), from the slope of the fit was calculated and results represented in Table 2. The data in Table 2 indicated that the crystallite size of SnSb, CoSnSb and SrSnSb are 10.38×10–2, 16.13×10–2 and 16.32×102 nm, respectively, with the order SrSnSb>CoSnSb>SnSb.

From data in Table 2 crystallite size of cobalt stannic antimonate and strontium stannic antimonate are higher those of stannic antimonate that may be related to doping insitu precipitation of cobalt and strontium with stannic antimonite. Also Table 2 indicated that the strain in ion exchangers decreases as the crystallite size increased which is an unusual phenomenon22.

Effect of gamma radiation on capacity of SnSb and M-SnSb: The ion exchange capacities of original and irradiated samples of SnSb and M-SnSb for Cd2+ and Co2+ ions were studied and the results were tabulated in Table 3. Table 3 showed that the capacity values increased for Cd2+ and Co2+ ions with increasing the irradiation doses. This increasing may be attributed to the mobility of Cd2+ and Co2+ ions, which increased with increasing the irradiation dosses.


CONCLUSION
Stannic antimonate, cobalt or strontium stannic antimonates prepared by sol-gel technique with an empirical formulas (SnSb.O(1.59).3.34H2O), (CoSnSb.O(1.51).4.18H2O) or (SrSnSb.O(1.5).H2O) were prepared and subjected to gamma doses of 10, 50 and 100 kGy to study the radiation stabilities of these compounds. Crystallite size and lattice strain were evaluated by Scherrer’s formula and Williamson-Hall (W.H) using X-ray peak broadening analysis. The total capacity for Co2+ and Cd2+ ions were calculated for stannic antimonates, cobalt and strontium doped stannic antimonates and found that there were no practically significant changes between the control and irradiated samples, showing that these exchangers are stable up to the levels of irradiation under investigation.


SIGNIFICANCE STATEMENT
This study discovered new materials such as stannic antimonate and its dopants and its resistance to radiation doses upto 100 kGy. Also, the study show high capacity for Co2+ and Cd2+ ions.


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