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Nucleation control in aggregation growth of strontium carbonate Microcrystals

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https://www.eduzhai.net American Journal of M aterials Science 2012, 2(5): 142-146 DOI: 10.5923/j.materials.20120205.02 Nucleation Controlled in the Aggregative Growth of Strontium Carbonate Microcrystals B. Sreedhar1, Ch. Satya Vani2, D. Keerthi Devi1, V. Sreeram3, M. V. Basaveswara Rao3,* 1Inorganic and Physical Chemistry Division, Indian Institute of Chemical Technology (Council of Scientific and Industrial Research), Hyderabad, 500607, Andhra Pradesh, India 2Department of Chemistry, SR International Institute of Technology, Rampally, Keesara (M ), RR District, 501301, Andhra Pradesh, India 3Department of Chemistry, Krishna University, M achilipatnam, 521001, Andhra Pradesh, India Abstract The in fluence of PABA(p-aminobenzoicacid) and HEEDTA (N-(2-hydro xyethyl) ethylenediamine- N, N, N- triacetic acid) on Strontionite crystals via simp le CO2 d iffusion route is described. The results showed that the experimental parameters have great influence on the shape evolution of products. The presence of templating species and varied pH are the key primary conditions for the g rowth morphology. Spike like crystals self assembled in the form o f flo wer like and cauliflower shaped cluster with high crystallin ity were identified. The crystals undergo an interesting morphology changes and have been characterized by X-ray d iffraction (XRD), Scanning Electron M icroscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR) techniques. Keywords Bio materials, Co mposite Materials, Crystal Gro wth, Electron Microscopy, p-amino Ben zoic Acid, N-(2hydro xyethyl) Ethylenediamine-N, N’, N’’- Triacet ic Acid 1. Introduction The ability to man ipulate the morphogenesis of materials through chemical synthesis is an important requirement of modern materials[1] chemistry, due to the fact that shape, dimension, and size of materials have great influence on their physico-chemical properties and their related applicat ions. Among the variety of mo rphologies, self-assembled structures have been extensively studied due to their potential applicat ions in various nanodevices[2,3]. However, only a few groups have examined synthetic methods that lead to assembled SrCO3 structures. Literature reports shows that, surfactants or templates, need to be disposed for obtaining pure sample[4,5]. Therefo re, it is still a challenge to develop simp le and reliable synthetic methods for the synthesis of self-assembled structures. St ront iu m carbonat e (SrCO3 ) is widely used start ing material o f strontium for preparing a variety of strontium compounds,[6-8]. This has two traditional main applicat ions. An additive in the production of glass for color television tubes and constituent of ferrite magnets[9,10]. In recent years, researchers have found add it ional app licat ions of SrCO3 in other fields. Zhang and co-workers[11] discovered nanosized SrCO3-based chemilu minescence sensor showing high select iv ity to eth ano l and n o response t o fo reign * Corresponding author: vbrmandava@yahoo.com (M.V.Basaveswara Rao) Published online at https://www.eduzhai.net Copyright © 2012 Scientific & Academic Publishing. All Rights Reserved substances, such as gasoline,ammonia and hydrogen. Sreedhar et al synthesized SrCO3 hierarchical structure by natural materials[12] and organic additives[13]. Different SrCO3 h ierarch ical structures, such as flower -like[14], bundle-like, du mbbell-like, hexagonal star-like[15, 16], branch-like[17], especially spherical or sphere-like[14-16, 18,] rods, wh iskers and ellipsoids,[19] fibers,[20] have been prepared using different methods, including reverse micelles,[21] solvothermal methods[22] liquid-liquid interfaces[23]. Though the methods are encouraging there is considerable scope for further study to improve the quality. SrCO3 microstructures, have attracted extraordinary attention due to their novel applications as sensors having chemilu menescence[24], catalyst[25, 26], co lor television tubes, chief constituent of ferrite magnets[27]. We are reporting the successful synthesis of SrCO3 structures of spike like and cauliflower shaped morphology, efficiently achieved by using two organic additives– PABA and HEEDTA with simple CO2 gas flo w d iffusion technique. 2. Experimental 2.1. Materials Para-aminobenzoicacid(C7H7O2N),N-(2hydro xyethyl) ethylenediamine-N ,NI, NII-tr iaceticac id (C10H18O7N2), Ammoniu m carbonate (NH4)2CO3, sodium hydro xide (NaOH) and strontium ch loride (SrCl2) were of analytical grade and used without further purificat ion. Double distilled water was used in all e xpe riments. 143 American Journal of M aterials Science 2012, 2(5): 142-146 2.2. Characterization X-ray diffraction measurements of the strontium carbonate hierarchial structures were recorded using a Rigaku diffracto meter (Cu rad iation, λ = 0.1546 n m) running at 40 kV and 40 mA (To kyo, Japan). FT-IR spectra of SrCO3 structures were recorded with a Thermo Nicolet Nexus (Washington, USA) 670 spectrophotometer. Crystals were collected on a round cover glass (1.2 cm), washed with deionized water and dried in a desiccator at room temperature. The cover g lass was then mounted on a SEM stub and coated with gold for SEM analysis. 2.3. Preparati on of SrCO3 Microcrystals A typical procedure for preparat ion of crystalline SrCO3 crystals was carried out as follows: In a g lass bottle 2.5 mmol SrCl2, 0.1mmol PA BA/HEEDTA were d issolved in 20 mL water and was stirred continuously to ensure complete solubility. Then the p H of the solution was adjusted to 7.0 and 10.0 by using 0.1M NaOH. A fter that the prepared solution was then covered with parafilm which was punched with three needle holes and placed in larger desiccator containing freshly crushed ammoniu m carbonate (20 g) at the bottom. After 24hr crystallizat ion, the parafilm was removed and the white precipitate deposited on the glass bottle centrifuged and washed thoroughly with distilled water, fo llo wed by ethanol and allowed to dry at room temperature fo r further crystallizat ion. Figure 1. SEM images of SrCO3 in the presence of PABA at varied pH conditions (a,b) pH 3.0, (c, d) pH 7.0, and (e, f) pH 10.0 Figure 2. SEM images of SrCO3 in the presence of HEEDTA at varied pH conditions (a, b) initial pH 3.0, (c, d) pH 7.0, and (e, f) pH 10.0 B. Sreedhar et al.: Nucleation Controlled in the A ggregative Growth of Strontium Carbonate M icrocrystals 144 3. Results and Discussion 3.1. Effect of Addi ti ves on the Morpholog y of SrCO3 Significant changes in the morphologies were observed when the pH of the reaction conditions varied between 7 and 10. Figure 1 and 2 shows the SEM images of SrCO3 structures by adding the additives PABA and HEEDTA at different pH conditions. In general SrCO3 dendrimers are obtained in the absence of additive[12], while in the presence of PABA at init ial p H 3.0, indiv idual spike like crystals were observed (Figure 1a, b). When the pH of the reaction mixtu re was increased to 7, the individual spikes aggregates to coniform like structures (Figure 1c, d). On further increasing the pH to 10.0, the spikes aggregates more closely and self assembled into flower like structures (Figure 1e, f). Figure 2a shows the SEM images of SrCO3 structures in the presence of the additive HEEDTA. Remarkab le changes in the morphology was observed with this addit ive and the shape of SrCO3 structures changed from dendrimeric to cauliflower bunch like structures with short spikes of subunits having smooth surface at in itial p H 3 (Figure 2 a, b). At neutral pH mixed phase of cau liflo wer bunches with rough surface and spadix shaped structures with fibre like units are identified (Figure 2c, d). At pH 10.0, mo rphology of the SrCO3 structures appears similar to that observed at pH 3 with rough surface (Figure 2 e, f). The strontianite crystals clearly aggregates into cauliflower bunch like and coniform structures in CO2 diffusion route. To the best of our knowledge, such close packed aggregates of strontionite crystals have not been observed in other bio mimet ic approaches to the growth of SrCO3 crystals. analyzed by FT-IR spectroscopy. The sharp peaks at 856, 703 cm-1 (Figure 5 a), 855, 701 cm-1 (Figure 5 b) and 857, 701 cm-1 (Figure 5 c) are in -plane and out-plane bending of CO32-. Figure 3. XRD pattern of SrCO3 in the presence of PABA (a) initial pH 3.0, (b) pH 7.0, and (c) pH 10.0 3.2. Structural Characterizati on of SrCO3 Microcrystals The XRD pattern of the isolated solids could be indexed to that orthorhombic structure of strontium carbonate and all the peaks are assigned by using JCPDS (05-418). The results implied that the aggregation did not alter the phase structure of SrCO3.To our expectation, the crystallinity nature of the product was sensitive to that pH conditions. At lower pH condition showed a greater crystallinity than the product prepared under higher pH condition, implying the influence of solution pH on the crystallinity. In Figure 3 the pattern of SrCO3 crystals obtained in aqueous solution displays the following diffraction peaks with (hkl) indices (110), (111), (021), (002), (121), (200), (130), (220), (040), (032), (041), (202), (132), (141) respectively. Similarly in figure 4, the diffraction peaks with (hkl) indices (110), (111), (021), (002), (121), (200), (112), (220), (032), (040), (132), and (113), of pure orthorhombic strontionite respectively. It may also be seen that the peak (111) is the strongest, suggesting that SrCO3 crystals obtained in aqueous solution grow main ly along with the (111) phase. Figure 4. XRD pattern of SrCO3 in the presence of HEEDTA (a) initial pH 3.0, (b) pH 7.0, and (c) pH 10.0 3.3. FTIR Studies To identify the growth mechanism and the effect of PA BA and HEEDTA on SrCO3 microstructures, the sample was Figure 5. FT-IR of SrCO3 microstructures nucleated (a) in the absence of an additive, (b) presence of PABA and (c) presence of HEEDTA 145 American Journal of M aterials Science 2012, 2(5): 142-146 The IR bands at 1476,1469 and 1465 cm-1 (Figure 5 a, b, c) correspond to the asymmetric stretching mode of C-O bond while the weak band at 1074 cm-1 (Figure 5 b, c ) is attributed to the symmetric C-O stretching vibration. The band at 3418 cm-1 (Figure 5 b) can be attributed to OH stretching vibration due to hydrogen bonding and or N-H stretch of the –NH2 group fro m the functional groups present in additives. The band at 3423 cm-1 (Figure 5 c) can be attributed to OH stretching vibration due to hydrogen bonding and or N-H stretch of the –NH2 group from the functional groups present in additive In comparison with Figures 5b, the C-O stretching vibration peak around 1465 cm-1 in Figure 5c, shifts to higher frequency by 4 cm-1 (1469 cm-1), suggesting that PABA and HEEDTA have different influence of SrCO3. This is probably due to the fact that the two organic mo lecules can adsorb onto the different planes of SrCO3 nuclei and influence the mode of crystal growth, resulting in litt le change of microstructure. 4. Conclusions In summary, un iform h ierarch ical SrCO3 co mp lex structures in the form of spike like and cauliflower bunch like units were efficiently obtained by a facile ammoniu m carbonate method in the presence of PABA and HEEDTA as additives. The present uniform hierarchical SrCO3 structures were self assembled by the related crystalline particles, assisted by the additives would enlarge the potential applications of strontium carbonate microstructures. This strategy may also be expected for the preparation of other meta l carbonates. REFERENCES [1] S. M ann., The Chemistry of Form, Angew. Chem. Int. Ed. 2000, 39(19), 3392-3406 [2] A.P. Alivisatos, Semiconductor Clusters, Nanocrystals & Quantum Dots,Science. 1996,271(5251), 933-37. [3] L.S.Zhong, J.S.Hu, H.P.Liang, A.M .Cao, W.G.Song, and L.J.Wan., 2006, Self-Assembled 3D Flower like Iron Oxide Nanostructures and Their Application in Water Treatment,Adv.M ater.18, 2426-2431. [4] T.K.Sau and C.J.M urphy., 2005, Self-Assembly Patterns Formed upon Solvent Evaporation of Aqueous Cet y lt rimet hy lammoniumBromid e-Coat ed Gold Nanop art icles of Various Shap es,Lan gmuir. 21(7),2923-2929. [5] H. C. Zeng and B. Liu., 2004, M esoscale Organization of CuO Nano ribbons:  Formation of “Dandelions, J. Am. Chem. Soc. 126(26), 8124-8125. [6] M . Akiyama, C. N. Xu, K. Nonaka and T. Watnabe., 1998, Intense visible light emission from Sr3Al2O6:Eu, Dy,Appl. Phys. Lett. 73, 3046-3049. [7] M . Akiyama, C. N. Xu, Y. Liu, K. Nonaka, and T. Watnabe., 2002, Influence of Eu, Dy Co-doped strontium aluminate composition on mechanoluminescence intensity, J.Lumin. 97(1), 13-18. [8] Z. L. Tang, F. Zhang, Z. T. Zhang, C. Y. Huang, and Y. H. Lin., 2000, Luminescent properties o SrAl2O4: Eu, Dy material prepared by the gel method, J.Eur. Ceram. Soc. 20, (12), 2129-2132. [9] J. M assone., 1983, Technology and uses of barium and strontium compounds. In Coope, M . B., Clarke, G.M ., Eds.; 5th Industrial M inerals Int. Cingr. (M adrid, Spain, 1982); M etal Bulletin: London, 115. [10] Roskill. 1989, The Economics of Strontium 1989, 5th ed.; Roskill Information Services: London, UK. [11] J. J. Shi, J. J. Li, Y. F. Zhu, F. Wei, and X. R. Zhang, 2002, Nanosized SrCO3-based chemiluminescence sensor for ethanol, Anal. Chim. Acta, 466(1), 69-78. [12] B. Sreedhar, Ch. Satyavani, D. Keerthi Devi, C. Rambabu, M . V. Basaveswara Rao, and M . Saratchandra Babu., 2011, Bioinspired Synthesis of M orphologically Controlled SrCO3 superstructures by natural gum acacia, Crystal Research Technology. 46(5), 485-492. [13] Ch.Satya vani, M . Sarat Chandra babu, K. Balakrishna, and C. Rambabu., 2010, Influence of Vitamin B3 on M orphosynthesis of CaCO3, BaCO3 and SrCO3 M icro and Nano Structures, Journal ofM etallurgy and M aterials Science, 52 (4) 351- 356. [14] M . G. M a, and Y. J. Zhu, 2007, A Simple Route to Synthesis of SrCO3 with Olive-Like and Flower-Like M orphologies, J. Nanosci. Nanotech. 7(12), 4552-4556. [15] J. Yu, H. Guo, and B. Cheng, 2006Shape evolution of SrCO3 particles in the presence of poly-(styrene-alt-maleic acid) J. Solid. State. Chem. 179, 800-803. [16] M . X. Zhang, J. C. Huo, Y. S. Yu, C. P. Cui, and Y. L. Lei, 2008, M orphology Control of SrCO3 Crystals using Complexons as M odifiers in the Ethanol-water mixtures, Chin. J. Struct. Chem. 27(10), 1223-1229 [17] M . G. M a, and Y. J. Zhu, 2008, M icrowave synthesis of SrCO3 one-dimensional nanostructures assembled from nanocrystals using ethylenediamine additive, M ater. Lett. 62, 2512-2515. [18] I. Sondi and E. M atijević, 2003, Homogeneous Precipitation by Enzyme-Catalyzed Reactions. 2. Strontium and Barium Carbonates , Chem. M ater. 15(6), 1322-1326. [19] M . H. Cao, X. L. Wu, X. Y. He, and C. W. Hu, 2005, M icroemulsion mediated solvothermal synthesis of SrCO3 nanostructures, Langmuir. 21(13), 6093–6096. [20] M . Balz, H. A.Therese, M . Kappl, L. Nasdala, W. Hofmeister, H. J. Butt, and W. Tremel., 2005, M orphosynthesis of strontianite nanowires using polyacrylate templates tethered onto self-assembled monolayers, Langmuir. 21(9), 3981–3986. [21] G. S. Guo, F. B. Gu, Z. H. Wang, H. Y. Guo., 2005, Low-temperature growth of single-crystal SrCO3 nano needles, Chin. Chem. Lett. 16(8), 1101–1104. [22] L. G. Shi, and F. L. Du., 2007, Solvothermal synthesis of SrCO3 hexahedral ellipsoids, M ater. Lett. 61(14-15), 3262–3264. B. Sreedhar et al.: Nucleation Controlled in the A ggregative Growth of Strontium Carbonate M icrocrystals 146 [23] S. Reddy, D. Rautaray, S. R. Sainkar, M . Sastry., 2003,M orphology of SrCO3 crystals grown at the interface between two immiscible liquids, Bull. M ater. Sci. 26 (3), 283–288. [24] J. J. Shi, J. J. Li, Y. F. Zhu, F. Wei, and X. R. Zhang, 2002, Nanosized SrCO3-based chemiluminescence sensor for ethanol, Anal. Chim. Acta. 466, 69-78. [25] K. Omata, N. Nukui, T. Hottai, Y. Showa, and M . Yamada, 2004, Strontium carbonate supported cobalt catalyst for dry reforming of methane under pressure, Catal. Commun. 5, 755-758. [26] L. Wang and Y. F. Zhu. 2005, Effects of Nanostructure on Catalytic Degradation of Ethanol on SrCO3 Catalysts, J. Phys.Chem. B 109(11), 5118-5123. [27] A. Roskill, The Economics of Strontium, 5th ed. (Roskill Information Services, London, UK, 1989).

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