Preparation and Characterization of Sodium Zirconium Phosphate Powder with Peculiar Morphology

doi:10.15541/jim20130602

Abstract

Abstract:

Single-phase Na₂Zr(PO₄)₂powders were directly synthesized by hydrothermal method using ZrOCl₂•8H₂O and sodium polyphosphate as raw materials, water as solvent. The effects of hydrothermal conditions and calcination temperature on the microstructure of sodium zirconium phosphate powders were investigated systemically by SEM, XRD and TG-DSC, etc. It is found that, when the molar ratio of raw materials is 1:2 (n(ZrOCl₂•8H₂O): n(Na₅P₃O₁₀)) without adjusting pH value, slices being assembled coil-like Na₂Zr(PO₄)₂powders with good dispersion and uniform size can be obtained after 14 h hydrothermal treatment at 140℃. Appropriate extension of time and increase of temperature are beneficial to the powder formation. The higher the temperature, the shorter time the desired powders form. After calcination, Na₂Zr(PO₄)₂ powders decompose and their morphology are destroyed. The growth mechanism of the sodium zirconium phosphate powders being prepared by hydrothermal method is explained by a basic growth unit model.

Key words: Na2Zr(PO4)2, peculiar morphology, hydrothermal method, growth unit, calcination

CLC Number:

TQ126

CHEN Jun-Jun, WANG Jing, HUI Xiang. Preparation and Characterization of Sodium Zirconium Phosphate Powder with Peculiar Morphology[J]. Journal of Inorganic Materials, 2014, 29(8): 839-844.

Figures/Tables 11

Fig. 1 XRD patterns of products obtained at different molar ratio of raw materials

Fig. 2 SEM images of products obtained at different molar ratios of raw materials (a) 1:2.4; (b) 1:2.0; (c) 1:1.8; (d) 1:1.6. Insets are enlarged images of part area in related images

Table 1 pH value of the solution with different molar ratio of raw materials before and after hydrothermal treatment

Molar ratio	1:2.4	1:2.0	1:1.8	1:1.6	1:1.4	1:1.2
Initial pH value	7.24	7.00	6.72	6.57	6.43	6.06
Final pH value	5.72	5.66	5.58	5.49	5.38	5.32

Fig. 3 SEM images of products obtained at different pH values (a) pH=8.0; (b) pH=6.0. Insets are enlarged images of part area in related images

Fig. 4 XRD patterns of products obtained at different temperatures

Fig. 5 SEM images of products obtained at different hydrothermal temperatures (a)100℃; (b)120℃; (c) 140℃; (d)160℃; (e)180℃; (f)200℃. Insets are enlarged images of part area in related images

Fig. 6 XRD patterns of products obtained under different hydrothermal time at 140℃

Fig. 7 SEM images of products obtained under different hydrothermal time (a) 4 h; (b) 6 h; (c) 8 h; (d) 10 h; (e)12 h; (f) 14 h. Insets are enlarged images of part area in related images

Fig. 8 TG-DSC curve of the product

Fig. 9 XRD patterns of the products calcined at 600℃ (a) and 900℃ (b)

Fig. 10 Morphologies of the products calcined at different 600℃ (a) and 900℃(b) Insets are enlarged images of part area in related images

References 18

[1]	PET'KOV V I. Complex phosphates formed by metal cations in oxidation states Ⅰ and Ⅳ. Russian Chemical Reviews, 2012, 81(1): 606-637.
[2]	ZHANG BIAO, GUO JING-KUN, HUANG XIAO-XIAN, et al. Properties of [NZP] structure-functional materials. Journal of Inorganic Materials, 1996, 11(1): 14-19.
[3]	SCHEETZ B E, AGRAWAL D K, BREVAL E, et al. Sodium zirconium phosphate(NZP) as a host structure for nuclear waste immobilization: a review. Waste Management, 1994, 14(6): 489-505.
[4]	BURDA C, CHEN X, NARAYANAN R, et al. Chemistry and properties of nanocrystals of different shapes. Chemical Reviews, 2005, 105(4): 1025-1102.
[5]	ZHANG Q, LIU S J, YU S H. Recent advances in oriented attachment growth and synthesis of functional materials: concept, evidence mechanism, and future. Journal of Material Chemistry, 2009, 19(1): 191-207.
[6]	PET'KOV V I, ASABINA E A. Complex phosphates, containing elements with oxidation degree +1 and +4. Physics Procedia, 2013, 44: 166-176.
[7]	ZHU LIN-HUA, LIAO XUE-PIN, LANG XIAO-CHUAN, et al. Synthesis of Ca1-xBaxZr4(PO4)6 phosphate ceramic and its thermal shock resistance performance of near-zero thermal expansion composition. Journal of Inorganic Materials, 2001, 16(3): 452-458.
[8]	YIN Z, SAKAMOTO Y, YU J, et al. Microemulsion based synthesis of titanium phosphate nanotubes via amine extraction system. Journal of the American Chemical Society, 2004, 126(29):8882-8883
[9]	LI Y H, LING Y H, BAI X D. Preparation and characterization of anisotropic ammonium titanium phosphate crystals via hydrothermal route. Key Engineering Materials, 2005, 280-283: 597-600.
[10]	PAVLOVA S N, SADYKOV V A, ZABOLOTNAYA G V, et al. The influence of solid precursors nature on structural, textural and surface properties of framework zirconium phosphates synthesized via mechanochemical activation. Solid State Ionics, 2001, 141-142: 683-688.
[11]	ZHANG XUE-HUA, LUO HAO-SU, ZHONG WEI-ZHUO. Anionic corrdination polyhedron growth units mode and its application in crystal growth. Science in China Series E, 2004, 34(3): 241-253.
[12]	PENN R L, BANFIELD J F. Morphology development and crystal growth in nanocrystalline aggregates under hydrothermal conditions: insights from titania. Geochimica et Cosmochimica Acta, 1999, 63(10): 1549-1557.
[13]	ECHEVERRÍA J, ALVAREZ S. Application of symmetry operation measures in structure inorganic chemistry. Inorganic Chemistry, 2008, 47(23): 10965-10970.
[14]	NAI J, WU J, GUO L, et al. Coordination polyhedra: a probable basic growth unit in solution for the crystal growth of inorganic nonmetallic nanomaterials?Crystal Growth Design, 2012, 12(5): 2653-2661.
[15]	AMBARISH D, AMIT D G, DEBRATA B, et al. A comparative study of conventionally sintered, microwave sintered and hot isostatic press sintered NZP and CZP structures interacted with fluoride. Ceramics International, 2013, 39(8): 9351-9359.
[16]	ORDÓÑEZ-REGIL E, CONTRERAS-RAMÍREZ A, FERNÁNDEZ- VALVERDE S M, et al. Crystal growth and thermoluminescence response of NaZr2(PO4)3 at high gamma radiation doses. Journal of Nuclear Materials, 2013, 443(1/2/3): 417-423.
[17]	GEORGE A, SEENA P T. Thermal studies on zirconium hydroxide gel formed by aqueous gelation. Journal of Thermal Analysis and Calorimetry, 2012, 110(3): 1037-1041.
[18]	BANFIELD J F, WELCH S A, ZHANG H, et al. Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products. Science, 2000, 289(5480): 751-754.