Na SHC Meeting Korea April 2016 Progress Report

Na. SHC Meeting Korea April 2016 Progress Report Dr Alistair Holdsworth

Background Project Plan • Synthesis and characterisation • Process optimisation and scaleup • Testing and verification • Performance analysis with daughter nuclei • Preparation of composites • Performance analysis of composites • Disposal • Recyclability • Vitrification and stability

Background Project Plan • Synthesis and characterisation • Process optimisation and scaleup • Testing and verification • Performance analysis with daughter nuclei • Preparation of composites • Performance analysis of composites • Disposal • Recyclability • Vitrification and stability

Background Metal Phosphates • AMPO 4, AMP 2 O 7 and A 2 M(PO 4)2 • A = NH 4, K, M = divalent, trivalent or tetravalent metal respectively • Selectivity • Similar systems demonstrate selectivity for Cs and Sr 1 -4 • Plate-like or mesoporous structures • Capacity • Theoretical capacities up to near parity (970 mg/g Cs) • Cost • Inexpensive commodity precursors • Ease of Preparation • Facile one-step synthesis, quantitative yield • Stability • Insoluble • Readily vitrified into a glassy form • Novelity • Received very little attention to date References 1) E. H. Borai et al, IAEA Report, 2008 2) L. Campao, Ph. D Thesis, 2003 3) N. P Dikiy, NSC, Ukraine, 2015 4) V. A. Burnell, Ph. D Thesis, 2011

Background Continuous Flow Synthesis • Advantages over batch: • Reproducibility • Batch to batch variation • High throughput capable • Short reaction time • Very adaptable (engineering) • Modularity • Supports a wide range of chemistries • Scalable (mg to kg in lab) • Material properties tunable • Particle size, crystallinity, phase, etc. • Rapid and scalable preparation of nanomaterials

Hydroxyapatite Ca 5(PO 4)3 OH XRD SEM

Calcium H-Phosphate (Brushite) – Ca. HPO 4 XRD SEM

Magnesium H-Phosphate Mg. HPO 4 XRD SEM

Tin (II) H-Phosphate Sn. HPO 4 XRD SEM

Cancrinite Na 6 Al 6 Si 6 O 24. Na. OH XRD SEM

Ammonium Mn Phosphate NH 4 Mn. PO 4 XRD SEM

Ammonium Fe Phosphate NH 4 Fe. PO 4 XRD SEM

Ammonium Co Phosphate NH 4 Co. PO 4 XRD SEM

Ammonium Ni Phosphate NH 4 Ni. PO 4 XRD SEM

Ammonium Zn Phosphate NH 4 Zn. PO 4 XRD SEM

Ion Exchange Testing • Ion exchange screening done using 0. 25 g of each compound in 25 ml of Cs, Sr or both in solution: • 4 ppm Cs, 2. 7 ppm Sr • Shaken overnight, allowed to settle. • Cs and Sr uptake analysed using ICP-MS. Formula Cs p. H Sr p. H Cs* Sr* p. H Mg. HPO 4 37. 9 6. 3 61. 1 7. 5 58. 9 60. 2 7. 5 Ca. HPO 4 0. 0 7. 2 50. 4 6. 0 15. 6 70. 5 5. 9 Sn. HPO 4 56. 3 5. 1 61. 5 5. 2 63. 6 63. 1 5. 5 HA 0. 0 6. 8 88. 0 6. 5 0. 9 85. 4 6. 4 Zeolite 98. 8 9. 2 99. 9 8. 6 98. 5 99. 9 8. 8 NH 4 Mn. PO 4 20. 1 6. 2 54. 6 6. 6 45. 5 57. 0 6. 5 NH 4 Fe. PO 4 86. 8 6. 6 99. 5 6. 8 90. 8 99. 5 6. 9 NH 4 Co. PO 4 58. 8 7. 7 84. 2 8. 1 65. 0 83. 7 7. 8 NH 4 Ni. PO 4 84. 3 7. 0 98. 6 6. 8 86. 4 98. 4 6. 9 NH 4 Zn. PO 4 63. 0 8. 0 99. 8 7. 8 67. 2 99. 7 7. 9 Key: Cs and Sr values are % of total solution content absorbed.

Ongoing and Future Work • Synthesis of and characterisation of remaining AMPO 4 • A = K, M = Mg, Ca, Ti. O, Cu, Sn • Screening of the above • Adsorption of Cs and Sr (and others) in small-scale batch (0. 5 g in 50 ml) • Preparation and testing of composites in PAN • Investigation of other systems • Phosphates • Hydroxyapatite (Sr removal) • Etc.