Incorporation of iodine into apatite structure: a crystal chemistry approach using Artificial Neural Network
Materials with apatite crystal structure provide a great potential for incorporating the long-lived radioactive iodine isotope (129I) in the form of iodide (I-) from nuclear waste streams. Because of its durability and potentially high iodine content, the apatite waste form can reduce iodine release rate and minimize the waste volume. Crystal structure and composition of apatite was investigated for iodide incorporation into the channel of the structure using Artificial Neural Network. A total of 86 experimentally determined apatite crystal structures of different compositions were compiled from literature, and 46 of them were used to train the networks and 42 were used to test the performance of the trained networks. The results show that the performances of the networks are satisfactory for predictions of unit cell parameters a and c and channel size of the structure. The trained and tested networks were then used to predict unknown compositions of apatite that incorporates iodide. With a crystal chemistry consideration, chemical compositions that lead to matching the size of the structural channel to the size of iodide were then predicted to be able to incorporate iodide in the structural channel. The calculations suggest that combinations of A site cations of Ag+, K+, Sr2+, Pb2+, Ba2+, and Cs+, and X site cations, mostly formed tetrahedron, of Mn5+, As5+, Cr5+, V5+, Mo5+, Si4+, Ge4+, and Re7+ are possible apatite compositions that are able to incorporate iodide. The charge balance of different apatite compositions can be achieved by multiple substitutions at a single site or coupled substitutions at both A and X sites. The results give important clues for designing experiments to synthesize new apatite compositions and also provide a fundamental understanding how iodide is incorporated in the apatite structure. This understanding can provide important insights for apatite waste forms design by optimizing the chemical composition and synthesis procedure.
Dynamic recovery in silicate-apatite structures under irradiation and implications for long-term immobilization of actinides
The irradiation responses of Ca2La8(SiO4)6O2 and Sr2Nd8(SiO4)6O2 with the apatite structure are investigated to predict their long-term behaviour as host phases for immobilization of actinide elements from the nuclear fuel cycle. Different ions and energies are used to study the effects of dose, temperature, atomic displacement rate and ionization rate on irradiation-induced amorphization and recrystallization. The dose for amorphization increases with temperature in two stages, below and above 150 K. In the high temperature stage relevant to actinide immobilization, the increase of amorphization dose with temperature exhibits a strong dependence on the ratio of ionization rate to displacement rate for the different ions. Data analysis using a dynamic model for amorphization reveals that ionization-induced processes, with activation energy of 0.15 ± 0.02 eV, dominate dynamic recovery for ions from Ne through Xe. For heavier Au ions or for alpha-recoil nuclei emitted in alpha decay of actinides, ionization becomes less dominant and dynamic recovery is controlled primarily by thermally-driven processes. In post-irradiation annealing studies of amorphous samples, epitaxial thermal recrystallization is observed at 1123 K, and irradiation-enhanced nucleation of nanocrystallites is observed under irradiation with heavier ions. The recrystallization temperature under irradiation decreases with increasing ion mass to a value of ∼823 K, which also defines the thermally-driven critical temperature for amorphization under irradiation with heavy ions. Some partial recovery due to alpha particle irradiation at 300 K is observed that suggests a self-healing mechanism in apatite phases containing actinides. Based on the results and dynamic model, the temperature and time dependences of amorphization in silicate-apatite host phases for actinide immobilization are predicted.
Traceability strategy for gear-pitch-measuring instruments: development and calibration of a multiball artifact
There is a strong demand to ensure the traceability of gear-measuring instruments (GMIs). We propose a multiball artifact (MBA) for the evaluation of pitch-measuring accuracy. The aim of the MBA is to transfer the minimum uncertainty from a calibrated value at the National Metrology Institute of Japan (NMIJ) to a measured value of GMIs at a shop floor. The MBA is composed of equally spaced high-accuracy balls around an axis. The pitch-measuring accuracy of GMIs is evaluated by measuring the angular pitch deviation of the balls instead of the angular pitch deviation of a gear. We calibrated the angular pitch deviation using a coordinate measuring instrument (CMM) at the NMIJ and adapting a multiple-orientation technique. We proposed a calibration strategy of the angular pitch deviation. The calibration value of the pitch deviation for the MBA at the NMIJ was obtained with a measurement uncertainty (U95) of 0.2 µm. We evaluated the pitch-measuring accuracy of a GMI using the calibrated MBA. Each value of U95 for the cumulative and single pitch deviations for the left and right flanks was less than or equal to 0.5 µm. The small uncertainty was transferred from the NMIJ to the GMI.