Ceramic Waste Forms Research Articles

Effect of neodymium on the glass formation, dissolution rate and crystallization kinetic of borophosphate glasses containing iron

Effect of neodymium on the glass formation, dissolution rate and crystallization kinetic of the borophosphate glass containing iron was investigated in detail. The results show that the solubility limit of Nd2O3 in the borophosphate glass is about 4 mol%. Partial crystallization occurs and monazite NdPO4 phase is detected in the glass containing 6 mol% Nd2O3. The density almost linearly increases with Nd2O3 content. The dissolution rates of the borophosphate glass are about 10−2 g m−2 d−1, indicating their stable structure and high aqueous chemical durability. This is consistent with the results of FTIR spectra and kinetic analysis, which show the strengthened glass structural network by incorporating Nd2O3. Moreover, the formation of NdPO4 phase induced by the excessively adding Nd2O3 does not degrade the chemical durability. The conclusions provide researchers with the role of Nd2O3 in borophosphate glasses and suggest a possibility of synthesizing glass ceramic waste forms by traditional melt-quenching method.

Titanium-doped iron phosphate based glass ceramic waste forms containing 50 wt% simulated nuclear waste

50 wt% of the simulated nuclear waste derived from the high level waste (HLW) in China is immobilized by using titanium-doped iron phosphate based glass ceramics. The effect of TiO2 content on the crystalline phases, structure and aqueous dissolution rate of the glass ceramic waste forms was investigated in detail. The results show that the crystalline phases of the obtained waste forms are monazite (Ce, La)PO4 accompanying with a small concentration of zirconium pyrophosphate ZrP2O7. The crystallization of ZrP2O7 phase is suppressed by adding TiO2 in the phosphate baseline glasses. Meanwhile, smaller grain size of the products is obtained. Moreover, the aqueous dissolution rates of the glass ceramic waste forms keep in the order of magnitude of 10−2 g m−2 d−1 after 14 leaching days, indicating their good chemical durability which are comparable to widely used borosilicate glasses and iron phosphate glasses/waste forms. The conclusions suggest that phosphate-based glass ceramics may potentially be an applicable matrix for the disposal of HLWs which are rich in actinide elements.

Synthesis and phase structure of (Cs0.8−xBa0.4+x)(Al3+1.6+ xTi4+6.4− x)O16 ceramics using sol-spray pyrolysis route for immobilizing radioactive cesium

In this paper, a sol-spray pyrolysis route was employed to fabricate (Cs, Ba)-hollandite ceramic waste forms. The high-phase purity (Cs0.8−xBa0.4+x)(Al1.6+xTi6.4−x)O16 (0 ≤ x ≤ 0.4) ceramics were synthesized at 1050 °C using the produced powders by sol-spray pyrolysis. The results show that all samples show tetragonal hollandite with rod morphology. Additionally, the sintered (Cs, Ba)-hollandite ceramics exhibit a good chemical durability. The normalized release rates of Cs and Ba were < 10−2 g m−2 d−1 after 14 days. These results indicate that hollandite ceramics are promising candidate for immobilizing radioactive cesium.

Thermodynamic assessment of the hollandite high‐level radioactive waste form

AbstractHollandite has been studied as a candidate ceramic waste form for the disposal of high‐level radioactive waste due to its inherent leach resistance and ability to immobilize alkaline‐earth metals such as Cs and Ba at defined lattice sites in the crystallographic structure. The chemical and structural complexity of hollandite‐type phases developed for high‐level waste immobilization limits the systematic experimental research that is required to understand phase development due to the large number of potential additives and compositional ranges that must be evaluated. Modeling the equilibrium behavior of the complex hollandite‐forming oxide waste system would aid in the design and processing of hollandite waste forms by predicting their thermodynamic stability. Thus, a BaO–Cs2O–TiO2–Cr2O3–Al2O3–Fe2O3–FeO–Ga2O3 thermodynamic database was developed in this work according to the CALPHAD methodology. The compound energy formalism was used to model solid solution phases such as hollandite while the two‐sublattice partially ionic liquid model characterized the oxide melt. Results of model optimizations are presented and discussed including a 1473 K isothermal BaO–Cs2O–TiO2 pseudo‐ternary diagram that extrapolates phase equilibrium behavior to regions not experimentally explored.

Simultaneous three‐dimensional elemental mapping of Hollandite and Pyrochlore material phases in ceramic waste form materials

AbstractDifferential X‐ray absorption contrast tomography was performed on model ceramic composite systems to image the 3D spatial distributions of Ga and Nd containing phases. The model material systems were fabricated such that they contained two constituent phases. Ga–doped Ba hollandite (Ba1.33Ga2.66Ti5.34O16), and pyrochlore (Nd2Ti2O7) which are under consideration as nuclear waste immobilization matrices. Two complementary techniques have been used to characterize the 3D distribution of phases. The analysis suggests that the 3D spatial distributions of hollandite and pyrochlore can be readily identified through the distributions Ga and Nd, respectively. These results represent a critical development towards characterizing the complex microstructure inherent to practical materials such as multiphase ceramic composite waste forms. Moreover, these methods can be applied to elucidate microstructural features that fundamentally determine the performance and properties of complex systems, which is central to the design of durable waste forms as well as many other real materials such fuel cells, batteries, ultra‐high temperature ceramics.

Phase formation at synthesis of murataite-crichtonite ceramics

Phase formation at synthesis of potential waste form for actinide immobilization was studied. Oxide mixture with composition (wt.%): 55 TiO2, 10 MnO, 10 CaO, 5 Al2O3, 5 Fe2O3, 5 ZrO2, and 10 Gd2О3 (trivalent actinide and neutron poison surrogate) was compacted under 200 MPa at room temperature and sintered for 1–6 h at temperatures from 1200 to 1350 °C. As follows from X-ray diffraction and electron microscopy studies, the ceramics obtained is composed of two structural varieties of murataite and crichtonite-type titanate. The results were compared to ceramic waste forms produced by melting and crystallization.

Glass structure and crystallization in boro-alumino-silicate glasses containing rare earth and transition metal cations: a US-UK collaborative program

ABSTRACTNuclear wastes generated from reprocessing of used nuclear fuel tend to contain a large fraction of rare earth (RE, e.g., Nd3+), transition (TM, e.g., Mo6+, Zr4+), alkali (A, e.g., Cs+), and alkaline earth cations (AE, e.g., Ba2+, Sr2+). Various strategies have been considered for immobilizing such waste streams, varying from nominally crystal-free glass to glass-ceramic to multi-phase ceramic waste forms. For glass and glass-ceramic waste forms, the added glass-forming system is generally alkali-alkaline earth-aluminoborosilicate (i.e., Na-Ca-Al-B-Si oxide). In a US-UK collaborative project, summarized here, we investigated the glass structure and crystallization dependence on compositional changes in simulated nuclear waste glasses and glass-ceramics. Compositions ranged in complexity from five – to – eight oxides. Specifically, the roles of Mo and rare earths are investigated, since a proposed glass-ceramic waste form contains crystalline phases such as powellite [(AE,A,RE)MoO4] and oxyapatite [(RE,AE,A)10Si6O26], and the precipitation of molybdenum phases is known to be affected by the rare earth concentration in the glass. Additionally, the effects of other chemical additions have been systematically investigated, including Zr, Ru, P, and Ti. A series of studies were also undertaken to ascertain the effect of the RE size on glass structure and on partitioning to crystal phases, investigating similarities and differences in glasses containing single RE oxides of Sc, Y, La, Ce, Nd, Sm, Er, Yb, or Lu. Finally, the effect of charge compensation was investigated by considering not only the commonly assessed peralkaline glass but also metaluminous and peraluminous compositions. Glass structure and crystallization studies were conducted by spectroscopic methods (i.e., Raman, X-ray absorption, nuclear magnetic resonance (NMR), optical absorption, photoluminescence, photoluminescence excitation, X-ray photoelectron spectroscopy), microscopy (i.e., scanning electron microscopy, transmission electron microscopy, electron probe microanalysis), scattering (i.e., X-ray and neutron diffraction, small angle measurements), and physical characterization (i.e., differential thermal analysis, liquidus, viscosity, density). This paper will give an overview of the research program and some example unpublished results on glass-ceramic crystallization kinetics, microstructure, and Raman spectra, as well as some examples of the effects of rare earths on the absorption, luminescence, and NMR spectra of starting glasses. The formal collaboration described here has resulted in the generation of a large number of results, some of which are still in the process of being published as separate studies.

Chemical evolution effects on phase and microstructure of [CsxBay][Ti3+2y+xTi4+8-2y-x]O16 ceramic waste forms for radioactive cesium immobilization

The effects of fission product transmutation on the structural stability of ceramic waste forms are a critical concern due to the changes of valence and ionic size, which can impair the stability of the host matrices. In this study, [CsxBay][Ti3+2y+xTi4+8-2y-x]O16 (0.3 ≤ x, y ≤ 0.75) ceramics were designed and successfully synthesized to immobilized 137Cs and its daughter product 137Ba. The evolution of phase and microstructure of the hollandite-ceramic waste forms were investigated by the substitution of Ba2+ into the Cs+ site and the incorporation of Ti3+ for charge compensation. The results show that the prepared hollandite ceramics exhibit excellent capacity to accommodate Cs+ and Ba2+ in its lattice while retaining a stable crystalline structure with a compact microstructure. Additionally, all elements of Cs, Ba, Ti and O homogeneously distributed in the sintered hollandite ceramics. These results further indicate that hollandite ceramics are a promising candidate for selective and durable immobilization of radioactive cesium.

Self-Propagating Synthesis and Characterization Studies of Gd-Bearing Hf-Zirconolite Ceramic Waste Forms.

Synroc is recognized as the second-generation waste matrice for nuclear waste disposal. Zirconolite is one of the most durable Synroc minerals. In this study, Gd and Hf were selected as the surrogates of trivalent and tetravalent actinide nuclides. Gd-bearing Hf-zirconolite (Ca1−xHf1−xGd2xTi2O7) ceramic waste forms were rapidly synthesized from a self-propagating technique using CuO as the oxidant. The results indicate that Gd can concurrently replace the Ca and Hf sites. However, Gd2O3 could not completely be incorporated into the lattice structure of zirconolite when the x value is higher than 0.8. The aqueous durability of selected Gd-Hf codoped sample (Hf-Gd-0.6) was tested, where the 42 days normalized leaching rates (LRi) of Ca, Cu, Gd and Hf are measured to be 1.57, 0.13, 4.72 × 10−7 and 1.59 × 10−8 g·m−2·d−1.

Compositional control of radionuclide retention in hollandite‐based ceramic waste forms for Cs‐immobilization

AbstractHollandite materials, as a class of crystalline nuclear waste forms, are promising candidates for the immobilization of radioactive elements, such as Cs, Ba, as well as a variety of lanthanide and transition‐metal fission products. In this study, three Ga‐doped titanate hollandite‐type phases, Ba1.33Ga2.67Ti5.33O16, Ba0.667Cs0.667Ga2Ti6O16, and Cs1.33Ga1.33Ti6.67O16, were synthesized using a solid‐state reaction route. All synthesized phases adopted a single phase tetragonal structure, as determined by powder X‐ray diffraction (XRD), and elemental analysis confirmed the measured stoichiometries were close to targeted compositions. Extended X‐ray absorption fine structure spectroscopy (EXAFS) was used to determine the local structural features for the framework of octahedrally coordinated cations. EXAFS data indicated that Cs1.33Ga1.33Ti6.67O16 possessed the most disordered local structure centered around the Ga dopant. The enthalpies of formation of all three hollandite phases measured using high‐temperature oxide melt solution calorimetry were found to be negative, indicating enthalpies of formation of these hollandites from oxides are thermodynamically stable with respect to their constituent oxides. Furthermore, the formation enthalpies were more negative and hence more favorable with increased Cs content. Finally, aqueous leaching tests revealed that high Cs content hollandite phases exhibited greater Cs retention as compared to low Cs content hollandite. While preliminary in nature, this work draws attention to the links between the capacity for radionuclide retention, atomistic level structural features and bulk thermodynamic properties of materials.

Synergistic effects of Ln and Fe Co-Doping on phase evolution of Ca1-xLnxZrTi2-xFexO7 (Ln = La, Nd, Gd, Ho, Yb) ceramics

Zirconolite (CaZrTi2O7) is one of the host ceramic waste forms for actinides immobilization. In this study, lanthanides were used as the surrogates for actinides and a series of solid solutions (Ca1-xLnxZrTi2-xFexO7; Ln = La, Nd, Gd, Ho, Yb) have been successfully fabricated to investigate the synergistic effects of Ln and Fe co-doping on phase evolution and solubility of Ln in zirconolite. Results show that zirconolite was found to co-exist with perovskite in the range 0.1 ≤ x ≤ 0.7 while zirconia, pseudobrookite, and perovskite become the major crystalline phases at 0.8 ≤ x ≤ 1.0 in the Ca1-xLaxZrTi2-xFexO7 ceramics. Both of zirconolite-2M and Zirconolite-3O were found in the Ca1-xNdxZrTi2-xFexO7 and Ca1-xGdxZrTi2-xFexO7 solid solutions. The phase transformation of zirconolite-2M to 3O occurs at x = 0.6 for Ca1-xNdxZrTi2-xFexO7 when this phenomenon happens at x = 0.9 for Ca1-xGdxZrTi2-xFexO7. The solubility of Ca1-xHoxZrTi2-xFexO7 to form single zirconolite-2M structure can be up to 0.9. Single zirconolite-2M was only detected within 0.1 ≤ x ≤ 0.6 in the Ca1-xYbxZrTi2-xFexO7 solid solutions. Lattice parameters of zirconolite-2M and zirconolite-3O were determined by Pawley refinement method. The lattice parameters of both zirconolite 2M and 3O gradually increase with increasing Nd and Fe contents in the Ca1-xNdxZrTi2-xFexO7 ceramics. For Ca1-xGdxZrTi2-xFexO7, the lattice parameter a has an increase with x increasing while b and c change slightly. For the Ho-Fe co-doped zirconolite-2M, the lattice parameter a shows an increasing trend, b and c demonstrate reverse trend when increasing Ho and Fe concentrations. Both b and c decrease with x increasing from 0.1 to 0.6 in the Ca1-xYbxZrTi2-xFexO7 while a has a slight change. The variation trends in the lattice parameters of zirconolite-2M phase in Ca1-xREExZrTi2-xFexO7 (REE = Nd, Gd, Ho, Yb) solid solutions are different, and such results may suggest different substitution mechanisms of lanthanide ions and Fe3+ in zirconolite.

Challenges in the Fabrication of Ceramic Technetium Waste Forms

ABSTRACTIn this research we can demonstrate, that fission technetium-99 can be successfully immobilized as tetravalent cation in solid state refractory oxides such as pyrochlores and perovskites. Pyrochlores show excellent performance in ASTM C1220-10 type corrosion testing and have the ability to structurally bond Tc-99 and therefore avoid the formation of highly-mobile, pertechnetate species under conditions of a generic repository. We have fabricated lanthanide technetium oxides using either dry-chemical ceramic processing, or wet-chemical coprecipitation methods. Tc pyrochlores have shown better Tc retention and corrosion resistance compared with Tc-containing LAWE4-type borosilicate glass, combined with 50-times higher waste loading. However, mechanical properties (fracture toughness, compressive strength) of the pyrochlores are lacking and the microstructure shows high open porosity of about 50 %. To improve these properties we tested a variety of measures such as hot-pressing or the combination of hot pressing and high-temperature synthesis, but the improvement was minor and Tc and the surrogate Ru were partly reduced. The presence of metallic inclusions has strong impact on Tc retention and release rates increased more than tenfold. We have further developed a wet-chemical coprecipitation synthesis route followed by calcination and a 4-days high-temperature sintering cycle for the model composition Sm2(Ru0.5Ti0.5)2O7 where titanium oxide was added as sintering agent. The ceramic surrogate waste forms showed improved theoretical densities of about 73 % combined with sufficient mechanical strength, while maintaining ruthenium in the tetravalent state.

Effects of ionic radius on phase evolution in Ln-Al co-doped Ca1-xLnxZrTi2-xAlxO7 (Ln = La, Nd, Gd, Ho, Yb) solid solutions

Zirconolite ceramic has been considered as a promising matrix to dispose high-level radioactive waste due to its excellent performance in immobilizing radionuclides. In this work, a series of zirconate solid solutions with stoichiometric Ca1-xLnxZrTi2-xAlxO7 (Ln = La, Nd, Gd, Ho, Yb; x = 0.1–1) were systematically studied to investigate the radius effect on their phase evolution. Powder X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive X-Ray spectrometry (SEM-EDX) were used to characterize the products. XRD and SEM results show that complete solid solutions of Ln and Al in zirconolite phase for Ca1-xLnxZrTi2-xAlxO7 cannot found. In the Ca1-xLaxZrTi2-xAlxO7 ceramics, single zirconolite phase cannot form, instead of multiple phases, such as zirconolite-2M, zirconia, perovskite and LaTi2Al9O19. In the Nd-Al co-doping ceramics, nearly single zirconolite-2M and zirconolite-3O were found at x ≤ 0.6 and 0.8 ≤ x ≤ 0.9, respectively. The miscibility gap between zirconolite-2M and 3O was found at x = 0.7. Single zirconolite-2M formed in the Gd-Al, Ho-Al and Yb-Al co-doped ceramics can only be detected in a compositional range of 0.1 ≤ x ≤ 0.8. Higher incorporation contents in these three series can form an additional phase cubic zirconia which is usually a ceramic waste form for radionuclides. Based on the XRD data, lattice parameters of zirconolite-2M and zirconolite-3O were calculated by Pawley refinement method. The evolution of lattice parameters of zirconolite-2M shows great difference between different lanthanide ions, indicating different substitution mechanisms in the Ln-Al co-doped zirconolite-2M.

Progress on Ongoing Waste form HIP projects at ANSTO

Abstract:Since the year 2000, Synroc has evolved from the titanate full-ceramic waste forms developed in the late 1970s to a hot isostatic pressing (HIP) technology platform that can be applied to produce glass, glass–ceramic, and ceramic waste forms and where there are distinct advantages over vitrification in terms of, for example, waste loading and suppressing volatile losses. This paper describes recent progress on waste form development for intermediate-level wastes from 99Mo production at ANSTO, spent nuclear fuel, fluoride pyroprocessing wastes and 129I. The microstructures and aqueous dissolution results are presented where applicable. This paper provides perspective on Synroc waste forms and recent process technology development in the nuclear waste management industry.

Atomistic scale investigation of cation ordering and phase stability in Cs-substituted Ba1.33Zn1.33Ti6.67O16, Ba1.33Ga2.66Ti5.67O16 and Ba1.33Al2.66Ti5.33O16 hollandite

The titanate-based hollandite structure is proposed as an effective ceramic waste form for Cs-immobilization. In this study, quantum-mechanical calculations were used to quantify the impact of A-site and B-site ordering on the structural stability of hollandite with compositions BaxCsy(MzTi8-z)O16, where M = Zn2+, Ga3+, and Al3+. The calculated enthalpy of formation agrees with experimental measurements of related hollandite phases from melt solution calorimetry. Ground state geometry optimizations show that, for intermediate compositions (e.g., CsBaGa6Ti18O48), the presence of both Cs and Ba in the A-site tunnels is not energetically favored. However, the decay heat generated during storage of the Cs-containing waste form may overcome the energetics of Ba and Cs mixing in the tunnel structure of hollandite. The ability of the hollandite structure to accommodate the radioparagenesis of Cs to Ba is critical for long term performance of the waste. For the first time, B-site ordering was observed along the tunnel direction ([001] zone axis) for the Ga-hollandite compositions, as well as the intermediate Al-hollandite composition. These compositionally dependent structural features, and associated formation enthalpies, are of importance to the stability and radiation damage tolerance of ceramic waste forms.

Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing

Melt processing of multi-phase ceramic waste forms offers potential advantages over traditional solid-state synthesis methods given both the prevalence of melters currently in use and the ability to reduce the possibility of airborne radionuclide contamination. In this work, multi-phase ceramics with a targeted hollandite composition of Ba1.0Cs0.3Cr1.0Al0.3Fe1.0Ti5.7O16 were fabricated by melt processing at 1675 °C and hot isostatic pressing (HIP) at 1250 and 1300 °C. X-ray diffraction analysis (XRD) confirmed hollandite as the major phase in all specimens. Zirconolite/pyrochlore peaks and weaker perovskite reflections were observed after melt processing, while HIP samples displayed prominent perovskite peaks and low-intensity zirconolite reflections. Melt processing produced specimens with large (>50 μm) well-defined hollandite grains, while HIP yielded samples with a more fine-grained morphology. Elemental analysis showed “islands” rich in Cs and Ti across the surface of the 1300 °C HIP sample, suggesting partial melting and partitioning of Cs into multiple phases. Photoemission data revealed multiple Cs 3d spin-orbit pairs for the HIP samples, with the lower binding energy doublets likely corresponding to Cs located in more leachable phases. Among all specimens examined, the melt-processed sample exhibited the lowest fractional release rates for Rb and Cs. However, the retention of Sr and Mo was greater in the HIP specimens.

Reactive spark plasma synthesis of CaZrTi2O7 zirconolite ceramics for plutonium disposition

Near single phase zirconolite ceramics, prototypically CaZrTi2O7, were fabricated by reactive spark plasma sintering (RSPS), from commercially available CaTiO3, ZrO2 and TiO2 reagents, after processing at 1200 °C for only 1 h. Ceramics were of theoretical density and formed with a controlled mean grain size of 1.9 ± 0.6 μm. The reducing conditions of RSPS afforded the presence of paramagnetic Ti3+, as demonstrated by EPR spectroscopy. Overall, this study demonstrates the potential for RSPS to be a disruptive technology for disposition of surplus separated plutonium stockpiles in ceramic wasteforms, given its inherent advantage of near net shape products and rapid throughput.

Phase Evolution of Sphene Based Ceramics during Annealing

CaO-TiO2-SiO2 (sphene) based ceramics has been prepared from a powder mixture (calcite, rutile and amorphous silica) using vibro-milling for homogenization and activation of the precursors. Sphene can be used for nuclear waste disposal. Although many approaches like multi-barrier, glass and ceramic waste forms are available for the nuclear waste disposal, the ceramic waste form is still attractive. In ceramics, because of its synthetic approach of immobilizing the radioactive waste, the radioactive nuclides are incorporated into solid solutions in an assemblage of synthetic mineralogical phase. Among various ceramic waste forms, synthetic rock (synroc) – sphene (CaTiSiO5) is currently receiving significant attention. The evolution of the phase composition during thermal treatment was investigated by thermal analyses and X-ray diffraction measurements. Also, morphology of was determined by scanning electron microscopy microscopy techniques.

Hot-isostatically pressed wasteforms for Magnox sludge immobilisation

Thermal treatment technologies offer many potential benefits for the treatment of radioactive wastes including the passivation of reactive species and significant waste volume reductions. This paper presents a study investigating the production of wasteforms using Hot-isostatic pressing technology for the immobilisation of Magnox sludges from the UK's Sellafield Site. Simulants considered physically representative of these sludges were used to determine possible processing parameters and to determine the phase assemblages and morphologies produced during processing. The study showed hot-isostatic pressing is capable of processing Magnox sludges at up to 60 wt% (oxide basis) into dense, mixed ceramic wasteforms. The wasteforms produced are a glass-bonded ceramic of mixed magnesium titanates, encapsulating localised grains of periclase. The ability to co-process Magnox sludges with SIXEP sand/clinoptilolite slurries has also been demonstrated. The importance of these results is presented through a comparison of volume reduction data, which shows HIPing may provide a 20-fold volume reduction over the current cementitious baseline and double the volume reduction attainable for vitrification technologies.

Transformation of Cs-IONSIV® into a ceramic wasteform by hot isostatic pressing

A simple method to directly convert Cs-exchanged IONSIV® IE-911 into a ceramic wasteform by hot isostatic pressing (1100 °C/190 MPa/2 hr) is presented. Two major Cs-containing phases, Cs2TiNb6O18 and Cs2ZrSi6O15, and a series of mixed oxides form. The microstructure and phase assemblage of the samples as a function of Cs content were examined using XRD, XRF, SEM and TEM/EDX. The chemical aqueous durability of the materials was investigated using the MCC-1 and PCT-B standard test methods. For HIPed Cs-IONSIV® samples, the MCC-1 normalised release rates of Cs were <1.57 × 10−1 g m−2 d−1 at 0–28 days, and <3.78 × 10−2 g m−2 d−1 for PCT-B at 7 days. The low rates are indicative of a safe long-term immobilisation matrix for Cs formed directly from spent IONSIV®. It was also demonstrated that the phase formation can be altered by adding Ti metal due to a controlled redox environment.