Hafnium absorption

Commercial-grade zirconium contains from 1 to 3% hafnium. Zirconium has a low absorption cross section for neutrons, and is therefore used for nuclear energy applications, such as for... 

Because the element not only has a good absorption cross section for thermal neutrons (almost 600 times that of zirconium), but also excellent mechanical properties and is extremely corrosion-resistant, hafnium is used for reactor control rods. Such rods are used in nuclear submarines. 

Analyses of alloys or ores for hafnium by plasma emission atomic absorption spectroscopy, optical emission spectroscopy (qv), mass spectrometry (qv), x-ray spectroscopy (see X-ray technology), and neutron activation are possible without prior separation of hafnium (19). Alternatively, the combined hafnium and zirconium content can be separated from the sample by fusing the sample with sodium hydroxide, separating silica if present, and precipitating with mandelic acid from a dilute hydrochloric acid solution (20). The precipitate is ignited to oxide which is analy2ed by x-ray or emission spectroscopy to determine the relative proportion of each oxide. 

Oxygen and nitrogen also are deterrnined by conductivity or chromatographic techniques following a hot vacuum extraction or inert-gas fusion of hafnium with a noble metal (25,26). Nitrogen also may be deterrnined by the Kjeldahl technique (19). Phosphoms is determined by phosphine evolution and flame-emission detection. Chloride is determined indirecdy by atomic absorption or x-ray spectroscopy, or at higher levels by a selective-ion electrode. Fluoride can be determined similarly (27,28). Uranium and U-235 have been determined by inductively coupled plasma mass spectroscopy (29). 

Hafnium neutron absorption capabilities have caused its alloys to be proposed as separator sheets to allow closer spacing of spent nuclear fuel rods in interim holding ponds. Hafnium is the preferred material of constmction for certain critical mass situations in spent fuel reprocessing plants where hafnium s excellent corrosion resistance to nitric acid is also important. 

Hafnium tetrafluoride [13709-52-9] is one component in the cladding layer of a proposed zirconium fluoride glass optical waveguide fiber composition which is expected to have a lower intrinsic light absorption than fused quart2 optical fiber (see Glass Fiber optics Fluorine compounds, inorganic-zirconium). 

Zirconium is often deterniined gravimetrically. The most common procedure utilizes mandelic acid (81) which is fairly specific for zirconium plus hafnium. Other precipitants, including nine inorganic and 42 organic reagents, are Hsted in Reference 82. Volumetric procedures for zirconium, which also include hafnium as zirconium, are limited to either EDTA titrations (83) or indirect procedures (84). X-ray fluorescence spectroscopy gives quantitative results for zirconium, without including hafnium, for concentrations from 0.1 to 50% (85). Atomic absorption determines zirconium in aluminum in the presence of hafnium at concentrations of 0.1—3% (86). 

Hafnium-free zirconium is particularly weU-suited for these appHcations because of its ductiHty, excellent oxidation resistance in pure water at 300°C, low thermal neutron absorption, and low susceptibiHty to radiation. Nuclear fuel cladding and reactor core stmctural components are the principal uses for zirconium metal. 

Cell constants, cesium and hafnium. .53, 55/ Cell coupled with absorption spectrophotometry, electrochemical... 

Hafnium may be measured by atomic absorption and emission spectroscopy, x-ray fluorescence, ICP-MS methods, and neutron activation. Such instrument methods are faster than wet methods and can measure the metal at trace levels. 

Hafnium dioxide is a high temperature refractory material. It is used for control rods in nuclear reactors. It has high stability and high thermal neutron absorption values. It also is used in special optical glasses and glazes. 

Use of hafnium instead of europium in atomic submarines for neutron absorption. 

A problem of obtaining zirconium with lowest possible contents of hafnium comes from construction requirements when using zirconium and its alloys in building nuclear reactors. The construction material must have good mechanical properties and must be resistant to corrosion in contact with heat carriers. Since reactor power is proportional to the quantity of neutrons, their absorption into construction materials should be as small as possible. Zirconium and its alloys are unique materials that satisfy these requirements. However, hafnium has approximately the same chemical characteristics as zirconium but it absorbs neutrons strongly. 

Because hafnium has a high absorption cross-section for thermal neutrons (almost 600 times that of zirconium), has excellent mechanical properties, and is extremely corrosion resistant, it is used to make the control rods of nuclear reactors. It is also applied in vacuum lines as a getter —a material that combines with and removes trace gases from vacuum tubes. Hafnium has been used as an alloying agent for iron, titanium, niobium, and other metals. Finely divided hafnium is pyrophoric and can ignite spontaneously in air. 

X-Ray Absorption Near-Edge Structure and Optical Properties of Hafnium Oxynitride Thin Films... 

The optical band gap of SI (4.3 eV) is larger than the simulated band gap (3.9 eV) of Hf02 (CN 7.0). The inherent error for the band gap calculation using DFT method is considered as reason about the difference (0.4 eV) between the optical band gap and the simulated band gap. However, the difference (1.7eV) between the optical (3.98 eV) and simulated band gap (2.28 eV) of S2 is larger than that of SI. Considering the difference (0.8 eV) between the optical band gap and the simulated band gap of the crystallized monoclinic hafnium oxide with the thickness of 900 nm, the transition rate for the optical absorption is suggested as another reason for the band gap difference of S2. 

The zirconium tetrachloride product must then be purified before reduction to metal. In particular, hafnium must be removed to less than 100 ppm Hf Zr because of the high neutron absorption cross-section it exhibits, and phosphorus and aluminum must be removed to even lower specifications due to their deleterious metallurgical impact on the final zirconium alloys. The tetrachloride product is first dissolved in water under carefully controlled conditions to produce an acidic ZrOCl2 solution. This solution is complexed with ammonium thiocyanate, and contacted with methyl isobutyl ketone (MIBK) solvent in a series of solvent extraction columns. Advantage is taken of the relative solubilities of Zr, Hf, and Fe thiocyanate complexes to accomplish a high degree of separation of hafnium and iron from the zirconium. 

Zirconium and hafnium react with hydrogen at temperatures above 700 °C, yielding an a-phase and hydrides with a limiting M H ratio of 1 2 (see Hydrides Solid State Transition Metal Complexes). Under hydrogen pressure, absorption... 

Zirconium hydroxide is precipitated by bases at lower pH than the hafnium compound. Zr and Hf are obviously unable to form true hydroxides, and these compounds are more correctly formulated as MO2 XH2O. Amorphous hydrous zirconia and hafhia (a-phase) transform to microcrystalline forms (/f-phase) with noticeable heat evolution. They lose water up to the composition MO2 H2O at 140 °C (Zr) or 155 °C (Hf). Hydrous zirconia has excellent absorptive capacity, particularly for oxygen-containing anions. For example, the concentration of S04 anions over hydrous zirconia is so low that no precipitate forms on the addition of barium salts to the filtrate. While the hydroxides of composition M(OH)4 are not stable, in alkaline solutions, M(OH)s are present and even M(0H)6 anions have been reported in very concentrated alkalis. Salts of these anions, such as Na2Hf(OH)6, can be isolated. 

Zirconium and hafnium have very similar chemical properties, invariably occur together in nature, and are difficult to separate. Yet their absorption cross sections for thermal neutrons are very different ... 

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