Hafnium, properties

Hafnium is a ductile metal with a brilliant silver luster. Its properties are considerably influenced by presence of zirconium impurities. Of all the elements, zirconium and hafnium are... 

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. 

Element 104, the first transactinide element, is expected to have chemical properties similar to those of hafnium. It would, for example, form a relatively volatile compound with chlorine (a tetrachloride). 

Study of the chemical properties of element 104 has confirmed that it is indeed homologous to hafnium as demanded by its position in the Periodic Table (20). Chemical studies have been made for element 105, showing some similarity to tantalum (25) no chemical studies have been made for elements 106—109. Such studies are very difficult because the longest-Hved isotope of 104 ( 104) has a half-Hfe of only about 1 min, of 105 ( 105) a half-Hfe of about 40 s, of 106 ( 106) a half-Hfe of about 1 s, and of elements 107—109 half-Hves in the range of milliseconds. 

Hafnium [7440-58-6] Hf, is in Group 4 (IVB) of the Periodic Table as are the lighter elements zirconium and titanium. Hafnium is a heavy gray-white metallic element never found free in nature. It is always found associated with the more plentiful zirconium. The two elements are almost identical in chemical behavior. This close similarity in chemical properties is related to the configuration of the valence electrons, and for zirconium and... 

Chemical Properties. Hafnium s normal stable valence is also its maximum valence of four. Hafnium exhibits coordination numbers of six. 

Most hafnium compounds have been of slight commercial interest aside from intermediates in the production of hafnium metal. However, hafnium oxide, hafnium carbide, and hafnium nitride are quite refractory and have received considerable study as the most refractory compounds of the Group 4 (IVB) elements. Physical properties of some of the hafnium compounds are shown in Table 4. 

Table 4. Physical Properties of Some Hafnium Compounds...

Hafnium tetrabromide [13777-22-5], HfBr, is very similar to the tetrachloride in both its physical and chemical properties. Hafnium tetraiodide [13777-23-6], Hfl, is produced by reaction of iodine with hafnium metal at 300°C or higher. At temperatures above 1200°C, the iodide dissociates to hafnium metal and iodine. These two reactions are the basis for the iodide-bar refining process. Hafnium iodide is reported to have three stable crystalline forms at 263—405°C (60). 

K. L. Komarek, ed.. Hafnium Physico-Chemical Properties of Its Compounds andEUhys, International Atomic Energy Agency, Vieima, 1981, pp. 11,13,14, 16. Covers tbermocbemical properties, phase diagrams, crystal stmcture, and density data on hafnium, hafnium compounds, and alloys. 

Zirconium and hafnium have very similar chemical properties, exhibit the same valences, and have similar ionic radii, ie, 0.074 mm for, 0.075 mm for (see Hafniumand hafnium compounds). Because of these similarities, their separation was difficult (37—40). Today, the separation of zirconium and hafnium by multistage counter-current Hquid—Hquid extraction is routine (41) (see Extraction, liquid—liquid). 

One must consider, too, the cost of the materials themselves. Some of the metals used in conventional nickel alloys - such as hafnium - are hideously expensive (at UK 100,000 tonne or US 150,000 tonne ) and extremely scarce and the use of greater and greater quantities of exotic materials in an attempt to improve the creep properties will drive the cost of blades up. But expensive though it is, the cost of the... 

The isolation and identification of 4 radioactive elements in minute amounts took place at the turn of the century, and in each case the insight provided by the periodic classification into the predicted chemical properties of these elements proved invaluable. Marie Curie identified polonium in 1898 and, later in the same year working with Pierre Curie, isolated radium. Actinium followed in 1899 (A. Debierne) and the heaviest noble gas, radon, in 1900 (F. E. Dorn). Details will be found in later chapters which also recount the discoveries made in the present century of protactinium (O. Hahn and Lise Meitner, 1917), hafnium (D. Coster and G. von Hevesey, 1923), rhenium (W. Noddack, Ida Tacke and O. Berg, 1925), technetium (C. Perrier and E. Segre, 1937), francium (Marguerite Percy, 1939) and promethium (J. A. Marinsky, L. E. Glendenin and C. D. Coryell, 1945). 

Table 21.1 summarizes a number of properties of these elements. The difficulties in attaining high purity has led to frequent revision of the estimates of several of these properties. Each element has a number of naturally occurring isotopes and, in the case of zirconium and hafnium, the least abundant of these is radioactive, though with a very long half-life ( Zr, 2.76%, 3.6 x 10 y Hf, 0.162%, 2.0 X 10 5 y). 

The effect of the lanthanide contraction on the metal and ionic radii of hafnium has already been mentioned. That these radii are virtually identical for zirconium and hafnium has the result that the ratio of their densities, like that of their atomic weights, is very close to Zr Hf = 1 2.0. Indeed, the densities, the transition temperatures and the neutron-absorbing abilities are the only common properties of these two elements which differ... 

The chemistry of hafnium has not received the same attention as that of titanium or zirconium, but it is clear that its behaviour follows that of zirconium very closely indeed with only minor differences in such properties as solubility and volatility being apparent in most of their compounds. The most important oxidation state in the chemistry of these elements is the group oxidation state of +4. This is too high to be ionic, but zirconium and hafnium, being larger, have oxides which are more basic than that of titanium and give rise to a more extensive and less-hydrolysed aqueous chemistry. In this oxidation state, particularly in the case of the dioxide and tetrachloride, titanium shows many similarities with tin which is of much the same size. A large... 

Generally, for the chemical engineer not particularly associated with atomic energy, unalloyed zirconium containing hafnium is an appropriate choice for those occasions which require the special corrosion resistant properties exhibited by the metal. 

Hafnium carbide (HfC) is an interstitial carbide which, with tantalum carbide, is the most refractory compound known. Its characteristics and properties are summarized in Table 9.4. 

In spite of its excellent properties, hafnium carbide has only limited industrial importance, possibly because of its high cost. Some experimental applications are as follows ... 

Hafnium nitride (HfN) is a refractory which is resistant to chemical attack. It is produced by CVD mostly on an experimental basis. Its properties and characteristics are summarized in Table 10.4. 

The low temperature ALD process for hafnium silicate films using HfCl2[N(SiMe3)2]2 and H2O was modified to improve the film properties by two different methods. With hydrogen peroxide, the silicon content in the film increased to Si/(Hf+Si)=0.2 at 2001 and the impurity levels decreased due to its strong oxidation effect. By introducing TBOS as an additional Si precursor, the silicon content in the film increased to Si/(Hf+Si)=0.5 at 200 °C and the hafiiium silicate films became fully oxidized with O/(Hf+Si)=2.0. 

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