Oxysalt cements

By contrast, the acidity of the metal salts used in these cements has a less clear origin. All of the salts dissolve quite readily in water and give rise to free ions, of which the metal ions are acids in the Lewis sense. These ions form donor-acceptor complexes with a variety of other molecules, including water, so that the species which exists in aqueous solution is a well-characterized hexaquo ion, either Mg(OH2)g or Zn(OH2)g. However, zinc chloride at least has a ternary rather than binary relationship with water and quite readily forms mixtures of Zn0-HCl-H20 (Sorrell, 1977). Hence it is quite probable that in aqueous solution the metal salts involved in forming oxysalt cements dissolve to generate a certain amount of mineral acid, which means that these aqueous solutions function as acids in the Bronsted-Lowry sense. 

Oxychloride cements have several phases, the main one being an oxysalt. Single-phase oxysalts are very insoluble in water and, hence, are suitable for outdoor applications such as structural materials. In practice, however, synthesizing single-phase materials has been difficult. Chlorides and sulfates are also produced as secondary phases, making these cements leachable in water. For this reason, their use has been limited. That does not, however, imply that their potential is limited. If some niche application of these materials is found as in the case of phosphate bonded ceramics, chances are that several other oxysalt cements may be discovered the same way as phosphate bonded ceramics described in this book. 

The Lewis definition covers all AB cements, including the metal oxide/metal oxysalt systems, because the theory recognizes bare cations as aprotic acids. It is also particularly appropriate to the chelate cements, where it is more natural to regard the product of the reaction as a coordination complex rather than a salt. Its disadvantages are that the definition is really too broad and that despite this it accommodates protonic acids only with difficulty. 

Oxysalt bonded cements are formed by acid-base reactions between a metal oxide in powdered solid form and aqueous solutions of metal chloride or sulphate. These reactions typically give rise to non-homo-geneous materials containing a number of phases, some of which are crystalline and have been well-characterized by the technique of X-ray diffraction. The structures of the components of these cements and the phase relationships which exist between them are complex. However, as will be described in the succeeding parts of this chapter, in many cases there is enough knowledge about these cements to enable their properties and limitations to be generally understood. 

The three major types of oxysalt bonded AB cement are the zinc oxychloride, the magnesium chloride and the magnesium oxysulphate cements. The bases employed, therefore, are either zinc oxide or magnesium oxide, both of which readily undergo hydration in aqueous solution, behaving as M(OH)2 species and acting as a source of hydroxyl ions. They are thus both clearly bases in the Bronsted-Lowry sense. 

These cements were the earliest of the oxysalt bonded cements to be prepared (Sorel, 1855) and their chemistry has been the subject of numerous investigations over the years. There are considerable difficulties associated with such investigations. Not only does the cement contain a complex mixture of different crystalline precipitates but it is unaffected by boiling water and dissolves only slowly in strong acids. Consequently separation or analysis of any of the phases which may be present is difficult. Nonetheless, as early as 1925 at least 17 crystalline compounds were claimed to occur in the zinc oxychloride cement (Mellor, 1925). 

Much of the initial development in CBCs occurred because of search for suitable dental cements. Wilson and Nicholson [8] have an excellent review of acid-base cements in their book with the same title. They discuss the following three types polyalkenoate, oxysalt, and phosphate bonded cements. 

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