Magnesium oxide cements

Douglas, W. H. (1978b). The metal oxide/eugenol cements. II. A diffuse reflectance spectrophotometric study of the setting of zinc oxide and magnesium oxide cements. Journal of Dental Research, 57, 805-9. 

The powder contains 2inc oxide and magnesium oxide (36), and the Hquid contains an aqueous solution of an acryHc polycarboxyHc acid. Water settable cements have been formulated by inclusion of the soHd polyacid in the powdered base component. The set cement mainly consists of partially reacted and unreacted 2inc oxides in an amorphous polycarboxylate matrix (27,28). 

Rock products - kiln Cement - dry Cement -wet Gypsum Alumina Lime Bauxite Magnesium oxide... 

Two methods are available for the preparation of the powder (Smith, 1969). In one, zinc oxide is ignited at 900 to 1000 °C for 12 to 24 hours until activity is reduced to the desired level. This oxide powder is yellow, presumably because zinc is in excess of that required for stoichiometry. Alternatively, a blend of zinc oxide and magnesium oxide in the ratio of 9 1 is heated for 8 to 12 hours to form a sintered mass. This mass is ground and reheated for another 8 to 12 hours. The powder is white. Altogether the powder is similar to that used in zinc phosphate cements. 

Most practical cements contain Mg " which is less strongly bound to the polyacrylate than Zn (Gregor, Luttinger Loebl, 1955a). Magnesium oxide forms a paste with PAA which sets to a plastic mass this is not hydrolytically stable, for when placed in water it swells and softens (Hornsby, 1977 Smith, 1982a). Moreover, if ZnO powder contains more than 10% MgO, the resultant cement deteriorates under oral conditions. 

As we have already shown, the presence of cations in orthophosphoric acid solution can have a decisive effect on cement formation. As noted above, Kingery (1950b) found it necessary to modify orthophosphoric add, by the addition of calcium, to obtain cement formation with calcium oxide. Also, Finch and Sharp (1989) had to modify orthophosphoric add, with either ammonium or aluminium, to achieve cement formation with magnesium oxide. 

Magnesium oxide is always blended with the zinc oxide prior to ignition. Magnesium oxide promotes densification of the zinc oxide, preserves its whiteness and renders the sintered powder easier to pulverize (Crowell, 1929). The sintered mixed oxide has been shown to contain zinc oxide and a solid solution of zinc oxide in magnesium oxide (Zhuravlev, Volfson Sheveleva, 1950). Specific surface area is reduced compared with that of pure zinc oxide and cements prepared from the mixed oxides are stronger (Crowell, 1929 Zhuravlev, Volfson Sheveleva, 1950). 

Magnesium (or magnesia) phosphate cements are based on the reaction between ignited magnesium oxide and acid phosphates, which are generally modified by the addition of ammonium and aluminium salts. The phosphates may be either in solution or blended in solid form with the magnesium oxide. In the latter form the cement is formed by mixing the powder blend with water. 

The most important characteristic of the magnesium oxide powder used in these cements is its reactivity (Glasson, 1963). Magnesium oxide needs to be calcined to reduce this, otherwise the cement pastes are too reactive to allow for placement. Surface area and crystal size are important and relate to the calcination temperature (Eubank, 1951 Harper, 1967 Sorrell Armstrong, 1976 Matkovic et ai, 1977). The lower reactivity of calcined magnesium oxide relates to a lower surface area and a larger crystallite size. 

Sugama Kukacka (1983b) described cements based on magnesium oxide and a 56% aqueous solution of ammonium polyphosphate (APP). The po wder was a fine magnesium oxide that had been calcined above 1300 °C and had a surface area of 1 to 5 m g . The reaction was strongly exothermic the cements set within 3 minutes and developed an early strength of 13-8 MPa after 1 hour and over 20 MPa after 5 hours. 

Figure 6.11 Scanning electron micrographs showing the microstructure of a cement formed from magnesium oxide and ammonium hydrogenphosphate solutions (Sugama Kukacka, 1983b).

Ando, Shinada Hiraoka (1974) examined cements formed by the reaction between magnesium oxide and concentrated aqueous solutions of aluminium dihydrogen phosphate. Later, Finch Sharp (1989) made a detailed examination of the cement-forming reaction and reported that the reaction yielded cements of moderate strength. 

Harper, F. C. (1967). Effect of calcination temperature on the properties of magnesium oxides for use in magnesium oxychloride cements. Journal of Applied Chemistry, 17, 5-10. 

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. 

The quality of magnesium oxychloride cements is highly dependent on the reactivity of the magnesium oxide used in their preparation. Typically, such oxides are prepared by calcination of the basic carbonate (Eubank, 1951 Harper, 1967), but their reactivity varies according to the conditions under which such calcination is carried out. As the reactivity alters so does the amount of oxide that can be incorporated into a cement relative to the amount of aqueous MgClj (Harper, 1967). 

Dead burned magnesium oxide is suitable as an expanding additive [368-370]. The expansion occurs by a hydration mechanism. The additive is particularly effective when used at setting temperatures greater than approximately 150° C. Enhanced adhesion of expanded cements can be achieved by the addition of urea-formaldehyde resins [1720]. 

Magnesia cement is largely composed of magnesium oxide (MgO). In practice, the MgO is mixed with fillers and rocks and an aqueous solution of magnesium chloride. This cement sets up (hardens) within 2-8 h and is employed for flooring in special circumstances. 

Similarly, basic magnesium chloride of indefinite composition is produced when magnesium hydroxide is mixed with magnesium chloride and water. The product is used as oxychloride cement (see Magnesium Oxide). 

METLCAP is a chemical cement that encapsulates, stabilizes, and solidifies hazardous heavy metals in solid form, in slurry form, or in solution. The cement is composed of magnesium oxychloride, which forms when magnesium chloride and magnesium oxide, with water, are mixed together with the metals. The hardened cement product is insoluble and itself becomes a usable resource as cement or as fill material. The METLCAP technology is applicable as an in sitn or ex situ treatment or for high-pressure injection grouting and construction of slnrry walls. Currently, the process is patented and commercially available from Stark Encapsulation, Inc. 

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