Synthesis and Structure Determination of the Quaternary Zinc Nitride Halides Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)
The quaternary series Zn2NCl1−yBry and Zn2NBr1−yIy were synthesized from solid-liquid reactions between zinc nitride and the respective zinc halides in closed ampoules, and the evolution of their crystal structures was investigated by single-crystal and powder X-ray diffraction. Zn2NX1−yX′y (X, X′ = Cl, Br, I) adopts the anti-β-NaFeO2 motif in which each nitride ion is tetrahedrally coordinated by four zinc cations, and the halide anions are located in the voids of the skeleton formed by corner-sharing [NZn4] tetrahedra. While Zn2NCl1−yBry crystallizes in the acentric orthorhombic space group Pna21 (No. 33), isotypic to Zn2NX (X = Cl, Br), the structure of Zn2NBr1−yIy is a function of the iodide concentration, namely, Zn2NBr (Pna21) for low iodine content and Zn2NI (Pnma) for higher (y ≥ 0.38).
Symmetry relations in wurtzite nitrides and oxide nitrides and the curious case of Pmc21
Binary and multinary nitrides in a wurtzitic arrangement are very interesting semiconductor materials. The group–subgroup relationship between the different structural types is established.
Hygroscopic Expansion of some Casting Investments
CREDIT is generally given to Taggart1 for introducing the cast gold inlay to the dental profession. Although he realized that gold shrinks when cooled from molten state to solid state of room temperature, the investment available to him did not supply sufficient compensation. In 1910, Van Horn2 published a paper dealing with a method by which he obtained the compensation by means of wax expansion. The next major research in connection with this problem was the work of Coleman3 at the National Bureau of Standards. He determined the gold shrinkage to be 1.25 per cent and presented a casting technic with compensation values of quantitative nature. The total compensation for the gold shrinkage was obtained by the combination of the setting and thermal expansion of the mold. This procedure is the general practice followed at the present time for compensation. There are some disadvantages to this method. Skinner has indicated the difficulty of obtaining smooth castings and the improper compensation for the casting shrinkage.4 It has been found by Hollenback5 and Scheu6a that castings made at a high temperature are rougher than those made at a low temperature (450° C.), depending upon the great difference in thermal expansion between plaster of Paris and silica, which causes a poor union of the fine particles. This may also result in friability and there may be some warpage due to the differential expansion. A method which provides sufficient compensation at a low mold temperature is the hygroscopic casting technic.b Wilson7 showed that certain plasters expand as much as 0.0044 inch to the inch by taking up moisture from the air. With this information at hand, Scheula, b tested some commercial investment to determine what results the addition of moisture would have. He found6b: (1) All of the casting investments that were tested expanded. (2) The thicker the mix, the greater the expansion. (3) A mix with hot water expanded more than one with cold water. (4) The time at which the mix is placed in the water is of great importance. It was found that if the mix is placed in the water early, it would not expand so much as when placed in a little later. It was also found that if the mix was placed in the water after a certain time, it could not expand to the maximal amount. (5) The temperature of the water in which the mix is placed is important, for two reasons; (a) the temperature of the water controls slightly the expansion of the investment, and (b) water at a temperature of 1000 F. slightly softens the wax pattern so that the fine margins are not marred while expansion is taking place. The mix should remain in the water at least 20 minutes to obtain the full expansion, after which time no further expansion is obtained.