Hostname: page-component-cd9895bd7-mkpzs Total loading time: 0 Render date: 2024-12-25T01:59:36.306Z Has data issue: false hasContentIssue false
  • English
  • Français

A Study of Solid-Solution Formation in the Milling of TiCl3—AlCl3 Powder Mixtures

Published online by Cambridge University Press:  06 March 2019

Zigmond W. Wilchinsky  and
Ralph W. Looney
Zigmond W. Wilchinsky
Affiliation:
Esso Research and Engineering Company Linden, New Jersey
Ralph W. Looney
Affiliation:
Esso Research and Engineering Company Linden, New Jersey
Get access

Abstract

Solid solutions of AlCl3 and TiCl3 were formed in all proportions by milling together dry powders of AlCl3 and TiCl3 (delta crystalline modification). For each composition, X-ray diffraction showed a single phase having a high degree of layer stacking disorder. These materials, including milled AlCl3, were isomorphous with the so-called delta modification of TiCl3.

The presence of solid solutions was investigated primarily by lattice parameter measurements made with a diffractometer and carried out with the aid of internal standards. For the milled materials, lattice parameter changes were observed not only with changes of composition, but also with the crystallite size. In terms of the system of hexagonal axes used for α TiCl3, the a parameter for the milled samples decreased with decreasing crystallite size, whereas the c parameter increased. In the samples examined, this effect was about the same order of magnitude as that due to changes in composition. In order to evaluate the effects due to composition alone, a correction was made for the effect of crystallite size, and the lattice parameters were then expressed as the limiting values one would obtain for very large crystals.

With increasing AlCl3 content, the a parameter decreased from 6.168 Å for no AlCl3 to 6.162 Å for 20 mol.% AlCl3. For higher AlCl3 content, a showed a relatively rapid and almost linear decrease to 5.921 Å for 100% Aids. The c parameter decreased from 17.73 Å for no AlCl3 to about 17.61 Å for 35 mol.% AlCl3, and thereafter decreased slowly to 17.58 Å for 100% AlCl3. The layer stacking disorder appeared to increase the lattice parameters in solid solutions containing less than 25 mol,% AlCl3. However, at 25% and 100% AlCl3, no significant effect was observed.

Type
Research Article
Information
Advances in X-Ray Analysis , Volume 7: Twelfth Annual Conference on Applications of X-ray Analysis, August 7-9, 1963 , 1963 , pp. 203 - 208
Copyright
Copyright © International Centre for Diffraction Data 1963

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Tornqvist, E. and Langer, A. W. Jr., Catalyst preparation Process, U.S. Patent No. 3,032,513, May 1, 1962.Google Scholar
2. Tornqvist, E. and Langer, A. W. Jr., Polymerization Catalyst, U.S. Patent No. 3,032,510, May 1, 1962.Google Scholar
3. Natta, G., Corradim, P., and Allegra, G., “The Different Crystalline Modifications of TiCl3, a Catalyst Component of the Polymerization of α-Olefins,” J. Polymer Sci. 51: 399, 1961.Google Scholar
4. Natta, G., Chim. e ind. 42(11) : 1207, 1960.Google Scholar
5. Tornqvist, E. and Langer, A. W. Jr., Fr. Patent No. 1,284,987, January 8, 1962.Google Scholar
6. Klemm, W. and Krose, E., “Magnetochemical Investigations. XLIX. The Magnetic Behavior of Titanium Trihalides,” Z. anorg. Chem. 253: 218, 1947.Google Scholar
7. Swanson, H. E. and Tatge, E., Fel, J. C.. Reports, NBS, 1950.Google Scholar
8. American Society for the Testing of Materials, X-Ray Powder Data Card File, 1962.Google Scholar
9. Azaroff, L. V., and Buerger, M. J., The Powder Method in X-Ray Crystallography, McGraw-Hill Book Co., Inc., New York, 1958, Chapter 15.Google Scholar