Preparation and magnetic properties of rare earth garnets and apatites

Author

Rostam Mondegarian, New Jersey Institute of Technology

Document Type

Dissertation

Date of Award

Spring 5-31-1976

Degree Name

Doctor of Engineering Science in Chemical Engineering

Department

Chemical Engineering and Chemistry

First Advisor

Lawrence Suchow

Second Advisor

Howard S. Kimmel

Third Advisor

Donald G. Lambert

Fourth Advisor

Ching-Rong Huang

Fifth Advisor

R. E. McMillan

Abstract

It has been found possible to prepare garnets with magnetic trivalent rare earth ions filling all or most dodecahedral sites while nonmagnetic Sc³⁺ ions fill all octahedral sites and magnetic Fe³⁺ ions fill all or most tetrahedral sites. Phase-pure garnets found include {RE_3-ySc_y}[Sc₂](Fe₃)O₁₂, where RE is Sm, Eu, Gd, Tb or Dy and y can be zero with Sm and Eu; {Nd₃}[Sc₂](Fe_zGa_3-z)O₁₂; and other Nd-Sc-Fe garnets of the type {Nd_3-(w+y)M_wS_cy}[Sc₂](Fe₃)O₁₂, where M is Gd, Y, and Lu.

Compositions chosen for magnetic studies were those with maximum allowable concentrations of magnetic ions on the dodecahedral and tetrahedral sites. In each case, dependence of magnetization on temperature was measured between room temperature and that of liquid helium. Measurements were also made at liquid helium temperature of the dependence of magnetization on applied field with values up to 60 k0e. Ordering ascribed to ferrimagnetism and perhaps also antiferromagentism has been observed. Saturation has not been obtained with the maximum field applied, apparently because of canting of magnetic ion moments when the octahedral sites contain only diamagnetic ions.

Calculations of structure factors have confirmed the structural formulae {Nd_2.7Yb_0.3}[Yb₂](Ga₃)O₁₂ and Pr₃ [Lu₂] (Ga₃)O₁₂; that is, rare earths fill all dodecahedral and octahedral sites.

Oxyapatites are typified by Ca₄La(PO₄)₃O and Ca Y₄(SiO₄)₃O (or A₅B₃O₁₃) and Ca₅(PO₄)₃O_0.5[]_0.5 (or A₅B₃O_12.5), where [] represents a vacancy. Such oxyapatites have in each formula unit as written here three A cations with one type of coordination and the other two another type, three tetrahedral B cations, and 13 or 12.5 oxide ions. These ionic ratios (3:2:3:13-12.5) are therefore very close to those found in garnets (3:2:3:12). Attempts were made to prepare rare earth-iron apatites in order to seek magnetic interactions like those in garnets, but apatites did not form.

Recommended Citation

Mondegarian, Rostam, "Preparation and magnetic properties of rare earth garnets and apatites" (1976). Dissertations. 1306.
https://digitalcommons.njit.edu/dissertations/1306