25.01.2013 Views

Developments in Ceramic Materials Research

Developments in Ceramic Materials Research

Developments in Ceramic Materials Research

SHOW MORE
SHOW LESS

You also want an ePaper? Increase the reach of your titles

YUMPU automatically turns print PDFs into web optimized ePapers that Google loves.

Synthesis, Spectroscopic and Magnetic Studies… 127<br />

Figure 23. Thermal evolution of (a) the neutron diffraction patterns of Cr(PO 3) 3 and (b) the ordered<br />

magnetic moments [M, Mx and Mz] <strong>in</strong> Cr(PO3) 3.<br />

b<br />

The thermal dependence of the ordered magnetic moments is different from that observed<br />

<strong>in</strong> the Fe(PO3)3 phase where the overall magnetic moment M, over the whole range of<br />

temperatures studied, is always lower than the Mx ref<strong>in</strong>ed magnetic component although <strong>in</strong><br />

both phases the x direction is the ma<strong>in</strong> direction to propagate the exchange <strong>in</strong>teractions via<br />

(PO4) tetraedra.<br />

In this way, the presence of three different sites for the metallic ions <strong>in</strong> the structure is not<br />

relevant enough to give rise to local reorientations of the ordered moments and a weak<br />

ferromagnetic component is not observed <strong>in</strong> M(PO3)3 (M= Cr, Mo). In the Fe(PO3)3 phase,<br />

the competition of the magnetic <strong>in</strong>teractions due to the higher sp<strong>in</strong> number <strong>in</strong> Fe(III) (S= 5/2)<br />

than <strong>in</strong> Cr(III) (S= 3/2) and its magnetically isotropic behavior, together with the possible<br />

frustration between ions <strong>in</strong> the (100) layers, and the electronic configuration (d 5 ), are<br />

probably responsible for the presence of a weak ferromagnetic component as observed from<br />

magnetization measurements.<br />

7.1.2. B-Type Cr(PO3)3<br />

The magnetic peaks for Cr2(P6O18) observed at 1.8 K <strong>in</strong> the D2B neutron diffraction data<br />

were <strong>in</strong>dex<strong>in</strong>g us<strong>in</strong>g the nuclear cell. In the crystal structure, the magnetic atoms occupy one<br />

crystallographic site <strong>in</strong> a 4e general position of P21/a space group, numbered, 1a, 1b, 1c and<br />

1d. The best agreement between the observed and calculated diffraction patterns (see Figure<br />

24) is obta<strong>in</strong>ed when the magnetic moments lie <strong>in</strong> the (100) plane (Mx = 0). The ref<strong>in</strong>ed<br />

magnetic components are My = 1.6(2) μB and Mz = 1.63(7) μB, with a resultant magnetic<br />

moment of 2.3(1) μB per Cr(III) ion. In the f<strong>in</strong>al ref<strong>in</strong>ement, the nuclear and magnetic<br />

discrepancy factors of Cr2(P6O18) are Rp = 6.37, Rwp = 9.05, χ 2 = 3.92, RBragg = 10.7 and Rmag<br />

= 12.5. The value of 2.3(1) μB at 1.8 K is lower than that of the experimental Cr(III) ion (3.09

Hooray! Your file is uploaded and ready to be published.

Saved successfully!

Ooh no, something went wrong!