MAPR2013 - Physical-chemistry of metals and ceramics

Chapter IV exercises - SOLUTIONS

Ex 1

a) You have to use the hard sphere model. Pure ZrO2 has the fluorite configuration,
which means that the Zr atoms are in a FCC lattice with O in all tetrahedral sites. The
atomic radius are 0.138nm for O and 0.084nm for Zr. The hard sphere model states
that in the compact direction of the crystal, the atoms (which are considered as spheres
with a fix radius) are in contact. Thus, you have to choose the compact direction and
use a bit of geometry in order to obtain :
√
a0 = 4 3/3(rO + rZr ) = 0.5127nm

Note that in this crystal the compact direction is the one linking a Zr at the cubic site to
a close O at a tetrahedral site (cf. slide 22). If you had hesitated between two directions,
just calculate the lattice parameter using both directions. The one in which you obtain
the biggest lattice parameter is the one you have to choose, that comes direclty from the
hard sphere assumption.
To calculate the density, you need to calculate the mass of one unit cell. A cell contains
4 atoms of Zr and 8 atoms of O, we find a mass of :
8 ∗ 16 + 4 ∗ 91.22
= 8.1846 · 10−22 g/cel
NAv

The volumetric mass density is ρ ≈ 6060[kg/m3 ].

The density is defined as ρx /ρwater which is about 6[-] in this case.

b) Here, you substitute 1/10 of ZrO2 by CaO. It means that you will have less oxygen
atoms than before in the calculation of the unit cell mass (we made the assumption that
the O−2 vacancy does not affect the size of the tetrahedral site). We then have :
√
a0 = 4 3/3(rO + rZr ∗ 0.9 + rCa ∗ 0.1) = 0.5192nm

(8 ∗ 0.9 + 4 ∗ 0.1) ∗ 16 + 4 ∗ 0.9 ∗ 91.22 + 4 ∗ 0.1 ∗ 40.08

= 7.7387 · 10−22 g/cell
NAv

And you find a density of ∼ 5.5 [-].

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Ex 2

To answer this, you have to remember the definition of spinels (slide 44 can be useful)
and check the number of unpaired electrons in each cation (slide 46 can be useful).
In normal spinel the 2 F e3+ occupy the octahedral sites and the M n2+ occupy the
tetrahedral sites, which leads to a total magnetization of :

Mtot = MOsites − MT sites = 2 ∗ MF e3+ − MM n2+ = 5[µB ]

In the inverse spinel, a F e3+ and the M n2+ occupy the octahedral sites and the second
F e3+ occupy the tetrahedral sites, which leads to a magnetization of :

Mtot = MOsites − MT sites = MF e3+ + MM n2+ − MF e3+ = 5[µB ]

One can see here that the magnetization is 5µB in both cases, so we cannot tell M nF e2 O4
compound is a normal or inverse spinel.

The addition of a fraction x of Zn2+ (with x ≤ 0.3) will have the following effect on
atom repartition :
• (1+x) F e3+ & (1-x) M n2+ in octahedral sites
• (1-x) F e3+ & x Zn2+ in tetrahedral sites
So, going from x = 0 to x = 0.3, we get a total magnetization going from 5µB to 6.5µB .

Ex 3

a) Each silicon atom is linked to four 21 O. So we can say that one Si brings two bridging
oxygen in the network. Similarly, we can say that each R atom introduced in the network
will result in one non-bridging oxygen. Indeed R will capture one half-oxygen atom which
becomes totally non-bridging (i.e. totally means from both its Si side and its R side).
We use the following equation to calculate the non-bridging oxygen fraction (be careful
with stoichiometry) :

# of NBO 5% · 2
= = 5.13% for an addition of 5% of R2 O
total # of O 95% · 2 + 5%

It leads to 10.5% and 16.2% for additions of 10% and 15% of R2 O, respectively.
b) You need at least three bridging O atoms per tetrahedron to have a connected network
(i.e. or maximum one non-bridging oxygen per tetrahedron). You then get a maximum
addition of :
x·2
= 0.25 → x = 22.22%
(1 − x) · 2 + x

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c) The addition of N aF will also open the structure. Indeed, the F − , which are mono-
valent, will substitute the O and thus open one apex (sommet) and N a+ will bind to
O atoms, and so will open another apex. Effect of F − is analog to effect of OH − , slide 55.

d)

# of NBO x% · 2
=
total # of O (100% − 5% − x%) · 2 + 5% · 3 + x% · 1

SiO2 - 5%Al2 O3 - x%R2 O NBO [%]

x=5 5
x = 10 10.3
x = 15 15.8
Connected network : maximum of 22.78% of R2 O.

Ex 4

Starting from the spinel stoechiometry (= Ba1/6 F e2 O3+1/6 ) to compare the two com-
pounds, we get 4/3F e3+ in octaheadral sites and 2/3F e3+ in tetrahedral sites (Ba2+
is not taken into account since it has no unpaired electron, 1s2 configuration). The
magnetization is 10/3µB , which is higher than the 3µB of CoF e2 O4 compound.

Mtot = MOsites − MT sites = 2/3 ∗ 2 ∗ MF e3+ − 1/3 ∗ 2 ∗ MF e3+ = 10/3[µB ]

Mtot = MOsites − MT sites = 1/2 ∗ 2 ∗ MF e3+ + 1 ∗ MCo2+ − 1/2 ∗ 2 ∗ MF e3+ = 3[µB ]

Ex 5

Since Li+ has no unpaired core electrons (1s2 configuration), the resulting magnetization
is only due to iron atoms. If they were in the same kind of site (normal spinel), their spins
would be added and the net magnetization would be ∼ 7.5µB . In order to obtain a mag-
netization of ∼ 2.6µB we have to consider the inverse spinel configuration which give than
0.5Li+ and 1.5F e3+ in octahedral sites and 1F e3+ in tetrahedral sites. Note you have to
rewrite the formula in order to have 2 iron atoms : Li0.5 F e2.5 O4 = Li0.5 F e0.5 F e2 O4 .
Normal : 2 ∗ 5 − 0.5 ∗ 5 = 7.5µB .
Inverse : 5 + 0.5 ∗ 5 − 5 = 2.5µB . Experimental uncertainties may occur in such mea-
surement.

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Ex 6 to 8

Use the same methodology as in previous exercises. Answers are :

• Ex6a : MgO is rocksalt structure (simple cubic structure, coordination 6), a =
0.424nm, d ≈ 3.51.
• Ex6b : a = 0.420nm, d ≈ 3.64.
• Ex7 : inverse.
• Ex8a : Mtot = 4µB (cf. slide 47); ex8b : Mtot = 4.6µB ; ex8c : Mtot = 7µB .

Ex 9

43.2 kg of talc ; 45 kg of kaolinite and 14.5 kg of alumina.