CHEM 455

Chemical Nanotechnology

Problem Set #2

(1) Unlike fluorides, metal oxides (MO2) with the fluorite structure only exhibit
anion conductivity at high temperatures (> 2000 °C). Suggest a reason for this.

(2) How would you expect the formation of color centers to affect the density of the
crystal, and why?

(3) Explain why crystalline solids are generally more defective as a result of
increasing the temperature.

(4)

Shown above is a TiO2 plane for a very poor sample of SrTiO3 (red = O2–; blue =
Ti4+). In the figure above label all of the defects present. You should find the
following: cation vacancy, Schottky defect, Frenkel defect, cation interstitial,
substitutional impurity, and anion vacancy. Note: Frenkel and Schottky defects
involve more than 1 point defect in close proximity to each other, while other point
defects can be isolated.
(a) Of these types of defects, which will alter the stoichiometry of the SrTiO3?
(b) Titanium has stable Ti2+, Ti3+, and Ti4+ oxidation states. Given this, it is
possible for SrTiO3 to be nonstoichiometric but remain electrically neutral
without the presence of an impurity other than Sr, Ti, or O? Explain.
(c) Suppose that gadolinium is doped into a sample of SrTiO3. Assuming that
it substitutes onto a Sr lattice position, what are the possible types of point
defects that could result?

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(5) Pb-Sn is an important binary alloy used for solders. Its phase diagram is given
below:

I. At 183 °C, at the point labeled A in the phase diagram:

(a) What phases are present?
(b) What is (are) the composition of the phase(s)?
(c) What is the relative amount of each phase present, in mass fraction?
(d) How many degrees of freedom are present at this point in the phase
diagram?

II. Now the temperature is lowered to 182 °C, at the point labeled B in the phase
diagram:
(e) What is the composition of each phase?
(f) What is the relative amount of each phase present, in mass fraction?
(g) How many degrees of freedom are present at this point in the phase
diagram?

III. The 𝛼 phase can be divided into two parts. The 𝛼 phase identified in Part I of
this problem does not change in any way as the temperature is lowered past the
eutectic line, and it is termed the proeutectic 𝛼. As the temperature decreases, the
liquid phase at the eutectic temperature solidifies into a structure consisting of
alternating layers of the 𝛼 and β phases. The 𝛼 phase found in this structure is
termed the eutectic 𝛼. The only difference between the two types of 𝛼 phase is

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 their place in the microstructure. What are the mass fractions of these phases at
the conditions at the point labeled B?
(h) Proeutectic 𝛼
(i) Eutectic 𝛼
(j) β

IV. Now consider the phase diagram as a whole:

(k) Pb and Sn do not form one-phase solid solutions at all compositions. Why
would you expect this?

(6) What are the (i) mole percent and (ii) weight percent of (a) Al2O3 in mullite
(Al6Si2O13), (b) Na2O in devitrite, and Y2O3 in yttrium iron garnet?