Engr 270 -- Materials Science and Engineering

TEST 4 -- Sample Solution

Part 2: Solve each of the following problems completely.

1. In this problem we are asked to show that the minimum cation-to-anion radius ratio for a
coordination number of four is 0.225. If lines are drawn from the centers of the anions, then
a tetrahedron is formed. The tetrahedron may be inscribed within a cube as shown below.

The spheres at the apexes of the tetrahedron are drawn at the corners of the cube, and
designated as positions A, B, C, and D. (These are reduced in size for the sake of clarity.)
The cation resides at the center of the cube, which is designated as point E. Let us now
express the cation and anion radii in terms of the cube edge length, designated as a. The
spheres located at positions A and B touch each other along the bottom face diagonal.
Thus,
AB = 2rA
But
2 2 2 2
(AB) = a +a = 2a
or
AB = a 2 = 2rA
And
2rA
a =
2

There will also be an anion located at the corner, point F (not drawn), and the cube
diagonal AEF will be related to the ionic radii as
(
AEF = 2 rA + rC )
(The line AEF has not been drawn to avoid confusion.) From the triangle ABF
(AB)2 + (FB)2 = (AEF)2

But,
 2rA
FB = a =
2
and
AB = 2rA
from above. Thus,
2
⎛2r ⎞
[( )]
2
(2 rA )
2
+ ⎜ A⎟
⎝ 2⎠
= 2 rA + rC

Solving for the r /r ratio leads to

C A
rC 6 − 2
= = 0.225
rA 2

2. A hypothetical AX type or ceramic material is known to have a density of 3.55 g/cm3, and a
unit cell of cubic symmetry with a cell edge length of 0.475 nm. The atomic weights of the A and
X elements are 60.2 and 16.0 g/mol, respectively. On the basis of this information, which of the
following crystal structures would you expect this ceramic compound to have: sodium chloride,
cesium chloride, zinc blende, diamond cubic, fluorite, and perovskite? Justify your choice(s).
(See table 12.4)
Answer: None of the suggested crystal structure (n’ = 3.0 formula units/units cell)

Solution:
Using Equation 12.1 and solving for n’
ρVC N A
n' =
∑A +∑A
C A

(3.55)(4.75 × 10 −8 ) 3 (6.023 × 10 23 )
n' =
(60.2 + 16.0)
n’ = 3.0 formula units/unit cell.

For the AX type ceramics, sodium chloride and zinc blende have n’=4, while cesium
chloride has n’=1. Therefore, none of the suggested crystal structures would work.

3. Consider two hypothetical ions A+ and X2- which have radii of 0.125 and 0.145 nm,
respectively. (See Table 12.2)

a. What is the coordination number for each A+ in the compound A2X? Answer: 8
b. Assuming that the crystal structure for this compound belongs to the cubic crystal system,
describe or draw a unit cell for A2X. Answer: A variant of fluorite crystal structure. A unit cell
would have eight interconnected cubes with X2- ions positioned at all cube corners; half of the
cube centers would be occupied by A+ ions.

Solution:

rA+ 0.125
a) Compute the cation-anion radius ratio: = = 0.862 .
rX 2 − 0.145
The coordination number is eight (Table 12.2).
 b) The crystal structure would be a variation of the fluorite crystal structure (Figure 12.5). A
unit cell would have eight interconnected cubes with X2- ions positioned at all cube
corners; half of the cube centers would be occupied by A+ ions.

4. The energy gap of Germanium is 0.66 eV. The electron mobility if 0.364 m2/V-s. The hole
mobility is 0.190 m2/V-s. The intrinsic hole concentration at room temperature (300 K) is 2.3 ×
1019 holes/m3.
a) Calculate the electrical conductivity of germanium (intrinsic) at room temperature.
b) Calculate the electrical conductivity of germanium (intrinsic) at 100°C. (|e| = 1.6 × 10-19 C,
and the k = 8.62 × 10-5 eV/K)
c) Germanium is to be doped with Antimony to produce an extrinsic n-type semiconductor.
What atomic density (in atoms/m3) is required to yield a conductivity of 104 (Ωm)-1. (Neglect
the conductivity of intrinsic germanium.)
Answers: a) 2.04 (Ωm)-1; b) 24.9 (Ωm)-1

Solution:

a) σ = n e (μ + μ )
e h

σ = (2.3 × 1019 )(1.6 × 10 −19 )(0.364 + 0.190)

= 2.04 (Ωm )
−1

σ2 ⎛ Eg ⎛ 1 1 ⎞⎞
b) = exp⎜⎜ − ⎜⎜ − ⎟⎟ ⎟
⎟
σ1 ⎝ 2k ⎝ T2 T1 ⎠ ⎠
⎛σ ⎞ 0.66 ⎛ 1 1 ⎞
ln⎜⎜ 2 ⎟⎟ = − −5 ⎜
− ⎟
⎝ σ1 ⎠ 2(8.62 × 10 ) ⎝ 373 300 ⎠

σ2=24.9 (Ωm)-1

5. Calculate the resistance of a 150-m long, 3.12-mm diameter copper wire at an ambient
temperature of 20°C. The electrical conductivity of the wire is 5.88 × 107 (Ωm)-1. How much
current will result if a voltage of 10 V is applied at the ends of the wire? Ans: 0.33 Ω.

L 1 L
R=ρ =
A σ A
R = : 0.33 Ω.
I = V/R = 10/0.33 = 30 A

6. Is it possible to have a random poly(ethylene-propylene) copolymer that has number- and

weight-average degrees of polymerization of 2500 and 2000, respectively, and number- and
weight-average molecular weights of 8,500 and 67,200 g/mol? Why or why not?
Answer: no. Mer molecular weights computed from weight-average and number-average
data are different

7. Molecular weight data from some polymer are tabulated below. Compute the (a) number-
average molecular weight, and (b) the weight-average molecular weight. (c) If it is known
 that the material’s number-average degree of polymerization is 477, which one of the
polymers listed in Table 14.3 is this polymer? Why?
Molecular wt.Range xi

8,000-20,000 0.05
20,000-32,000 0.15
32,000-44,000 0.21
44,000-56,000 0.28
56,000-68,000 0.18
68,000-80,000 0.10
80,000-92,000 0.03

(a) From the tabulated data, we are asked to compute Mn , the number-average molecular

weight. This is carried out below.

Molecular wt.
Range Mean M x xM
i i i i
8,000-20,000 14,000 0.05 700
20,000-32,000 26,000 0.15 3900
32,000-44,000 38,000 0.21 7980
44,000-56,000 50,000 0.28 14,000
56,000-68,000 62,000 0.18 11,160
68,000-80,000 74,000 0.10 7400
80,000-92,000 86,000 0.03 2580

_________________________

Mn = ∑ xiMi = 47,720 g/mol

(b) From the tabulated data, we are asked to compute M w , the weight- average molecular

weight. This determination is performed as follows:

Molecular wt.
Range Mean M w wM
i i i i
8,000-20,000 14,000 0.02 280
20,000-32,000 26,000 0.08 2080
32,000-44,000 38,000 0.17 6460
44,000-56,000 50,000 0.29 14,500
56,000-68,000 62,000 0.23 14,260
 68,000-80,000 74,000 0.16 11,840
80,000-92,000 86,000 0.05 4300

_________________________
Mw = ∑ wiMi = 53,720 g/mol

(c) We are now asked if the number-average degree of polymerization is 477, which of the
polymers in Table 14.3 is this material? It is necessary to compute m in Equation (14.4a)
as

Mn 47, 720 g/mol

m = = = 100.04 g/mol
n 477
n

The mer molecular weights of the polymers listed in Table 14.3 are as follows:

Polyethylene--28.05 g/mol
Polyvinyl chloride--62.49 g/mol
Polytetrafluoroethylene--100.02 g/mol
Polypropylene--42.08 g/mol
Polystyrene--104.14 g/mol
Polymethyl methacrylate--100.11 g/mol
Phenol-formaldehyde--133.16 g/mol
Nylon 6,6--226.32 g/mol
PET--192.16 g/mol
Polycarbonate--254.27 g/mol

Therefore, polytetrafluoroethylene is the material since its mer molecular weight is closest to
that calculated above.