CME 300 Properties of Materials

ANSWERS Homework 2 October 5, 2011

Problems from Callister p. 78

r = 1.431 Å so a = 2√2 r = 4.048 Å

d(110) = a/√2 = 2r = 2.862Å

d(310) = a/√10 and a = 4r/√3 = 4 1.249/√3 Å = 2.884

d(310) = 0.912 Å
d = λ/(2sinθ) so 2θ = 2 asin(λ/2d) = 45.9°

r = 1.241 Å a = 4r/√3 = 2.866Å

d(111) = a/√3 = 1.655Å
d(211) = a/√6 = 1.170Å

a) d(311) = λ/(2sinθ) = 0.711Å/(2sin(18.06°)) = 1.147Å

b) r = a/(2√2) for FCC
a = d(311) √(11) = 3.803Å
r = 3.803Å/(2√2) = 1.345Å

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a) d(211) = λ/(2sinθ) = 1.659Å/(2 sin(37.95°)) = 1.347Å
b) For BCC r = √3a/4
a = d(211) √(6) = 3.301Å
r = √3 3.301Å/4 = 1.429Å

d(hkl) = a/√(h2+k2+l2) = λ/(2sinθ) = 1.542Å/(2sin(22.26°)) = 2.035Å

r = 1.246Å for Nickel FCC so a = 1.246 Å 2√2 = 3.524Å
For FCC the first 6 reflections are (111), (200), (220), (311), (222), (400) so by trial and error we
find this is the (111) reflection.

Need to measure the peak positions from the plots,

Plane 2θ d = λ/(2sinθ) a = d √(h2+k2+l2)
(111) 32° 2.80Å 4.84Å
(200) 37° 2.43Å 4.88Å
(220) 53° 1.73Å 4.89Å
(311) 63.5° 1.47Å 4.86Å

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(222) 66° 1.42Å 4.90Å
(400) 77.2° 1.24Å 4.94Å
(331) 86° 1.13Å 4.93Å
(420) 89° 1.10Å 4.92Å
(422) 99.8° 1.01Å 4.94Å

The higher angle values are probably better for “a” since there is less relative error in the angle at
higher values.

(110), (200), (211), (220), (310), (222) for BCC

The following diagram shows how the peaks are spaced for BCC, basically evenly spaced peaks.

Compare the FCC in this diagram to the spacing’s of the peaks in Figure 3.21 above, i.e. 2: 1: 2
signature.

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(a) At a glance you can see that the spacing’s are even so it is likely a BCC crystal if it is a metal.
For BCC the first 5 peaks are (110), (200), (211), (220), (310). (Indexing a diffraction pattern is
usually a bit more involved than this. Many diffractometers have a search procedure that will
solve the composition of the sample for you.)
(b) d = λ/(2sinθ) θ: (110) 40.2° , (200) 58°, (211) 73°, (220) 83.5°, (310) 101°
d(110) = 2.24Å
d(200) = 1.59Å
d(211) = 1.29Å
d(220) = 1.16Å
d(310) = 1.00Å
(c) a = d √(h2+k2+l2) r = √3a/4
a(110) = 3.17Å 1.37Å
a(200) = 3.18Å 1.38Å
a(211) = 3.16Å 1.37Å
a(220) = 3.28Å 1.42Å
a(310) = 3.16Å 1.37Å
Reported value for r is: 1.36Å

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This question is vague since there are two possibilities for covalent materials, generally covalent
materials crystallize as a molecular unit such as napthylene or polyethylene so the covalent
bonds are not particularly important in deciding the crystal structure, the crystalline structure is
decided by weaker interactions such as hydrogen bonding and van der Waals interactions. For
these materials the formation of a glass is quite common depending on the rate of crystallization.
I believe that Callister is referring to materials like diamond and graphite where the crystal is
composed of 3-d covalent bonds. In this case the formation of the crystal is like a chemical
synthesis of an organic material and it is very difficult to form a glass since the bonding needs to
be tetrahedral in diamond and there is little room for misplacement of bonds. For ionic
materials like NaCl it is also difficult to form a glass since the simple ionic structure and strong
ionic nature forces the material to crystallize and misplaced units carry a high energy penalty.
For other ionic materials such as SiO2, glass formation is common. This material has a
combination of tetrahedral bonding and ionic bonds so formation of the structure is quite
complex and misplaced atoms are common. The system can be locked into a disordered
structure or a glass. If the glass is annealed it can crystallize. The tendency to form a glass is
also related to the kinetics, particularly the viscosity of the melt. NaCl has a low viscosity in the
melt while SiO2 has a high viscosity melt. So issues involved in glass formation are the
complexity of the crystalline structure, the viscosity of the melt, generally the difficulty of
moving the atoms or molecules into a crystalline lattice, the more difficult the more likely it is
that a glass will form.

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11) Sketch the diffraction pattern from an FCC, BCC and HCP metals as well as the diffraction
pattern from an amorphous solid. What does the peak position of the amorphous halo indicate?

The peak position for the amorphous halo is associated with the root mean square separation
distance for the atoms, dRMS = λ/(2sinθ)

12) Derive Bragg’s Law using the specular reflection analogy.

13) What can the breadth of a diffraction peak indicate? That is, for two copper samples if one
displays a broad diffraction peak while the other displays a sharp peak what is the difference
between the two samples? What about for two aluminum samples.

The breadth of a diffraction peak can be related to small crystalline grains, residual stress in the
crystals or thermal vibrations. For a typical copper sample the most likely source for peak
broadening is residual stress. For a typical aluminum sample the most likely source for peak
broadening is thermal vibrations. This has to do with the ability of atoms to move in the crystal

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structure in aluminum. To see broadening due to small crystallite size the crystals or grains need
to be much less than a micron in size, i.e. nano-size crystals show broadening.

14) The following images are photographic diffraction patterns from aluminum foil and a
polyethylene bag. Explain why the aluminum shows dots in the Debye-Scherer rings and the
polymer does not. Explain why the polymer peaks are broader than those of aluminum. Explain
why the aluminum pattern shows arcs rather than complete rings.

The aluminum sample has rather large crystals or grains that are oriented in a drawn foil sample.
The grains are so large that in the x-ray beam (20µm by 1 cm) there are only about 50-100 grains
in the beam so each grain yields a spot for a given reflection if the planes are aligned property for
diffraction to occur. The grains have a preferred orientation relative to the draw direction so that
reflections for a given plane show up as arcs centered on the preferred direction of orientation.
The two Debye Scherer rings shown for this FCC structure are the (111) and (200) reflections.

For the polyethylene sample the crystal structure is orthorhombic with a central chain offset in
orientation. The structure ends up looking something like an FCC structure so the diffraction
pattern has a motif reminiscent of FCC, in that there are two prominent peaks at low-q. The
polyethyelene sheet also displays some degree of orientation due to the brighness of the peaks at
the top and bottom of the figure. The peaks are broad because these crystals have a thickness on
the order of 100Å or 10 nm so they are nano-crystals. The broader the peak the smaller the
crystalline thickness.

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