MS/ME503

Homework -1

Prob. 1. A specimen consisting of a 5 mm thick strip of Fe-15 atomic%Cr, sandwiched

between two 20 cm long pure Fe bars (see figure), is heated at 1600K.

Using the origin shown above (x=0 at midpoint of Fe-Cr alloy), derive expressions for the
Cr concentration, C(x,t), across the entire specimen for the following conditions:
a) At 'very short' times.
b) At 'short' times.
c) At 'long' times.
d) At 'very long' times.
Can you guesstimate (at least to order of magnitude) the time intervals at which the above
cases will be valid?
DATA:
Density of Fe-Cr solid solution of all compositions, = 7.19 gm/cm3.
Diffusion coefficient of Cr at 1600K, D = 10-13m2/s
Prob. 2. A spherical steel pressure vessel, 1 m in diameter, 5 cm in thickness is used to
contain a process that generates atomic H by a chemical reaction at 600C. To avoid
problems with H embrittlement of the steel, the pressure vessel is periodically purged and
the H baked out of the steel wall. After purging and bakeout, the H concentration in the
wall is negligibly low. Reactants are then introduced into the vessel, and the kinetics of H
production are such that the surface concentration on the inside wall increases linearly
with time, i.e., H(0,t) = kt, where k = 10-6 gm/cm3-s.
The diffusion coefficient of H in steel at 600C, DH = 10-6 cm2/s.

a) Derive the solution for H(x,t) that will be valid for a one-day period after the reaction
starts. Please orient your solution with the origin (x=0) at the inner surface of the wall.
Clearly state and justify all assumptions made.
b) A specification to prevent cracking requires that the reaction be stopped and the vessel
purged if the average H concentration exceeds 0.05 gm/cm3 in a layer extending from the
inner surface to a depth of 1mm. Setup, but do not solve, the equation to check if it is safe
to run the reactor continuously for one day.
c) If the solubility limit of H in steel is 0.2 gm/cm3, schematically show how the
concentration profile of H in the reactor wall will change with time. If the rate of
production of H in the vessel is 2.5X10-3 gm/s, what will be the steady state concentration
profile of H. Pay attention to details in the concentration plots and indicate numerical
values on the plots wherever possible. Is it safe to operate the reactor under steady state
conditions?
d) When the walls reach steady state concentration profile, will the pressure in the tank
change with time? If so, what is dP/dt?
e) How would the steady state diffusion profile change if i) D is a decreasing function of
composition and ii) D is an increasing function of composition (qualitative answer only
required, sketch shape of concentration profiles and justify).

Prob. 3. A 7-inch thick Fe plate has a uniform concentration of hydrogen. How long will
it take to remove 90% of the hydrogen if the plates are heated and the surface hydrogen
concentration of the plate surfaces are held at zero. Assume that the diffusion coefficient
of hydrogen in the plate at the temperature of anneal is 10-4 cm2/s.
Prob. 4. Rechargeable Li-ion batteries require Li ions to diffuse into a layered oxide
cathode material. Titanium oxide (TO) is a potential cathode material. Assume that the TO
particles are spherical, with a radius of 10 m. Assume that these particles do not have any
Li to start with. Assume that the surface of these particles quickly reach a concentration of
c*. The diffusivity of Li in TO is 10-12 cm2/s.
i) How long will it take for the center of the TO particles to reach a concentration of c*/2?
Assume initially, that only the first term of the solution can be used. Justify that this is a
good assumption.
ii) Now assume that the particles were 100 nm in diameter. How long will it take for this
case? Is the first term only assumption still good?
iii) A123 Systems is a Li-ion battery manufacturer who showed that using nano-sized
cathode powders dramatically reduced the charging times of these rechargeable batteries.
Based on your calculations, does this make sense?

Prob. 5. Interdiffusion experiments were recently carried out in the medium-tedium (Md-
Te) binary alloy system. Md and Td both have FCC crystal structures in which diffusion is
isotropic, i.e., independent of crystallographic direction; and they both exhibit complete
solid solubility. The experiment consisted of placing inert markers between two Md and
Td single crystals, and annealing the couple for 180 hours at 1000C. The figure below
shows the concentration profile measured after the anneal, along with the location of the
Matano interface and the inert markets.
a) Calculate the vacancy flux across the plane of the inert markers at t = 180 hours.
b) Calculate how far the Matano interface has moved with respect to the Md-rich end of
the sample after 180 hours.
DATA
atomic mass: MMd = 65 g/mole, MTd = 32.1 g/mole
density: Md = 6.5 g/cm3, Td = 3.21 g/cm3
lattice constant: aMd = 4, aTd = 4
Vmix = 0 in the Md-Td system