5.

(a) Compare interstitial and vacancy atomic mechanisms for diffusion. (b) Cite two reasons why interstitial diffusion is normally more rapid than vacancy diffusion.

Solution (a) With vacancy diffusion, atomic motion is from one lattice site to an adjacent vacancy. Self-diffusion and the diffusion of substitutional impurities proceed via this mechanism. On the other

hand, atomic motion is from interstitial site to adjacent interstitial site for the interstitial diffusion mechanism. (b) Interstitial diffusion is normally more rapid than vacancy diffusion because: atoms, being smaller, are more mobile; (1) interstitial

and (2) the probability of an empty adjacent interstitial site is

greater than for a vacancy adjacent to a host (or substitutional impurity) atom.

5.10 Show that

Cx =

x2 B exp Dt 4 Dt

is also a solution to Equation 5.4b. The parameter B is a constant, being independent of both x and t.

Solution

It can be shown that x2 B exp Dt 4 Dt

Cx =

is a solution to
C 2C = D t x 2

simply by taking appropriate derivatives of the Cx expression. When this is carried out,
x2 x2 1 exp 2 Dt 4 Dt

2C B C = D = 2 1/ 2 t 3/ 2 t x 2D

5.11 Determine the carburizing time necessary to achieve a carbon concentration of 0.45 wt% at a position 2 mm into an ironcarbon alloy that initially contains 0.20 wt% C. Use the diffusion data for -Fe in Table 5.2. The surface concentration is to be maintained at 1.30 wt% C, and the treatment is to be conducted at 1000C.

Solution In order to solve this problem it is first necessary to use Equation 5.5:

C x C0 x = 1 erf 2 Dt Cs C0

wherein, Cx = 0.45, C0 = 0.20, Cs = 1.30, and x = 2 mm = 2 10-3 m. Thus,

x Cx C0 0.45 0.20 = = 0.2273 = 1 erf 2 Dt 1.30 0.20 Cs C0

or
x erf = 1 0.2273 = 0.7727 2 Dt

By linear interpolation using data from Table 5.1

z 0.85 z 0.90

erf(z) 0.7707 0.7727 0.7970

z 0.850 0.7727 0.7707 = 0.900 0.850 0.7970 0.7707

From which
z = 0.854 = x 2 Dt

Now, from Table 5.2, at 1000C (1273 K)

 148,000 J/mol D = (2.3 10 -5 m2 /s) exp (8.31 J/mol- K)(1273 K)

= 1.93 10-11 m2/s Thus,

2 103 m (2) (1.93 1011 m2 /s) (t)

0.854 =

Solving for t yields t = 7.1 104 s = 19.7 h

5.D3 The wear resistance of a steel shaft is to be improved by hardening its surface. This is to be accomplished by increasing the nitrogen content within an outer surface layer as a result of nitrogen diffusion into the steel. The nitrogen is to be supplied from an external nitrogen-rich gas at an elevated and constant temperature. The initial nitrogen content of the steel is 0.002 wt%, whereas the surface concentration is to be maintained at 0.50 wt%. For this treatment to be effective, a nitrogen content of 0.10 wt% must be established at a position 0.40 mm below the surface. Specify appropriate heat treatments in terms of temperature and time for temperatures between 475C and 625C. The preexponential and activation energy for the diffusion of nitrogen in iron are 3 10-7 m2/s and 76,150 J/mol, respectively, over this temperature range.

Solution This is a nonsteady-state diffusion situation; thus, it is necessary to employ Equation 5.5, utilizing the following values for the concentration parameters: C0 = 0.002 wt% N Cs = 0.50 wt% N Cx = 0.10 wt% N

Therefore
0.10 0.002 Cx C0 = 0.50 0.002 Cs C0 x = 0.1968 = 1 erf 2 Dt

And thus
x 1 0.1968 = 0.8032 = erf 2 Dt

Using linear interpolation and the data presented in Table 5.1

z 0.9000 y

erf (z) 0.7970 0.8032

0.9500

0.8209

y 0.9000 0.8032 0.7970 = 0.8209 0.7970 0.9500 0.9000

From which

y =

x = 0.9130 2 Dt

The problem stipulates that x = 0.40 mm = 4.0 10-4 m. Therefore

4.0 104 m = 0.9130 2 Dt

Which leads to Dt = 4.80 10-8 m2

Furthermore, the diffusion coefficient depends on temperature according to Equation 5.8; and, as stipulated in the problem statement, D0 = 3 10-7 m2/s and Qd = 76,150 J/mol. Hence

Q Dt = D0 exp d (t) = 4.80 10 -8 m2 RT

76,150 J/mol 8 2 10 -7 m2 /s) exp (t) = 4.80 10 m (8.31 J/mol - K)(T)

(3.0

And solving for the time t 0.160 9163.7 exp T

t (in s) =

Thus, the required diffusion time may be computed for some specified temperature (in K). Below are tabulated t values for three different temperatures that lie within the range stipulated in the problem.

Temperature (C)

Time s h

500 550 600

22,500 11,000 5800

6.3 3.1 1.6

5.22 The diffusion coefficients for silver in copper are given at two temperatures:

T (C) 650 900 (a) Determine the values of D0 and Qd. (b) What is the magnitude of D at 875C?

D (m2/s) 5.5 1016 1.3 1013

Solution (a) Using Equation 5.9a, we set up two simultaneous equations with Qd and D0 as unknowns as follows:
Qd 1 R T1

ln D1 = lnD0

ln D2 = lnD0

Qd 1 R T2

Solving for Qd in terms of temperatures T1 and T2 (923 K [650C] and 1173 K [900C]) and D1 and D2 (5.5 10-16 and 1.3 10-13 m2/s), we get

Qd = R

ln D1 ln D2 1 1 T1 T2

(8.31 J/mol - K) ln (5.5 10 -16) ln (1.3 10 -13) 1 1 1173 K 923 K

= 196,700 J/mol

Now, solving for D0 from Equation 5.8 (and using the 650C value of D)

Q D0 = D1 exp d RT 1

196, 700 J/mol = (5.5 10 -16 m2 /s) exp (8.31 J/mol - K)(923 K)

= 7.5 10-5 m2/s

(b) Using these values of D0 and Qd, D at 1148 K (875C) is just

196, 700 J/mol D = (7.5 10 -5 m2 /s) exp (8.31 J/mol - K)(1148 K)

= 8.3 10-14 m2/s

Note: this problem may also be solved using the Diffusion module in the VMSE software. Open the Diffusion module, click on the D0 and Qd from Experimental Data submodule, and then do the following: 1. In the left-hand window that appears, enter the two temperatures from the table in the book (converted from degrees Celsius to Kelvins) (viz. 923 (650C) and 1173 (900C), in the first two boxes under the column labeled T (K). Next, enter the corresponding diffusion coefficient values (viz. 5.5e-16 and 1.3e-13). 3. Next, at the bottom of this window, click the Plot data button. 4. A log D versus 1/T plot then appears, with a line for the temperature dependence for this diffusion system. At the top of this window are give values for D0 and Qd; for this specific problem

these values are 7.55 10-5 m2/s and 196 kJ/mol, respectively

5. To solve the (b) part of the problem we utilize the diamond-shaped cursor that is located at the top of the line on this plot. Click-and-drag this cursor down the line to the point at which the entry under the Temperature (T): label reads 1148 (i.e., 875C). The value of the diffusion coefficient at this temperature is given under the label Diff Coeff (D):. For our problem, this value is 8.9 10-14 m2/s.

5.23 Below is shown a plot of the logarithm (to the base 10) of the diffusion coefficient versus reciprocal of the absolute temperature, for the diffusion of iron in chromium. Determine values for the activation energy and preexponential.

Solution This problem asks us to determine the values of Qd and D0 for the diffusion of Fe in Cr from the plot of log D versus 1/T. According to Equation 5.9b the slope of this plot is equal to
Qd 2.3 R

(rather

Q than d since we are using log D rather than ln D) and the intercept at 1/T = 0 gives the value of R

log D0. The slope is equal to log D1 log D2 (log D) = 1 1 1 T1 T2 T

slope =

Taking 1/T1 and 1/T2 as 0.65 10-3 and 0.60 10-3 K-1, respectively, then the corresponding values of
D1 and D2 are 2.81 10-16 and 1.82 10-15, as noted in the figure below.

The values of log D1 and log D2 are 15.60 and 14.74, and therefore,
Qd = 2.3 R (slope)

Qd = 2.3 R

log D1 log D2 1 1 T1 T2

15.60 (14.74) = (2.3)(8.31 J/mol- K) (0.65 103 0.60 103 ) K1

= 329,000 J/mol Rather than trying to make a graphical extrapolation to determine D0, a more accurate value is obtained analytically using Equation 5.9b taking a specific value of both D and T (from 1/T) from the plot given in the problem; Therefore
Q D0 = D exp d RT
329,000 J/mol = (1.0 10 -15 m2 /s) exp (8.31 J/mol - K)(1626 K)

for example, D = 1.0 10-15 m2/s at T = 1626 K (1/T = 0.615 10-3 K-1).

= 3.75 10-5 m2/s

7.

Core 9.01

8.

Core 9.02

9. (A)

Conc. of Al

10E-18/cm3

(B) D = D0 exp(

E ) RT

ln D = ln D0 + ( E / RT )
Solve this equation at both 1100oC and 1000oC,

E = 5.12 105 J / mol

Here we use E and provided diffusivity at 1300oC to calculate D at 900oC

D900 = 1.91 10 16 cm 2 / sec

9.1 Consider the sugarwater phase diagram of Figure 9.1.

(a) How much sugar will dissolve in 1500 g water at 90C (194F)? (b) If the saturated liquid solution in part (a) is cooled to 20C (68F), some of the sugar will precipitate out as a solid. What will be the composition of the saturated liquid solution (in wt% sugar) at 20C? (c) How much of the solid sugar will come out of solution upon cooling to 20C?

Solution (a) We are asked to determine how much sugar will dissolve in 1000 g of water at 90C. From the solubility limit curve in Figure 9.1, at 90C the maximum concentration of sugar in the syrup is about 77 wt%. It is now possible to calculate the mass of sugar using Equation 4.3 as

Csugar (wt%) =

msugar msugar + mwater

100

77 wt% =

msugar msugar + 1500 g

100

Solving for msugar yields msugar = 5022 g (b) Again using this same plot, at 20C the solubility limit (or the concentration of the saturated solution) is about 64 wt% sugar. (c) The mass of sugar in this saturated solution at 20C (m' sugar ) may also be calculated using Equation 4.3 as follows: m' sugar m' sugar + 1500 g

64 wt% =

100

which yields a value for m'sugar of 2667 g. Subtracting the latter from the former of these sugar concentrations yields the amount of sugar that precipitated out of the solution upon cooling m"sugar ; that is
m" sugar = msugar m sugar = 5022 g 2667 g = 2355 g

9.11 A copper-nickel alloy of composition 70 wt% Ni-30 wt% Cu is slowly heated from a temperature of 1300C (2370F). (a) At what temperature does the first liquid phase form? (b) What is the composition of this liquid phase? (c) At what temperature does complete melting of the alloy occur? (d) What is the composition of the last solid remaining prior to complete melting?

Solution Shown below is the Cu-Ni phase diagram (Figure 9.3a) and a vertical line constructed at a composition of 70 wt% Ni-30 wt% Cu.

(a) Upon heating from 1300C, the first liquid phase forms at the temperature at which this vertical line intersects the -( + L) phase boundary--i.e., about 1345C. (b) The composition of this liquid phase corresponds to the intersection with the ( + L)-L phase boundary, of a tie line constructed across the + L phase region at 1345C--i.e., 59 wt% Ni; (c) Complete melting of the alloy occurs at the intersection of this same vertical line at 70 wt% Ni with the ( + L)-L phase boundary--i.e., about 1380C;

(d) The composition of the last solid remaining prior to complete melting corresponds to the intersection with -( + L) phase boundary, of the tie line constructed across the + L phase region at 1380C--i.e., about 79 wt% Ni.