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(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: (1) interstitial
atoms, being smaller, are more mobile; 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
B ⎛ x2 ⎞
Cx = 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
B ⎛ x2 ⎞
Cx = exp ⎜− ⎟
Dt ⎝ 4 Dt ⎠
is a solution to
∂C ∂ 2C
= D
∂t ∂x 2
simply by taking appropriate derivatives of the Cx expression. When this is carried out,
∂C ∂ 2C B ⎛ x2 ⎞ ⎛ x2 ⎞
= D = ⎜⎜ − 1 ⎟⎟ exp ⎜⎜− ⎟⎟
∂t ∂x 2 2 D 2 t 3/ 2
1/
⎝ 2 Dt ⎠ ⎝ 4 Dt ⎠
5.11 Determine the carburizing time necessary to achieve a carbon concentration of 0.45 wt% at a
position 2 mm into an iron–carbon alloy that initially contains 0.20 wt% C. The surface
concentration is to be maintained at 1.30 wt% C, and the treatment is to be conducted at 1000°C.
Use the diffusion data for γ-Fe in Table 5.2.
Solution
C x − C0 ⎛ x ⎞
= 1 − erf ⎜ ⎟
Cs − C0 ⎝ 2 Dt ⎠
Cx − C0 0.45 − 0.20 ⎛ x ⎞
= = 0.2273 = 1 − erf ⎜ ⎟
Cs − C0 1.30 − 0.20 ⎝ 2 Dt ⎠
or
⎛ x ⎞
erf ⎜ ⎟ = 1 − 0.2273 = 0.7727
⎝ 2 Dt ⎠
z erf(z)
0.85 0.7707
z 0.7727
0.90 0.7970
From which
x
z = 0.854 =
2 Dt
2 × 10−3 m
0.854 =
(2) (1.93 × 10−11 m2 /s) (t)
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
Cx − C0 0.10 − 0.002
=
Cs − C0 0.50 − 0.002
⎛ x ⎞
= 0.1968 = 1 − erf ⎜ ⎟
⎝ 2 Dt ⎠
And thus
⎛ x ⎞
1 − 0.1968 = 0.8032 = erf ⎜ ⎟
⎝ 2 Dt ⎠
z erf (z)
0.9000 0.7970
y 0.8032
0.9500 0.8209
From which
x
y = = 0.9130
2 Dt
4.0 × 10−4 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
(3.0 × 10 -7 m2 /s) exp ⎢− ⎥ (t) = 4.80 × 10 m
2
⎣ (8.31 J/mol - K)(T) ⎦
0.160
t (in s) =
⎛ 9163.7 ⎞
exp ⎜− ⎟
⎝ T ⎠
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 Time
(°C) s h
T (°C) D (m2/s)
650 5.5 × 10–16
900 1.3 × 10–13
(a) Determine the values of D0 and Qd.
(b) What is the magnitude of D at 875°C?
Solution
(a) Using Equation 5.9a, we set up two simultaneous equations with Qd and D0 as unknowns as
follows:
Qd ⎛ 1 ⎞
ln D1 = lnD0 − ⎜ ⎟
R ⎜⎝ T1 ⎟⎠
Qd ⎛ 1 ⎞
ln D2 = lnD0 − ⎜ ⎟
R ⎜⎝ T2 ⎟⎠
Solving for Qd in terms of temperatures T1 and T2 (923 K [650°C] and 1173 K [900°C]) and D1 and
ln D1 − ln D2
Qd = − R
1 1
−
T1 T2
= −
[ ]
(8.31 J/mol - K) ln (5.5 × 10 -16) − ln (1.3 × 10 -13)
1 1
−
923 K 1173 K
= 196,700 J/mol
Now, solving for D0 from Equation 5.8 (and using the 650°C value of D)
⎛Q ⎞
D0 = D1 exp ⎜⎜ d ⎟⎟
⎝ RT1 ⎠
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” (650ºC) and “1173” (900ºC), in the first two
boxes under the column labeled “T (K)”. Next, enter the corresponding diffusion coefficient values
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., 875ºC). 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
Qd
plot of log D versus 1/T. According to Equation 5.9b the slope of this plot is equal to − (rather
2.3 R
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
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)
log D1 − log D2
Qd = − 2.3 R
1 1
−
T1 T2
⎡ − 15.60 − (−14.74) ⎤
= − (2.3)(8.31 J/mol- K) ⎢ ⎥
⎣ (0.65 × 10−3 − 0.60 × 10−3 ) K−1 ⎦
= 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; for example, D = 1.0 × 10-15 m2/s at T = 1626 K (1/T = 0.615 × 10-3 K-1).
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) ⎦
Conc. of Al
10E-18/cm3
0 t
E
(B) D = D0 exp(− )
RT
ln D = ln D0 + (− E / RT )
Solution
(a) We are asked to determine how much sugar will dissolve in 1000 g of water at 90°C. From
the solubility limit curve in Figure 9.1, at 90°C 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
msugar
Csugar (wt%) = × 100
msugar + mwater
msugar
77 wt% = × 100
msugar + 1500 g
(b) Again using this same plot, at 20°C 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 20°C (m' sugar ) may also be calculated using
m' sugar
64 wt% = × 100
m' sugar + 1500 g
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
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 1300°C, the first liquid phase forms at the temperature at which this
vertical line intersects the α-(α + L) phase boundary--i.e., about 1345°C.
(b) The composition of this liquid phase corresponds to the intersection with the (α + L)-L phase
boundary, of a tie line constructed across the α + L phase region at 1345°C--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 (α + L)-L phase boundary--i.e., about 1380°C;
(d) The composition of the last solid remaining prior to complete melting corresponds to the
intersection with α-(α + L) phase boundary, of the tie line constructed across the α + L phase region at
1380°C--i.e., about 79 wt% Ni.