Materials Science ME 306

LAB #3

Diffusion

Victor Li (U91093053)

Alexandros Oratis

Gregory Schneiter

Syed Shabbar Shirazi

John Subasic

Kamolnat Tabattanon

Section C3

2014 March 21

Professor Ryan

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1. Introduction

Diffusion is an important thermodynamic process with many practical uses in

manufacturing and is a crucial process for life processes and nature. In solids, the only

mechanism for atomic transport is diffusion, where there is a net movement of atoms from

regions of high concentration toward regions of low concentration. In this lab, the mechanisms of

diffusion and the derivation of diffusion constants are explored through the observation of the

diffusion of a Copper Nickel system, specifically dimes. The samples have been heat treated for

8 and 16 hours at temperatures of 900C, 950C, 1000C, and 1050C. Because diffusion is a

thermodynamic process, an input of heat or activation energy is needed for the process to occur.

Normally, the diffusion constant changes with concentration, but the assumption that it remains

constant as concentration changes is made to simplify calculations and avoid Ficks 2nd law.

2. Theory

Diffusion can be categorized as a steady or non-steady state process. Steady state diffusion is

independent of time and can be modeled by Ficks first law, = . This law states that the

net flux, J is equal to the product of the diffusion coefficient D and the concentration gradient.

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Similarly, Ficks second law, = 2, models non-steady state diffusion, demonstrating that

the diffusion coefficient depends upon the concentration or position and varies with time, as the

material diffuses further. Another key equation that reveals diffusion as a thermodynamic

process, where an energy barrier must be overcome by the atoms, is = 0 exp( ). Here, Q

represents the activation energy of the material diffusing in another and is accompanied by the

temperature factor RT. Lastly, the approximation of the depth of diffusion using ,

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where D and t are the diffusion coefficient and diffusion time respectively, is appropriate for

the diffusion of a Copper Nickel system.

3. Experiment and Method

In the experiment of the diffusion of a Copper Nickel system, digital images of six samples were

taken at 100x magnification on a microscope for the determination of the width of diffusion from

the inclusion layer to the etchant line in the copper. The 100x image scale was subsequently

measured in pixels using the imageJ software, and the number of divisions on the scale was

recorded. Fifteen measurements of the depth of diffusion for each sample were then taken in

pixels and recorded. The depth of diffusion of each sample and the time of diffusion were

utilized to calculate the diffusion coefficient using . Plots of ln() vs 1/T for samples

exposed to 8 hour and 16 hour diffusion were generated and a linear fits were then created based

on the data sets. The method of calculating the activation energy of diffusion, Q, and diffusion

constant, 0 , is based on the equation, = 0 exp( ). Taking the natural log of both sides,

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results in the Arrhenius equation, = () + 0 . Afterwards, the slope of the linear fit

was equated to and the y-intercept was equated to 0 to find the activation energy and

diffusion constant.

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4. Results

Fig.1 Sample #2 Fig.2 Sample #3

Fig.3 Sample #4 Fig. 4 Sample #5

Fig.5 Sample #6 Fig. 6 Sample #7

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 Data # Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7
1050C
1000C 16hr 900C 8hr 1000C 8hr 950C 16hr 16hr 950C 8hr
Length (pixels)
1 836.153 628.204 692.682 508.063 637.257 465.394
2 748.385 524.061 516.48 444.072 582.697 410.366
3 688.047 568.69 549.181 376 502.299 338.373
4 584 652.196 693.467 548.525 560.985 664.686
5 692.416 612.209 544.5 363.186 596.657 568.577
6 732 744.172 530.69 404.079 477.46 584.452
7 644.05 712.281 592.5 404.969 368.196 542.498
8 744 701.381 544.5 317.616 569.407 536.954
9 692.012 588.218 350.657 380.021 672.19 36.222
10 660.012 592.054 601.345 408.96 812.63 588.054
11 732.011 556.058 682.783 540.37 997.156 528.136
12 744 632.013 569.098 368.782 648.049 541.479
13 756.095 596.013 560.143 380.189 1028 556.676
14 696.046 716 533.667 436.293 539.348 565.134
15 804.487 756.095 485.831 449.141 937.034 620.013
Table 1 Table representing the data, specifically the width of diffusion, measured by one group for each of the six
samples. A total of 90 measurements were taken by each group.

The six samples in Figures 1 through 6 were taken at 100x magnification on a microscope. Each

group measured and recorded the diffusion depth of the samples fifteen times for more accurate

results. The data in Table 1was obtained by measuring the perpendicular distance from the

inclusion layer to the etchant line in the copper using imageJ software in units of pixels. Prior to

measuring, the scale for converting pixels to millimeters was measured. The ninety

measurements for each sample were averaged together, converted to centimeters, and used in

making the necessary calculations for analysis.

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5. Analysis and Discussion

(1)

Sample # Temperature (C) Time (hrs) Diffusion Width (cm)

2 1000 16 0.172

3 900 8 0.159

4 1000 8 0.151

5 950 16 0.0995

6 1050 16 0.185

7 950 8 0.126

Table 2: Shows the sample number and corresponding diffusion temperature, time, and width

Calculate Diffusion Width for Sample #2:

0.1 1
= ( )( )( )( )
1 1000

10 0.1 1
= (754.2917733 ) ( )( )( ) = .172
439.1334 1 10

This procedure is used for calculating the diffusion width for all proceeding samples.

(2)

Activation

Sample # Diffusion Coefficient Diffusion Constant Energy

(2 /) (c2 /)
( )

2 5.14 107 1.76 107 2 / 3.43 /

3 8.78 107

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 4 7.91 107

5 1.72 107

6 5.94 107

7 5.51 107

Calculate Diffusion Coefficient for Sample #2:

2
=

(.172)2
= = 5.14 107 2 /
3600
(16 )
1

Calculate Diffusion Constant for 8 Hour Diffusion Samples:

Fig 7. Graph showing the natural log of the diffusion coefficient vs. the inverse of temperature for the 8 hour
diffusion samples and a linear fit based on the data set. The y-intercept and slope are displayed.

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 = ln(0 )

0 = 15.55 = 1.76 107 2 /

=

4184
1726 =
8.314 1 1

= 3.43 /

Calculate Diffusion Constant and Activation Energy for 16 Hour Diffusion Samples:

Fig 1. Graph showing the natural log of the diffusion coefficient vs. the inverse of temperature for the 16 hour
diffusion samples and a linear fit based on the data set. The y-intercept and slope are displayed.

= ln(0 )

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 0 = 2.293 = 9.90 2 /

=

4184
21790 =
8.314 1 1

= 43.3 /

Do and Q values can be averaged together since the values are constants:

9.902 /+1.76107 2 /
0 = = 4.952 /
2

43.3 + 3.43
= = 23.4/
2

(3)

Table 3: These are the tabulated values for the diffusion constant and activation energy.

The values of 0 and calculated in this experiment vary with the first row of values, where the

diffusing species is Cu and the host metal is Ni, by a moderate degree for both values.

4.95 2.3
% 0 = 100 = 53.5%
4.95

61.5 23.5
% = 100 = 61.8%
61.5

Several factors could have influenced this difference. Taking more measurements of the

diffusion width to avoid certain outliers and errors can be considered. Other factors include the

diffusion temperature and time conditions and calculation errors. Since the scope of this

experiment only included measuring the diffusion width of samples exposed at 4 temperatures

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and two times. Taking more measurements at a combination of different temperatures and times

would lead to a more accurate linear fit with more data points to consider in the approximation.

(4) Activation energies are not the same for Cu->Ni and Ni->Cu because Cu and Ni have

different properties. Factors that influence activation energy and, thus, rate of diffusion are

crystal structure, bonding, atomic radius, density of material, etc. For example, open crystal

structures, materials with secondary bonding, smaller diffusing atoms, and lower density

materials diffuse may require lower activation energies than those of closed-packed structures,

materials with covalent bonding, larger diffusing atoms, and higher density materials.

6. Conclusion

The diffusion of a Copper Nickel system was successfully observed and modelled by measuring

the depth of diffusion of six samples exposed to a minimum temperature of 900C and a

maximum temperature of 1050 C. Although the diffusion constant depends on concentration

based on Ficks second law, it is assumed independent of it for the purposes of this experiment.

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