The Discovery and Acceptance of the Kirkendall Effect http://www.tms.org/pubs/journals/JOM/9706/Nakajima-9706.

html

The following article appears in the journal JOM,

49 (6) (1997), pp. 15-19.
JOM is a publication of The Minerals, Metals & Materials Society

Historical Insight

The Discovery and Acceptance of the CONTENTS

Kirkendall Effect: The Result of a
INTRODUCTION
Short Research Career KIRKENDALL’S CAREER
THE FIRST PAPER (1939)
Hideo Nakajima AND D.Sc. DISSERTATION
THE SECOND PAPER (1942)
THE THIRD PAPER (1947)
Editor’s Note: Some of the artwork employed here was photographically reproduced from MEHL’S CRITICISM AND
existing publications. As a result, the quality of the images is sometimes less than ideal. EXPERIMENTS
WHY KIRKENDALL
In the 1940s, it was a common belief that atomic diffusion took place via a direct STOPPED HIS RESEARCH
exchange or ring mechanism that indicated the equality of diffusion of binary CAREER
elements in metals and alloys. However, Ernest Kirkendall first observed CONCLUSION
inequality in the diffusion of copper and zinc in interdiffusion between brass and ACKNOWLEDGEMENTS
copper. This article reports how Kirkendall discovered the effect, now known as References
the Kirkendall Effect, in his short research career.

INTRODUCTION
The fragrance of flowers in a corner of a room drifts even to far distances. When one droplet of ink is dripped into a cup of
water, the ink soon spreads, even without stirring, and quickly becomes invisible. These facts show that even if there is no
macroscopic flow in a gas or a liquid, molecular movement (i.e., diffusion) can take place, and different entities can mix with
each other.

Is atomic diffusion possible in a solid metal where atoms arrange themselves regularly? The answer is yes. Although atomic
diffusion in solids is far slower than that in gases and liquids, diffusion does take place. The diffusion in solids is clearly
related to various processes such as recrystallization, precipitation, and oxidation. Such study of the diffusion in solids was
initiated just 100 years ago when Sir Roberts-Austen1 discovered the diffusion phenomenon of gold in solid lead in 1896.
For a long time afterward, people believed that atomic diffusion occurred by a direct exchange mechanism or a ring
mechanism in metallic crystals (Figure 1).

In 1947, Ernest Kirkendall reported the results

of experiments on the interdiffusion between
copper and zinc in brass and observed the
movement of the interface between the
different phases due to high-temperature
interdiffusion, now called the Kirkendall
Effect. This phenomenon supported the idea
that atomic diffusion occurs through vacancy
exchange. Since its discovery, the Kirkendall
Effect has been found in various alloy
systems, and studies on lattice defects and
diffusion developed significantly. The a b c
Kirkendall Effect is important in connection Figure 1. The atomic diffusion mechanism showing (a) a direct exchange mechanism,
with bonding between different materials and, (b) ring mechanism, and (c) vacancy mechanism.
in particular, raises the practical concern of
controlling and suppressing the voids that are produced in the boundary region at a bonding interface. Today, the effect has
been taken into account in various fields in materials science and technology such as structural materials welding, metals and
ceramics powders sintering, thin films, and large-scale integration.

When the International Conference on Diffusion in Metals and Alloys was held in 1988 in Balatonfured, Hungary, S.
Rothman of Argonne National Laboratory (and also the editor of Journal of Applied Physics) told me of an episode during

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the discovery of the new effect by Kirkendall. Kirkendall’s idea had been criticized by many researchers, but he kept trying
until his interpretation had almost been accepted. When a search committee was set up to determine Kirkendall’s possible
promotion to associate professorship, one of the referees, R.F. Mehl of the Carnegie Institute of Technology (an authority on
diffusion), rejected Kirkendall’s promotion. Shortly thereafter, Kirkendall gave up his academic career and took a job as
secretary of the American Institute of Mining and Metallurgical Engineers (AIME). Although the story related by Rothman
was certainly interesting to me, my boss at that time (H.B. Huntington, Rensselaer Polytechnic Institute) told a different
version of the story, and I wondered which version was right.

Fifty years have passed since Dr. Kirkendall finished his academic career. Fortunately, several friends informed me that he
was still in good health, and I succeeded in calling him when I was staying in Canada in 1993. I was so excited to talk with
him; he politely replied to my various inquiries and kindly suggested I visit him at his home "since such a telephone
conversation is not sufficient." At that time, I could not visit him because I had to leave Canada to return to Japan within a
few days. Two months later, I finally visited his home and interviewed him. Based on that meeting, this article reports how
Kirkendall discovered the Kirkendall Effect in a short research career in which he produced only three papers. 2,4

KIRKENDALL’S CAREER
Ernest Kirkendall was born in Michigan in 1914. He graduated from Wayne College (later Wayne University) in 1934, was
awarded a master’s degree in 1935 and a doctor of science in 1938 from the Metallurgy Department at the University of
Michigan. He was an instructor at Wayne University from 1937 to 1941 and an assistant professor from 1941 to 1946, during
which time he wrote the famous paper "Zinc Diffusion in Alpha Brass" with Smigelskas.4 From 1947 to 1965, he served as
secretary of AIME; he then became a manager at the United Engineering Trustees. He concluded his career as a vice
president of the American Iron and Steel Institute from 1966 and 1979.

To illustrate the importance of his discovery, the Kirkendall Effect Symposium on Interdiffusion and Phenomena that
Depend on Net Vacancy Flows was held during the TMS Fall Meeting in October 1991. I heard that this was successful
meeting, attended by authors such as professors Turnbull, Balluffi, Huntington, Cahn, and Heumann, who had contributed to
lattice defects and diffusion research in the period following the discovery of the Kirkendall Effect.

THE FIRST PAPER (1939) AND D.Sc. DISSERTATION

In 1935, Kirkendall began his research work under the direction of Upthegrove in the Metallurgy Department at University
of Michigan. At the beginning, he learned much from the reviews by Desch (1912), 5 Mehl (1936),6 and Krynit-sky (1937).7
He developed much interest in atomic diffusion phenomena in solid metals and, in particular, was significantly influenced by
Mehl’s review. Furthermore, he was much interested in equilibrium-phase diagrams, particularly the phase separation of
-brass and -brass resulting from the cooling of -brass alloy. For his research topic, he selected diffusion in brass, which was
a combination of those two interests. Although such research had already been done by several researchers, most were
nothing more than qualitative discussions, and none of the research could elucidate the key questions until quantitative
evaluation and discussion had been achieved. Thus, Kirkendall wanted to measure the diffusion coefficients of copper and
zinc in -brass quantitatively with high accuracy by using a "new method." The result was his D.Sc. disertation, 2 which
reported zinc diffusivities in brass at three different temperatures.

The side face of the -brass plate-shaped specimen (100 mm in length and about 3
mm in thickness) was first mirror-polished; it was then electroplated with 250 mm
thickness of copper (Figure 2). The specimens were annealed in vacuum at 723 K for
about 10 ks to make hydrogen desorb from the specimens. Diffusion anneals were
carried out in a muffle electric furnace at a specific temperature and for a specific
duration. After water quenching, a part of the specimen was cut off, while the
remainder was used for successive diffusion anneals. The metallographic observation
of the polished surface A was performed with an optical microscope. X-ray
diffraction was taken from the polished surface B after each sectioning step of 25-75
µm thickness to measure the lattice parameters, which were then converted to
determine the zinc concentration in -brass (Figure 2).

After diffusion anneals, an -brass phase layer grows on both sides of the bonding
interface of copper and -brass (Figure 3). The -brass layer inside the interface
Figure 2. A schematic of the specimen consists of large columnar grains so that the / phase boundary is clear. On the
used for the study of the first paper.2
other hand, since the copper-rich -brass phase outside the interface has the same
crystal structure as the copper phase, the boundary is not distinct.

Kirkendall told me, "The quantitative analysis of the work was possible owing to two points—the -brass phase in between
the original (bonding) interface and the final / interface always grows uniformly in thickness, and the / interface can be
observed clearly with the optical microscope. If the / interface and the columnar grains formed on the inside of the original

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copper -brass interface had not been distinct, the Kirkendall Effect would not have been discovered. Thus, I was lucky to
choose the system of copper and brass originally." He measured the concentration profiles of copper diffusion in -brass
phase surrounded by both the original and the / interfaces.

Although his first paper2 did not mention it, he

told me, "I had noticed that the location of the
original interface after diffusion anneal was
different from the Boltzmann-Matano interface
when I was a graduate student. And I did not
necessarily think about the possibility of
inequality of the diffusivities of copper and zinc
(Dcu DZn)." The Boltzmann-Matano interface
fixes two equal areas on the concentration profile a b e f
c(x); it is the plane through which equal amounts
of material have moved in positive and negative
directions.

At that time, it was common belief that atomic

diffusion took place via a direct exchange or ring
mechanism. None of the researchers proposed
other mechanisms. Thus, according to his
advisor’s suggestion, "I preferred to explain the c d g h
movement of the original interface as due to
Figure 3. Metallographic observation (magnified 200x) at (a) as bonded, (b) one
volume change between - and -brass; -brass hour, (c) one hour, (d) four hours, (e) ten hours, (f) 24 hours, (g) 96 hours, and (h)
has fcc close-packed structure while -brass has 96 hours.
bcc less close-packed structure." Moreover, he
concluded that on the assumption of the equality of the diffusivities of copper and zinc, diffusion of these elements must
have occurred by the ring mechanism in which four or more atoms participate. He recalled that if he had insisted on the
inequality of these diffusivities to interpret the original boundary migration, Upthegrove would have opposed Kirkendall’s
Sc.D. thesis defense.

THE SECOND PAPER (1942)

After Kirkendall had completed his Sc.D. program, he was appointed an instructor at Wayne University. After he returned to
his old school, he wrote his second paper.3 In the abstract he asserted, "That this cyclic interchange in lattice position of
solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this
paper." The first paper and the dissertation did not reflect his own thought significantly. However, by this time he was no
longer influenced by his advisor; he wrote the second paper as a single author after he had confirmed the validity of his
experiments by repeating the measurements.

When he moved from the University of Michigan to Wayne University, Wayne had
only just been promoted to university status, and there was very limited equipment
in the laboratory. At the time, a friend who had been an alumnus of the University of
Michigan and was now on the staff of Ford Motor Company was working on the
manufacture of x-ray tubes. He gave Kirkendall the blueprints, manuals, and various
small parts of an x-ray tube, and Kirkendall made an x-ray tube by himself. As the
CoK -ray was the most effective for brass samples, an x-ray tube with a cobalt
target was produced. Furthermore, he obtained a high-voltage power supply for
Röntgen photography from a local dentist, and set up the x-ray diffraction
apparatus.

Disc-shaped specimens of 15 mm in diameter were used (Figure 4). Muntz metal

with 60.6% copper, 0.1% total impurities, and the balance in zinc was used for the
Figure 4. A schematic of a disc-shaped specimen, whose surface was electroplated with copper 5.12 mm in thickness. After
specimen used for the second paper.3 the diffusion anneals, metallographic observation of a section of the specimen was
done with the optical microscope, and the displacement between the original
interface and the / phase boundary was measured. After each removal of a 200-250 µm thick layer by a lathe, x-rays were
directed onto the specimen to measure the surface lattice parameter, which yielded zinc concentration profiles in the
specimen.

Figure 5 shows metallographic observations after successive diffusion anneal at 1,053 K up to 2,523.6 ks. As seen in the
figure, a layer with -brass phase was formed on both sides of the original interface. In particular, the -brass phase on the
-brass side consisted of large columnar grains, and the / interface was very clear because of the different crystal structures
in -brass (fcc) and -brass (bcc). On the other hand, in the copper-rich -brass phase, neither a distinct difference in the
grain size nor a clear -brass/copper interface boundary was observed because the crystal structure was the same. Figure 6

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depicts the zinc concentration profiles after the different anneals at 1,053 K.

According to Fick’s first law, diffusion mass flux (dm) across the
section A in the direction of a concentration gradient (dc/dx) for the
time interval (dt) can be expressed as

dm = -DA (dc/dx) dt

where D is diffusivity. Thus, one obtains

D = m /(average dc/dx) t

Applying the above equation to the result shown in Figure 6, the Figure 5. Metallographic observation at the successive
average of the diffusivity at 26% Zinc concentration at 1,053 K was diffusion anneal at 1,053 K until 2,523.6 ks: (a) one
hour, (b) six hours, (c) 24 hours, (d) 96 hours, (e) 701
hours, and (f) 701 hours.
D 3.8 X 10-13 m2s-1

This paper concluded that, at most, one-fifth of the movement of the original interface was due to volume shrinkage
accompanied by the phase change from - to -brass, while the remaining four-fifth was attributed to the zinc diffusion being
faster than that of copper. This explanation was in contrast to that in the first paper 2 and in the dissertation.

The paper1 was published in 1942. In the same year, Huntington and Seitz 8
evaluated the activation energy for self-diffusion in copper using electron theory
and suggested that self-diffusion occurs by a vacancy mechanism. However,
most researchers in the field did not fully recognize the significance of the paper.
World War II began, and neither paper received enough attention. I asked
Kirkendall whether he had known the existence of the Huntington-Seitz paper.
He had not; even after he wrote the third paper, he did not notice it.

THE THIRD PAPER (1947)

Alice Smigelskas, a student, joined the Kirkendall research a few years after the
second paper was published. In Kirkendall’s laboratory, there was only one
handmade electric furnace that often had to be used for diffusion annealing for
as long as two months. Smigelskas often had to adjust the furnace temperature,
Figure 6. Zinc concentration profiles after sitting down beside the furnace, because the furnace controller at that time was
different anneals at 1,053 K. not performing well. Kirkendall, reminiscing, said "In the early morning of
Christmas Day she called to tell me that she could not control the furnace so as
to lower the temperature. I was urged to come to my laboratory in a hurry, even
though there was a heavy snowfall, leaving my wife and small children at home."

There were two main features of the third paper. First, 70-30 brass (70% copper and 30% zinc) was adopted in order to avoid
the large volume change from -brass to -brass. Second, insoluble thin wires of molybdenum were inserted in the bonding
interface between the copper and the brass for clear observation of the movement of the original interface.

A brass bar 180 mm long and about 19 mm wide was surface-ground and polished with
abrasive paper. Molybdenum wires 127 mm in diameter were stretched lengthwise along
each of the two plane surfaces. The specimen was then electroplated with copper to a depth
of 250 mm or more during a period of four days. The bar consisted of an -brass core,
molybdenum wires, and a heavy layer of electroplated copper. Figure 7 is a sketch of the
cross section of the bar. Diffusion was carried out at 1,058 K for various lengths of time.
The distance between the two sets of molybdenum wire were measured, which identified
parallel diffusion planes or interfaces. X-ray diffraction was also carried out to obtain
diffusion penetration profiles. Figure 7. A sketch of a cross
section of a bar-shaped specimen
Kirkendall found a shrinkage of the brass core. Figure 8 shows the shift of each from the third paper.4
interfacehalf the total decrease in interface-to-interface distance. On the basis of the sample
analysis described in the second paper, the interdiffusion coefficient was evaluated from these diffusion penetration profiles
as

D 4 X 10-13 m2 s-1

This was in good agreement with the previous value 3.8 X 10 -13 m2s-1. In this way, he confirmed good reproducibility.
Furthermore, he also confirmed from the metallographic observation that zinc diffused into the copper faster than the copper
diffused into the brass.

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Thus, the significant result was the demonstration that when diffusion takes
place in -brass, the zinc diffuses much more rapidly than copper. Such
diffusion was accompanied by the shrinkage of the high-zinc -brass from
which zinc diffused out. It was stressed that studies of diffusion and related
phenomena consider an unequal interchange of solute and solvent atoms
during diffusion and that a mass shift of metal including the interface might
result. Finally, he concluded that "diffusion formulas based on an equal
interchange of solute and solvent atoms and a substantially stationery
interface will be in error."

MEHL’S CRITICISM AND EXPERIMENTS

Figure 8. The annealing time dependence of
interface shift.
When Kirkendall completed his work for the third paper,4 World War II had
ended. Most researchers’ interests shifted from military and applied research
toward basic research. In such circumstances, the diffusion problem
identified by Kirkendall drew much attention from many people. The paper was submitted to the editorial office of
Transactions of the AIME in April 1946, where the referee was a leading figure, R.F. Mehl, director of the Metals Research
Laboratory, Carnegie Institute of Technology. He rejected the submitted manuscript for more than six months because he
thought it was wrong. Mehl was also a consultant of the Climax Molybdenum Company Research Laboratory; Parke and
Ham of the Climax Molybdenum Company, friends of Kirkendall who were unable to look on with indifference any longer,
suggested to Mehl that, in fairness, he should criticize and make comments with his opinion in the discussion section of the
paper’s presentation at a meeting, instead of refusing its publication. At last, Mehl accepted their suggestion, and the
Smigelskas-Kirkendall paper4 was published in 1947. It consisted of five pages of text and, surprisingly, eight pages of
comments and discussion. (In those days, comments and discussion were freely published; there was enough space.)

Mehl still doubted the Kirkendall paper. Meanwhile, L.C.C. daSilva from Brazil joined his laboratory as a graduate student.
In order to verify that the Kirkendall Effect was wrong, Mehl let the student carry out systematic experiments for
interdiffusion, not only in Cu/ -brass, but also in Cu/Sn -solid solution, Cu/Al -solid solution, and in Cu/Ni, Cu/Au, and
Ag/Au diffusion couples. To the contrary of Mehl’s expectation, daSilva found that the marker movement was confirmed
and undoubtedly associated with the manner in which atoms move during diffusion (i.e., the Kirkendall Effect was
reproducible). Mehl continued to believe, however, that diffusion took place by a direct exchange mechanism so that D A=
D B.

A diffusion seminar was held October 21-27, 1950, during the 32nd ASM National Metal Congress at Chicago, where
top-ranking diffusion researchers such as L.S. Darken, C. Wells, J. Bardeen, C. Herring, H.B. Huntington, F. Seitz, R.F.
Mehl, D. Turnbull, and J.E. Burke joined together. The details of the seminar were reported in the literature. 9 In this
conference most of the attendees approved the validity of the Darken equation, which supported D A DBin interdiffusion, the
vacancy mechanism proposed by Huntington and Seitz, and the Kirkendall Effect. During the conference, Seitz thoroughly
persuaded Mehl, who, as before, had opposed the vacancy mechanism and the Kirkendall Effect. After a few days, he
admitted the validity of the Kirkendall Effect. Mehl himself officially announced in the closing remarks that the Kirkendall
Effect was acceptable and that, moreover, his student had much data to confirm the reproducibility of the effect for several
alloying systems.10

WHY KIRKENDALL STOPPED HIS RESEARCH CAREER

The search committee for professorships in American universities are in the habit of involving
several off-campus members. From 1945 to 1946, Kirkendall was a prospective candidate for
promotion to associate professor. According to a rumor at the time, Mehl’s rejection of the
Kirkendall Effect stopped Kirkendall from receiving the promotion to associate professorship,
and he gave up to pursue his academic career and change his job to secretary of AIME. Was it
true?

This question was my motivation to investigate the episode relating to Kirkendall. I was invited
to his home and had already spent as long as six hours enjoyably talking with him. If I were to
ask such a severe question directly, I was afraid that I would be impolite. But if I did not, I might
regret it later without having solved the problem. Accidentally (and fortunately), he offered me
his favorite Danish schnapps, Cherry Heering. My feelings became more comfortable, and I Ernest Kirkendall
realized this was a good opportunity to ask such severe questions. The doctor replied, "My
promotion to associate professor had already been approved. The rumor was never reliable! The salary of the secretary of the
AIME headquarters in New York City was attractive; it was more than twice the university’s just after World War II. I had
three children and had to pay high tuitions for their schools and living expenses if living away from home. For this economic
reason, I preferred the job change."

I asked him if he would have continued his research career if more people had accepted the Kirkendall Effect earlier, but he

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replied that he did not attribute much significance to the discovery, at least at that time. Although C.S. Smith tried to
persuade him to stay at the university, he preferred the administrative job from an economic point of view, and even if he had
accepted the promotion and stayed at the university, he would not have had any positive prospects for his research because of
insufficient research facilities.

CONCLUSION
After Kirkendall retired from his research life, he did not see Mehl for a long time. However, he visited Mehl just before he
died. Mehl heartily apologized to Kirkendall for his strong opposition concerning his review of the third paper. He added, "I
wish I had an effect which had my name like your Kirkendall Effect," and he asked Kirkendall to shake hands and be
reconciled.

ACKNOWLEDGEMENTS
I appreciate Dr. and Mrs. Kirkendall for their invitation, fruitful conversation, and useful comments on the manuscript. I
express my condolences to the loss of Mrs. Kirkendall on January 5, 1997. I also thank S. Rothman of Argonne National
Laboratory and J. Manning of the National Institute of Standards and Technology, M. Koiwa of Kyoto University, J.
Philibert of the University of Paris, and A.D. LeClaire of the Open University for useful information, and R.W. Cahn of the
University of Cambridge for valuable comments on the manuscript.

References
1. W.C. Roberts-Austen, Phil. Trans. Roy. Soc., A187 (1896), pp. 383-415.
2. E. Kirkendall, L. Thomassen, and C. Upthegrove, "Rates of Diffusion of Copper and Zinc in Alpha Brass," Trans. AIME,
133 (1939), pp. 186-203.
3. E.O. Kirkendall, "Diffusion of Zinc in Alpha Brass," Trans. AIME, 147 (1942), pp. 104-110.
4. A.D. Smigelskas and E.O. Kirkendall, "Zinc Diffusion in Alpha Brass," Trans. AIME, 171 (1947), pp. 130-142.
5. C.H. Desch, Repts. Brit. Assn. for Advancement of Sci., 82 (1912), pp. 348-372.
6. R.F. Mehl, Trans. AIME, 122 (1936), pp. 11-56.
7. A.I. Krynitsky, Metals and Alloys, 8 (1937), pp. 138-144; 173-179; 261.
8. H.B. Huntington and F. Seitz, Phys. Rev., 61 (1942), pp. 315-325.
9. Atom Movements (Metals Park, Ohio: ASM, 1951).
10. L.C.C. daSilva and R.F. Mehl, Trans. AIME, 191 (1951), pp. 155-173.

ABOUT THE AUTHOR

Hideo Nakajima is currently a professor at the Institute of Scientific and Industrial Research at Osaka University.

Copyright held by The Minerals, Metals & Materials Society, 1997

Direct questions about this or any other JOM page to [email protected].

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