ANL-6684

Chemistry
( T I D - 4 5 0 0 , 22nd Ed.)
AEC R e s e a r c h and
Development Report

ARGONNE NATIONAL LABORATORY

9700 South Cass Avenue
Argonne, Illinois 60440

THE MECHANISM AND KINETICS OF THE REACTION

BETWEEN NICKEL AND FLUORINE
by
R. L, J a r r y , W. H. Gunther,
and J. F i s c h e r

C h e m i c a l Engineering Division

August 1963

O p e r a t e d by The University of Chicago

under
C o n t r a c t W-31 - I 0 9 - e n g - 3 8
with the
U. S. Atomic E n e r g y C o m m i s s i o n

DISCLAIMER
This report was prepared as an account of work sponsored by an
agency of the United States Government. Neither the United States
Government nor any agency Thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or
usefulness of any information, apparatus, product, or process
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otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States
Government or any agency thereof.

DISCLAIMER
Portions of this document may be illegible in
electronic image products. Images are produced
from the best available original document.

TABLE O F CONTENTS
Page
ABSTRACT
I.
II.

III.

IV.
V.
VI.

INTRODUCTION

MECHANISM OF THE NICKEL-FLUORINE REACTION

A.

M a t e r i a l s , A p p a r a t u s , and E x p e r i m e n t a l P r o c e d u r e

B.

R e s u l t s and Discussion

11

THE KINETICS OF THE REACTION OF NICKEL WITH

FLUORINE. ,

15

A.

M a t e r i a l s , A p p a r a t u s , and E x p e r i m e n t a l P r o c e d u r e . . . . .

15

B.

R e s u l t s and D i s c u s s i o n

17

SUMMARY

25

ACKNOWLEDGMENTS

26

BIBLIOGRAPHY

27

LIST O F FIGURES

No.

Title

1.

Migration P r o c e s s e s in G a s - M e t a l Reactions

2.

Calculated Concentration of Radioactivity in Oxide Layer

Page
6

Based on the Cationic Vacancy Mechanism

3.

Nickel-63 Plating Cell

4.

Wedge Specimen for Impinging Scale E x p e r i m e n t

5.

M i c r o g r a p h of Impinging Nickel F l u o r i d e Scales

12

6.

M i c r o g r a p h of Impinging Nickel Oxide Scales . . . . . . . . . . . .

12

7.

M i c r o g r a p h of Autoradiographic Emulsion Showing

Nickel-63 Activity in Nickel F l u o r i d e Scale
M i c r o g r a p h of Autoradiographic Emulsion Showing
Nickel-63 Activity in Nickel Oxide Scale

8.
9.

10
.

10

13
13

Apparatus for the Study of the Kinetics of the N i c k e l - F l u o r i n e

Reaction

15

10.

Reaction V e s s e l and Nickel Block.

16

11.

Linear Plot of Rate of Reaction of Nickel with Fluorine in

the T e m p e r a t u r e Range from 300 to 600 C

12.

18

Logarithmic Plot of Rate of Reaction of Nickel with F l u o r i n e

in the T e m p e r a t u r e Range from 300 to 600 C . . . . . .

18

A r r h e n i u s Plot of P a r a b o l i c Rate Constants for the Reaction

Ni + F j -> NiF2 in the T e m p e r a t u r e Range from 300 to 600 C . .

19

Comparison of the Reaction between Fluorine and Nivac and

A-Nickel in the T e m p e r a t u r e Range from 400 to 600 C

20

The Fluorination of A-Nickel in the T e m p e r a t u r e Range from

400 to 600 C . . . . . . . . . . . . . . . . . . . . . . . .

21

16.

P r e s s u r e Dependence of the N i c k e l - F l u o r i n e R e a c t i o n . . . . . .

24

17.

Rate of Change of Scale Thickness as a Function of Fluorine

Pressure

24

13.
14.
15.

LIST O F TABLES
No.

Title

Page

1.

P a r a b o l i c Rate Constants for the N i c k e l - F l u o r i n e Reaction

Over the T e m p e r a t u r e Range from 3 00 to 600 C. . . . . . . . .

19

Nickel Fluoride Scale T h i c k n e s s e s after 1000 Min of

Reaction Timie for A - N i c k e l .

22

P a r a b o l i c Rate Constants for the N i c k e l - F l u o r i n e Reaction

at 500 C and Fluorine P r e s s u r e s of 100, 350 and 700 m m . .

22

The Effect of P r e s s u r e on the Rate of Buildup of A-Nickel

F l u o r i d e Scale at 600 C

23

2.

3.

4.

THE MECHANISM AND KINETICS OF THE REACTION

BETWEEN NICKEL AND FLUORINE
by
R. L. J a r r y , W. H. Gunther, and J. F i s c h e r

ABSTRACT
The mechanisxn and kinetics of the nickel-fluorine reaction have
been studied. M a r k e r (isotopic t r a c e r ) e x p e r i m e n t s , in which radioactive
nickel-63 was used, and s c a l e - i m p i n g e m e n t e x p e r i m e n t s , in which two
s c a l e s formed during the r e a c t i o n w e r e forced to impinge upon each other,
w e r e c a r r i e d out to d e t e r m i n e whether nickel or fluorine m i g r a t e s through
the nickel fluoride s c a l e f o r m e d during the fluorination of nickel. Similar
e x p e r i m e n t s w e r e p e r f o r m e d with the nickel-oxygen s y s t e m to verify the
e x p e r i m e n t a l r e s u l t s obtained in the nickel-fluorine study with those obtained in a r e a c t i o n of known m e c h a n i s m . The radioactive t r a c e r e x p e r i m e n t s indicated that fluorine m i g r a t e s through the growing fluoride scale.
This was shown by the lack of m o v e m e n t of the radioactive t r a c e r , which
was found at the nickel fluoride scale-fluorine gas interface. In the nickeloxygen e x p e r i m e n t s , the radioactivity was found to be distributed through
the oxide s c a l e in a m a n n e r p r e d i c t e d from the known m e c h a n i s m . This
r e s u l t was in a c c o r d with the accepted m e c h a n i s m for that reaction,
namely, that nickel m i g r a t e s through the nickel oxide scale to the nickel
oxide-gas interface. In the fluoride s c a l e - i m p i n g e m e n t e x p e r i m e n t s , the
existence of an interface between the two s c a l e s growing from opposing
s u r f a c e s indicated that fluorine is the m i g r a t i n g s p e c i e s . In the oxide
s c a l e - i m p i n g e m e n t e x p e r i m e n t s , a continuous scale was formied, thereby
indicating that nickel is the m i g r a t i n g species in this c a s e .
The k i n e t i c s of the nickel-fluorine reaction have been studied b e tween 300 and 600 C using high-purity and c o m m e r c i a l nickel. The p a r a bolic r a t e constants for the r e a c t i o n with high-purity nickel w e r e found to
be 9.8, 81, 4 6 1 , and I860 (/j g F z / s q cm)^ p e r minute at 300, 400, 500, and
600 C, r e s p e c t i v e l y .
No significant difference in reaction r a t e s for the two types of
nickel was noted except in the initial portion (less than 500 min) of the r e action period. The p a r a b o l i c r a t e was found to be independent of the p r e s s u r e of fluorine over the range of 100 to 700 m m Hg when the thickness of
the nickel fluoride scale was 10* A or l e s s . After a scale having a thickn e s s of about 10 A had been deposited, the r a t e of scale formation was
found to v a r y with the one-half power of the fluorine p r e s s u r e .

I. INTRODUCTION
Fluorine is used in fluoride volatility processing of spent nuclear
reactor fuels to convert uranium and plutonium to their respective hexafluorides. The best material of construction for use with fluorine at elevated temperatures, say 500 to 600 C, is nickel. Fluorine reacts with
nickel to form a coherent, adherent scale of nickel fluoride which acts
protectively by diminishing the rate of reaction. Several investigations
of the corrosion of nickel have been reported,(1 "3) and a recent publication summarizes the data available at the present time.(4) No description
of the mechanism of the nickel-fluorine reaction has been reported.
Oxidation reactions of metals and alloys which result in protective
scales, that is, a scale which controls the reaction rate in some manner
proportional to its thickness, have been treated according to the theory
developed by Wagner.(5) According to this theory, metal or nonmetai ions
are considered to be transported
across the growing scale to a reacFigure 1
tion interface. Concurrently with
MIGRATION PROCESSES IN GAS
the ion transport, vacancies, repreMETAL REACTIONS
senting vacant lattice sites, and
electrons travel through the scale,
thereby maintaining electrical neutrality across the scale. This scheme
is shown diagramimatically in Figure 1. It follows from this consideration that in the case for which
3xietal-ion migration predominates
the reaction occurs at the scale-gas
interface. When nonmetal-ion mi(A) Outward Migration of Positively Charged Metal Ions and Electrons, Reaction
,.
-, . ^^.^^ ^.i,^ ^ ^ . , ^ + 4 . ^ ^
Occurs at d)
g ration predominates, the reaction
(B) Inward Wigration of Negatively Charged Nonmetai Ions and Outward Migration O C C U r S a t t h e m e t a l - S C a l e i n t e r f a c e ,
of Electrons Reaction Occurs at (2)
^^^ classical example of the use of
this mechanistic approach has been the study of the oxidation of copperw)
in which it was shown that the copper ions migrated to the oxide-gas
interface.
The Wagner Theory further states that reactions producing protective scales follow a parabolic reaction rate law. The oxidation of nickel
has also been shown to follow the parabolic rate law,(6) and measurements
of the diffusion of nickel and oxygen in nickel oxide(7) have shown that the
diffusion rate of nickel is greater by several orders of magnitude than that
of oxygen.

Since reaction sites for the m i g r a t i n g m e t a l and nonmetai ions a r e

different (the f o r m e r r e a c t s at the s c a l e - g a s interface, the l a t t e r r e a c t s at
the m e t a l - s c a l e interface), the determination of the reaction site can s e r v e
as a m e a n s of elucidating the m e c h a n i s m of a reaction. Two different a p p r o a c h e s w e r e used to indicate the location of the reaction site in this
study of the nickel-fluorine reaction. To check the e x p e r i m e n t a l methods
with a reaction of known m e c h a n i s m s i m i l a r experiments w e r e p e r f o r m e d
with the nickel-oxygen s y s t e m . In the f i r s t experimental approach, a
radioactive t r a c e r , n i c k e l - 6 3 , was used as a s e l f - m a r k e r . Nickel-63 was
plated on the s p e c i m e n s to be fluorinated or oxidized and the radioactivity
in the r e a c t e d specimiens was located by autoradiographic m e a n s .
It is possible to p r e d i c t the position of the activity in the resulting
scale on the b a s i s of the work c a r r i e d out by Bardeen and associates.(S)
In this work, the expected distribution of the radioactive s e l f - m a r k e r was
calculated according to the Wagner t h e o r y and verified experimentally for
the copper-oxygen s y s t e m . Additional verification of the expected d i s t r i b u tion of the activity was obtained by Castellan and Moore.wj
The solid curve of Figure 2 shows the expected distribution when
m e t a l - i o n m i g r a t i o n p r e d o m i n a t e s . In this case, t h e r e is a diminution of
the radioactive t r a c e r from the oxide-gas interface to the m e t a l - s c a l e
interface. F o r the case in which nonmetal-ion m i g r a t i o n through the scale
p r e d o m i n a t e s , the isotopic t r a c e r would not be involved and the activity
would appear in a n a r r o w band at the s c a l e - g a s interface as shown by the
dotted line in F i g u r e 2. In the investigation of the oxidation of uranium by
Schnizlein et aL,(!'-') the isotope uranium-235 was used as a s e l f - m a r k e r .
The concentration of the alpha activity of the uranium-235 at the oxide-gas
interface showed that m i g r a t i o n of the nonmetai, oxygen, predominated in
this reaction.

Figure 2
CALCULATED CONCENTRATION O F
RADIOACTIVITY IN OXIDE LAYER
BASED ON THE CATIONIC
VACANCY MECHANISM

0.25

0.50

0.75

RELATIVE DISTANCE FROM METAL

The second technique used an e x p e r i m e n t in which the c h a r a c t e r of

the interface, at the point at which two s c a l e s of the s a m e m a t e r i a l , nickel
fluoride or nickel oxide, growing toward each other from n e a r l y p a r a l l e l
nickel s u r f a c e s would m e e t , as an indication of the m e c h a n i s m . (This t e c h nique will be r e f e r r e d to h e r e a f t e r as the "impinging s c a l e " technique.) If
m e t a l a t o m s w e r e the p r i n c i p a l species m i g r a t i n g through the scale to
r e a c t at the s c a l e - g a s interface, the two scale surfaces growing toward
one another would fuse into one scale as the m e t a l ions from one scale
surface m i g r a t e d into the other. If the mechanismi w e r e dependent on the
m o v e m e n t of the nonmetai a c r o s s the forming s c a l e s , the two s c a l e s would
not fuse upon coming together, and an interface would be p r e s e n t . This
technique was used by Schnizlein(lO) to identify the diffusing species in
the oxidation of u r a n i u m .
The kinetics of the nickel-fluorine reaction w e r e studied over the
t e m p e r a t u r e range from 300 to 600 C by a m a n o m e t r i c technique.

IL MECHANISM O F THE NICKEL-FLUORINE REACTION

A. M a t e r i a l s , A p p a r a t u s , and E x p e r i m e n t a l P r o c e d u r e
The fluorine used in this work was p r o c u r e d from the G e n e r a l
Chemical Company. The purity of the fluorine was a s s a y e d to be 98.2 v / o
by the m e r c u r y r e a c t i o n m e t h o d . ( l l ) Hydrogen fluoride was removed from
the fluorine by passing the gas through a sodium fluoride t r a p kept at about
100 C.
The nickel used was c o m m e r c i a l A-nickel which had a purity of
99.4 p e r c e n t . Analyses by c h e m i c a l and s p e c t r o g r a p h i c m e a n s showed that
the principal i m p u r i t i e s , e x p r e s s e d in p a r t s per million, w e r e as follows:
m a n g a n e s e , 2800; carbon, 700; iron, 1000; silicon, 800; and copper, 500.
The nickel-63 t r a c e r was obtained from Oak Ridge National Labor a t o r y in 5-mc lots as an acid chloride solution. Nickel-63 is a pure beta
e m i t t e r with an energy of 63 kev. A s m a l l amount of nickel-59, with a
K - c a p t u r e X r a y of 1.07 Mev, was p r e s e n t as a contaminant to the extent
of about 0.01 p e r c e n t . This g a m m a activity was not objectionable as it did
not interfere with the a u t o r a d i o g r a p h i c p r o c e s s .
Two types of stripping film w e r e used in this work: Kodak E x p e r i m e n t a l P e r m e a b l e Base Stripping F i l m , which consisted of b-jl emulsion
overload with 5 jU of gelatin on a r o l l - f i l m backing., and Kodak Autoradiographic Filxn AR-10, which consisted of a 5-/i-thick emulsion overlaid with
10 /i of gelatin on a g l a s s - p l a t e backing. Because of the g r e a t e r thickness
of the AR-10 film, it was found to be e a s i e r to handle for this type of u s e .
The fluorination and oxidation e x p e r i m e n t s w e r e c a r r i e d out in
e l e c t r i c a l l y heated tube r e a c t o r s . The tube r e a c t o r for the fluorinations
was a 2-ft section of 2-in. nickel pipe with a welded plate at one end and a
flange c l o s u r e at the other. A thermocouple tube made of -j-in. nickel tubing
was welded through the top flange and extended to the midpoint of the r e a c tion tube. Hooks welded to the thermocouple tube w e r e used to support the
sainple s p e c i m e n s . A second--in. nickel tube, which was also welded
through the top flange, and which extended to within one inch of the bottom
of the r e a c t i o n tube, s e r v e d as an inlet for fluorine g a s . The tube r e a c t o r
for the oxidation e x p e r i m e n t s was a 10-in. section of 2 - i n . - d i a m e t e r nickel
tubing with a welded cap at one end and a flange c l o s u r e at the other.
A nickel manifold connected to the r e a c t o r s y s t e m s provided a c c e s s
for vacuum, fluorine and oxygen s o u r c e s , and p r e s s u r e - m e a s u r i n g devices.
Both Bourdon-type gages and a B o o t h - C r o m e r null-point gage w e r e used for
pressure measurements.

T e m p e r a t u r e "was maintained by tube furnaces through a p r o p o r t i o n ally circuited V a r i a c controlled by a p y r o m e t e r c o n t r o l l e r . The p y r o m e t e r

was activated by a c h r o m e l - a l u m e l thermocouple
Figure 3
in the thermocouple well of the r e a c t o r . A s e c ond
c h r o m e l - a l u m e l thermocouple in the r e a c t o r
NICKEL-63 PLATING
was used in conjunction with a Brown potentioCELL
m e t e r for m e a s u r i n g and r e c o r d i n g the r e a c tion t e m p e r a t u r e .
(-) CATHODE

I 24/4C

Nickel containing the nickel-63 t r a c e r

was plated on the nickel coupons with the plating
cell shown d i a g r a m m a t i c a l l y in Figure 3. The
cell was constructed of 3 0 - m m P y r e x tubing,
80 m m in length, capped with a 24/40 standard
t a p e r joint. The platinum leads w e r e sealed
through the P y r e x for support without a t t e m p t ing to produce g a s - t i g h t s e a l s .

The coupons to be plated with nickel-63

w e r e one cm by five cm by 0.16 cm, and w e r e
polished with o n e - m i c r o n diamond paste and
then d e g r e a s e d using acetone. The acid chloride
NICKEL COUPON
solution containing the nickel-63 was made basic
soLUTiorv
LEVEL
with ammonia to form the t e t r a a m m i n e complex.
A plating time of about 15 m i n at 1 0 m a and
2.2 v was r e q u i r e d to obtain a 2 -/i-thick plate
of nickel. Only the lower 1-2 cm of the coupon
was plated, the r e m a i n d e r of the coupon being m a s k e d with paraffin. The
thickness of the plate was calculated from the weight gain of the coupon,
the g e o m e t r i c a r e a , and the t h e o r e t i c a l c r y s t a l density of nickel.
Coupons used for the impinging scale e x p e r i m e n t s w e r e one cm by
three cm by 0.16 era. A r e a c t i o n specimen was p r e p a r e d by welding
two coupons together along the o n e - c m edges so as to make an angle of
about one degree between s u r f a c e s , as shown in F i g u r e 4.
Figure 4
WEDGE SPECIMEN FOR IMPINGING
SCALE EXPERIMENT
'\

018cm

The plated coupons and welded impinging scale specimens w e r e

r e a c t e d with fluorine or oxygen in the following m a n n e r . The p r e p a r e d
coupons w e r e placed in the r e a c t o r , and the s y s t e m was evacuated and
tested for l e a k s . Following this step, the r e a c t a n t gas was admitted and
the heating period was begun. This p r o c e d u r e was followed because it
was found that s t a r t i n g the heating cycle after the fluorine was admitted
to the r e a c t o r produced a m o r e a d h e r e n t s c a l e . Fluorinations w e r e c a r r i e d
out at 600 to 700 C for p e r i o d s of 24 to 36 h r . The oxidations w e r e run at
about 1000 C for p e r i o d s of 48 to 72 h r . After the r e a c t i o n period, the
r e a c t o r was evacuated and allowed to cool slowly for a period of about
12 to 24 hr before the s a m p l e s w e r e r e m o v e d .
In o r d e r to examine the s p e c i m e n s m e t a l l o g r a p h i c a l l y or apply the
autoradiographic emulsion, the coupons w e r e mounted in Bakelite. The
mounts w e r e then sectioned n o r m a l l y to the short axis of the coupon for
the nickel-63 s p e c i m e n s and n o r m a l l y to the long axis for the impinging
scale s p e c i m e n s .
The a u t o r a d i o g r a p h i c technique d e s c r i b e d by G o m b e r g l l ^ ) was used
in these e x p e r i m e n t s . The specimen, mounted in Bakelite, was p r e p a r e d
by polishing with 600 g r i t m e t a l l o g r a p h i c p a p e r . The mount was then cleaned
in an u l t r a s o n i c bath to e n s u r e the r e m o v a l of r e s i d u a l activity s p r e a d over
the surface during the polishing.
The emulsion, which was about 5-/J. in t h i c k n e s s , plus the 5 - or
10-,a-thick gelatin l a y e r , was r e m o v e d from the filmi backing. The e m u l sion, active side down, was floated onto the surface of the specimen using
a drop of w a t e r containing a t r a c e of wetting agent. An exposure time of
five days was used, after which the emulsion was developed. After developm e n t the e m u l s i o n was r e m o v e d from the mount and mounted on a standard
m i c r o s c o p e slide. Removal of the developed einulsion from the specimen
was found d e s i r a b l e b e c a u s e the background made it difficult to observe the
details of the exposed emulsion. The activity and replication of the surface
could easily be o b s e r v e d when the emulsion was mounted on the glass slide.
F r o m the r e p l i c a t e d surface it was possible to identify the interface regions
without ambiguity,
B. Results and D i s c u s s i o n
The r e s u l t s of the impinging scale e x p e r i m e n t s a r e shown in F i g u r e s 5 and 6 which a r e m i c r o g r a p h s of s a m p l e s which have been r e a c t e d
with fluorine and oxygen, r e s p e c t i v e l y . It is a p p a r e n t from Figure 5, that
the impinging fluoride s c a l e s a r e s e p a r a t e d by an interface, which indicates
that fluorine m i g r a t e d from the g a s - s o l i d interface through the fluoride scale
to the n i c k e l - n i c k e l fluoride interface and that m e t a l m i g r a t i o n was negligible.

Figure 5
MICROGRAPH O F IMPINGING NICKEL F L U O R I D E SCALES

JOOu:

A -

A and A\ nickel substrates; B and B', nickel fluoride scales; C, interface between nickel fluoride scales.
Figure 6
MICROGRAPH O F IMPINGING NICKEL OXIDE SCALES

lOOn

.*>. %

^ -9 ^ ^

^ \ '

A and A\ nickel substrates; B, continuous nickel oxide scale.

13

I n F i g u r e 6, a c o n t i n u o u s o x i d e s c a l e i s s e e n b e t w e e n t h e t w o m e t a l
s u r f a c e s . T h i s c o n f i r m s the fact that the m e t a l m i g r a t e s t h r o u g h the m e t a l
oxide s c a l e , a n d r e a c t s at the m e t a l o x i d e - g a s i n t e r f a c e to p r o d u c e a c o n tinuous oxide film.
C o n s i d e r a b l e p o r o s i t y in t h e n i c k e l oxide s c a l e is e v i d e n t in the
m i c r o g r a p h r e p r o d u c e d i n F i g u r e 6. T h e a d j a c e n t m e t a l s u r f a c e s , w h i c h
w e r e e t c h e d to p r o v i d e m o r e c o n t r a s t w i t h the s c a l e , a l s o exhibit p o r o s i t y .
T h e p o r o s i t y of t h e o x i d e s c a l e c a n b e a t t r i b u t e d t o t h e r e m o v a l of c a t i o n
v a c a n c i e s by c o n d e n s a t i o n and p r e c i p i t a t i o n within the oxide p h a s e . This
m e c h a n i s m f o r t h e r e m o v a l of c a t i o n v a c a n c i e s f r o m t h e m e t a l o x i d a t i o n
s y s t e m w a s p r o p o s e d by B i r c l i e n a l l . ( 1 3 ) T h e v a c a n c i e s a r e p r e s e n t in the
s y s t e m a s a r e s u l t of c a t i o n d i f f u s i o n d u r i n g t h e r e a c t i o n . T h e p r e s e n c e
of w h a t a p p e a r t o b e v o i d s i n t h e m e t a l s u b s t r a t e m a y b e t h e r e s u l t of t h e
p r o d u c t i o n of v a c a n c i e s a t t h e m e t a l - o x i d e i n t e r f a c e a n d t h e i r s u b s e q u e n t
m i g r a t i o n to the g r o w i n g v o i d s within the m e t a l . T h i s , a c c o r d i n g to
V e r m i l y e a , ' 1 4 ) r e s u l t s f r o m t h e m o v e m e n t of a t o m s f r o m t h e m e t a l i n t o
the oxide f r o m positions other than p r e f e r r e d sites, e.g., l a t t i c e - s t e p
positions.
The r e s u l t s obtained for the radioactivity t r a c e r e x p e r i m e n t s a r e
s h o w n i n F i g u r e s 7 a n d 8. F i g u r e 7 i s a m i c r o g r a p h of t h e a u t o r a d i o g r a p h
of t h e n i c k e l f l u o r i d e s c a l e . T h i s m i c r o g r a p h c l e a r l y s h o w s a n a r r o w b a n d
Figure 7
MICROGRAPH OF AUTORADIOGRAPHIC EMULSION
SHOWING NICKEL-63 ACTIVITY IN NICKEL
FLUORIDE SCALE

Figure 8
MICROGRAPH OF AUTORADIOGRAPHIC EMULSION
SHOWING NICKEL-63 ACTIVITY IN NICKEL
OXIDE SCALE

lOOfi

A, original location of nickel substrate; B, nickelnickel fluoride interface; C, nickel fluoride scale;
D, darken zone in emulsion due to radioactivity;
E, location of nickel fluoride-fluorine gas interface;
F, original location of dental rubber mounting.

A, original location of nickel substrate; B, nickelnickel oxide interface; C, nickel oxide scale;
D, darkened area of emulsion due to radioactivity;
E, location of nickel oxide-oxygen gas interface;
F, original location of Bakelite mounting.

of activity at the position of the scale-fluorine i n t e r f a c e . The line, indicated by a r r o w E in F i g u r e 7, locates the position of the s c a l e - g a s i n t e r face. The width of the d a r k e n e d portion of the einulsion is g r e a t e r than the
thickness of the portion of the nickel fluoride film occupied by the r a d i o active nickel because of the d i s p e r s i o n of the beta r a y s in the 5-,u-thick
emulsion. F r o m the location and distribution of the radioactivity, it can be
deduced that fluorine is the m i g r a t i n g species in this reaction and that it
m i g r a t e s through the nickel fluoride film to the m e t a l surface w h e r e it
r e a c t s with the nickel.
Figure 8 is a m i c r o g r a p h of an a u t o r a d i o g r a p h of the nickel oxide
scale. The nickel activity is seen to p e n e t r a t e into the nickel oxide s c a l e .
The l i n e a r penetration n o r m a l to the surface of the film is as m u c h as
70 p e r c e n t of the thickness of the oxide film.
Bardeen(8) p r e d i c t e d that the activity would extend to the n i c k e l nickel oxide interface. However, the diminution of the activity close to
the interface m a y not be r e s o l v e d in the autoradiograph. In addition,
Birchenall(l3) has pointed out that the expected distribution of radioactive
t r a c e r has been found by other w o r k e r s to drop off rapidly in the region
near the m e t a l - o x i d e interface. He has postulated that this effect is due
to an abrupt change in the diffusion coefficient owing to the porosity in
the scale n e a r the m e t a l - o x i d e interface. P o r o s i t y has been observed in
the nickel oxide s c a l e s produced in these e x p e r i m e n t s and could t h e r e f o r e
account for the activity distribution found in Figure 8.
The r e s u l t s obtained in both types of m a r k e r e x p e r i m e n t s indicate
that fluorine, r a t h e r than nickel, m i g r a t e s through the fluoride scale d u r ing the c o u r s e of the r e a c t i o n . Fluorine could r e a c h the m e t a l surface by
g r o s s m o v e m e n t through p o r e s and c r a c k s in the fluoride scale or by some
t r a n s p o r t p r o c e s s through the bulk of the s c a l e . Since the kinetics of the
r e a c t i o n have been shown to follow a p a r a b o l i c r a t e , * it is m o r e likely
that the m e c h a n i s m involves the t r a n s p o r t of fluorine through the bulk of
the nickel fluoride s c a l e . Resolution of the mode of t r a n s f e r of fluorine
from the gas phase through the fluoride scale r e q u i r e s further e x p e r i m e n t a l work. The evidence obtained fromi the m a r k e r e x p e r i m e n t s for
the nickel-oxygen r e a c t i o n is in a c c o r d with the accepted m e t a l - i o n diffusion m e c h a n i s m for that r e a c t i o n .

*See Section III of this r e p o r t .

15

III.
A.

T H E KINETICS O F THE REACTION OF NICKEL WITH FLUORINE

M a t e r i a l s , Apparatus, and E x p e r i m e n t a l

Procedure

Both h i g h - p u r i t y nickel and c o m m e r c i a l A - n i c k e l w e r e used in

t h e s e e x p e r i m e n t s . The h i g h - p u r i t y nickel, d e s i g n a t e d by the n a m e N i v a c ,
w a s o b t a i n e d f r o m t h e C r u c i b l e S t e e l C o m p a n y a n d w a s p r e p a r e d by v a c u u m m e l t i n g . A n a l y s e s of t h e N i v a c n i c k e l b y c h e m i c a l a n d s p e c t r o g r a p h i c
n i e a n s i n d i c a t e d 9 9 . 9 2 p e r c e n t n i c k e l . T h e p r i n c i p a l i m p u r i t i e s , in p a r t s
p e r million, w e r e as follows: cobalt, 300; iron, 400; c a r b o n , 82; oxygen,
2 8 ; a n d n i t r o g e n , 3 1 . T h e p r o p e r t i e s of t h e A - n i c k e l a r e d e s c r i b e d i n
Section II.A.
The fluorine u s e d in t h e s e e x p e r i m e n t s w a s purified by distillation
a n d w a s a s s a y e d by r e a c t i o n w i t h m e r c u r y . ( 1 1 ) It w a s f o u n d to b e 9 9 . 9 3 v / o
p e r c e n t f l u o r i n e . T h e i m p u r i t i e s in p a r t s p e r m i l l i o n as d e t e r m i n e d by
m a s s s p e c t r o g r a p h i c a n a l y s i s of t h e r e s i d u a l g a s w e r e a s f o l l o w s : o x y g e n ,
396; w a t e r , 117; n i t r o g e n , 78; c a r b o n
Fi,.;urc J
d i o x i d e , 30; s i l i c o n t e t r a f l u o r i d e , 30;
a n d a r g o n , 12.
APPAR\TUS FOR THE iTUDY OF THE
*
KINLTICS OF THE NICKELFLUORINE REACTION
^^^ s y s t e m u s e d f o r t h e s e
m e a s u r e m e n t s is shown schematically
. ' , IANT [R/Fttar.-E
i n F i g u r e 9. I t c o n s i s t s of ( l ) a r e a c -
'

t i o n v e s s e l cind t u b e f u r n a c e , (2) a m a n r.^-j^l'^ll^t

-"^'-rrr' "''
ifold with o u t l e t s for v a c u u m , f l u o r i n e
I
I ^-J-.^-^ , -[...
supply, and the p r e s s u r e - m e a s u r i n g
" ' ' ' "" "^
" '
' ^
d e v i c e s , a n d (3) a t h e r m o s t a t t e d s e c j
"
i .
t i o n c o n t a i n i n g c a l i b r a t e d v e s s e l s of
wr.jf,- u^ip
^
^ ui' - = '
d i f f e r e n t v o l u m e s . T h e v o l u m e s of
1
, .^i,
a p p r o p r i a t e p o r t i o n s of t h e m a n i f o l d ,
.A n-r
""^f
the t h e r m o s t a t t e d v e s s e l s , and the
p r e s s u r e transmitter section were det e r m i n e d by P V T m e a s u r e m e n t s , u s i n g
^ Fjpr
^a...r
a water-calibrated standard volume.
%L:: J K E L i i - '
FL

ll\lH TUBF FU^NA E

-^

T h e i n t e r n a l s u r f a c e s of t h e r e action v e s s e l s s e r v e d as the nickel r e actant. The vessels w e r e fabricated from either Nivac sheet or A-nickel
tubing and s h e e t by h e l i u m - s h i e l d e d a r c welding. The v e s s e l s w e r e about
4 i n . i n l e n g t h a n d o n e i n c h in d i a m e t e r ; e a c h v e s s e l h a d a v o l u m e of a b o u t
4 7 c c a n d a n a r e a of a b o u t 9 5 s q c m . T h e N i v a c n i c k e l s h e e t w a s a b o u t
20 m i l s i n t h i c k n e s s a n d h a d b e e n v a c u u m a n n e a l e d ; t h e A - n i c k e l w a s u s e d
a s r e c e i v e d . D u r i n g t h e f o r m i n g a n d w e l d i n g of t h e v e s s e l s , s p e c i a l c a r e
w a s t a k e n t o p r e v e n t c o n t a n i i n a t i o n of t h e m e t a l , a n d t h e f a b r i c a t i o n w a s
b r o k e n up into steps b e t w e e n which the s u b a s s e m b l i e s w e r e cleaned and
d e g r e a s e d . A l e n g t h of - g - - i n . - d i a m e t e r A - n i c k e l t u b i n g w a s w e l d e d t h r o u g h
t h e t o p p l a t e of e a c h v e s s e l t o s e r v e a s t h e c o n n e c t i o n t o t h e m a n i f o l d .

16

The r e a c t i o n v e s s e l s w e r e held in a 10-in.-long nickel cylinder

which in turn fitted snugly into a 2-|--in. tubular furnace. This section of
the a p p a r a t u s is shown schematically in F i g u r e 10. In addition to the hole
drilled to hold the r e a c t i o n v e s s e l s , two thermocouple wells w e r e drilled
in the block, one t e r m i n a t i n g at the level of the midpoint and the other at
the bottom of the r e a c t i o n v e s s e l . The t e m p e r a t u r e of the tube furnace
was controlled by m e a n s of a p y r o m e t e r - i n d i c a t o r - c o n t r o l l e r through a
proportional c i r c u i t e d V a r i a c . The p y r o m e t e r was actuated by the output
of a c h r o m e l - a l u m e l thermocouple placed n e a r the r e s i s t a n c e winding of
the tubular furnace.
F i g u r e 10
REACTION A^ESSEL AND NICKEL BLOCK
TO MANIFOLD

.1

HOKE 413 A VALVE

SWAGELOK FITTING

NICKEL BLOCK
10 ID LONG
2 1/Zm DIAMETER

CONTROL
THERMOCOUPLE

ARGON

P l a t i n u m - 9 0 p e r c e n t platinum, 10 p e r c e n t rhodium thermocouples

w e r e used to sense the t e m p e r a t u r e of the r e a c t i o n v e s s e l . A Rubicon
type B potentiometer and a s s o c i a t e d standard cell and galvanometer w e r e
utilized to m e a s u r e the output of the t h e r m o c o u p l e s . T e m p e r a t u r e control
during a r e a c t i o n period was within one degree C.

The p r e s s u r e s on the i n e r t side of the nickel diaphragms of the

B o o t h - C r o m e r e l e c t r i c a l p r e s s u r e t r a n s m i t t e r s w e r e m e a s u r e d with either
a well-type m e r c u r y m a n o m e t e r or a U-tube m a n o m e t e r filled with
Octoil-S.
At the s t a r t of an e x p e r i m e n t the nickel v e s s e l was attached to the
n-ianifold, evacuated., and t e s t e d for l e a k s . The evacuated v e s s e l was then
heated to the r e a c t i o n t e m p e r a t u r e and fluorine was admitted to a p r e s s u r e
of 700 m m of Hg, At this points p r e s s u r e and time r e c o r d i n g s w e r e s t a r t e d .
The changes in p r e s s u r e w e r e r e c o r d e d at suitable tinie i n t e r v a l s : at
y - m i n i n t e r v a l s for the f i r s t 1-2 min, at l-niin i n t e r v a l s for the f i r s t half
hour5 and then at gradually lengthening t i m e i n t e r v a l s as the r e a c t i o n slowed
down. The p r e s s u r e in the s y s t e m was kept within 25 m m of the initial
p r e s s u r e by interi-nittent additions of fluorine as the p r e s s u r e dropped.
P r e s s u r e readings during the initial r a p i d portion of the reaction w e r e made
with a m e r c u r y m a n o m e t e r . Subsequent readings w e r e made using an
Octoil-S-filled m a n o m e t e r to utilize its g r e a t e r sensitivity.
F o r overnight periods., when the apparatus was left unattended, one
of the b a l l a s t volumes was included in the reaction s y s t e m so t h a t the p r e s s u r e in the s y s t e m would not drop below the specified value. The quantity
of fluorine in the r e a c t i o n volume was calculated from values of the p r e s s u r e ,
volumesj and t e m p e r a t u r e s of the various sections of the a p p a r a t u s involved,
B. R e s u l t s and Discussion
The r e s u l t s obtained in the nickel-fluorine kinetic e x p e r i m e n t s with
Nivac nickel over the t e m p e r a t u r e r a n g e from 300 to 600 C a r e shown in
F i g u r e 11, in which micrograi-ns of fluorine consumed per sq c m of nickel
surface a r e plotted v e r s u s the r e a c t i o n time in m i n u t e s . The e x p e r i m e n t s
w e r e run for about 2000 min at each t e m p e r a t u r e .
In F i g u r e 12 the data a r e p r e s e n t e d as a log-log function of the s a m e
coordinates used in F i g u r e 11, In the construction of these plots the data
for the f i r s t minute of r e a c t i o n time w e r e discarded, because the reaction
is initially governed by a r a n d o m selection of reaction sites due to activity
differences over the nickel s u r f a c e . The reaction p r o c e e d s rapidly on these
s i t e s in the m a n n e r of a nucleation p r o c e s s which., by subsequent outgrowth
and c o a l e s c e n c e of growth s i t e s , r e s u l t s in a continuous fluoride scale over
the entire nickel s u r f a c e . In the initial phase, the r e a c t i o n is not controlled
by the t r a n s p o r t of fluorine through a nickel fluoride b a r r i e r , as is the c a s e
once a continuous fluoride scale is p r e s e n t over the entire nickel surface.

18

F i g u r e 11
LINEAR P L O T OF RATE OF REACTION OF NICKEL WITH FLUORINE
IN THE TEMPERATURE RANGE FROM 300 TO 600 C
F l u o r i n e P r e s s u r e : 700 25 m m
Material:
Nivac nickel

2000

F i g u r e 12
LOGARITHMIC P L O T OF RATE OF REACTION OF NICKEL WITH
FLUORINE IN THE TEMPERATURE RANGE FROM 300 TO 600 C
Fluorine P r e s s u r e :
Material:
Nivac Nickel:
Fluorine:

700 + 25 m m
99.92%
99.93%

1000

54,800

5,480 111

100
TIME,minutes

1000

54 8

19

F o r these log-log plots the r e c i p r o c a l s of the slopes a r e the values

of n in the equation w"- = kt, in which w is the fluorine consumed per sq
c m of nickel surface, k is the reaction r a t e constant, and t is the t i m e .
Values of n d e t e r m i n e d graphically from the plots of F i g u r e 12 a r e listed
above the a p p r o p r i a t e linear sections. These values indicate that the reaction
initially follows a parabolic r a t e law, but that after a period of time the
r e a c t i o n slows down, conforming to a cubic or slower r a t e . The parabolic
r a t e constants a r e listed in Table 1, and the logarithms of these r a t e constants a r e plotted v e r s u s l / T in F i g u r e 13. The slope of this plot yields an
activation energy of 17 k c a l / m o l e .
Table 1
PARABOLIC RATE CONSTANTS FOR THE NICKELFLUORINE REACTION OVER THE TEMPERATURE
RANGE FROM 300 TO 600 C
M a t e r i a l : Nickel, Nivac 99.92%
F l u o r i n e , 99.93%

Temperature
(C)

Value of
n

Parabolic
Rate Constant
(MgFz/sq c m ) V m i n

300
400
500
600

1.9
1.9
2.2
1.9

9.8
81.0
461
1860

F i g u r e 13
ARRHENIUS PLOT OF PARABOLIC RATE
CONSTANTS FOR THE REACTION
Ni + F2 - NiFa IN THE TEMPERATURE RANGE FROM
300 TO 600 C

13

600

530

14
15
l/T, K X 10^
400
TEMPERATURE, C

20

R e s u l t s obtained in e x p e r i m e n t s with A - n i c k e l at 400, 500, and

600 C a r e shown in F i g u r e 14; included on the plot a r e the data for Nivac
nickel at the same t e m p e r a t u r e s . F r o m these data, it is a p p a r e n t that the
reaction between fluorine and A-nickel is slower at a given t e m p e r a t u r e
than that between fluorine and Nivac nickel. This difference is g r e a t e s t
during the initial p e r i o d s of the r e a c t i o n s , and b e c o m e s l e s s pronounced
with time and at higher t e m p e r a t u r e s . This is i l l u s t r a t e d by the fluorine
consunaption and scale thickness data at various r e a c t i o n t i m e s . The scale
t h i c k n e s s e s w e r e calculated by use of the t h e o r e t i c a l density for nickel
fluoride: 4.63 g/cm^ based on X - r a y data.
F i g u r e 14
COMPARISON OF THE REACTION BETWEEN FLUORINE
AND NIVAC AND A-NICKEL IN THE TEMPERATURE
RANGE FROM 400 TO 600 C
P r e s s u r e : 700 25 m m
M a t e r i a l : NV - Nivac, 99.92% purity
AN - A-nickel, ~99.4% purity

1000
TIME, minutes

The data show that the r a t e of formation of nickel fluoride scale at

600 C b e c o m e s identical for the two nickel s a m p l e s at reaction t i m e s
g r e a t e r than 500 min. At 500 C this leveling off of the r a t e of scale formation does not occur until 1000 min of r e a c t i o n time have elapsed. At
400 C it would apparently r e q u i r e a longer r e a c t i o n period than that used
in these experii-nents to r e a c h the leveling-off period. F r o m these data it
can be concluded that, after a c e r t a i n scale thickness has been formed the
continuing fluorine consumption of the s y s t e m will be constant and independent of the purity of the nickel.
At the p r e s e n t time an explanation for the difference in reactivity
can be attributed to two v a r i a b l e s : (l) the differences in purity and
(2) the grain size of the two types of nickel. Differences in the amounts of

the main i m p u r i t i e s in the two types of nickel, in p a r t s per million, a r e iron,

400 v e r s u s 1000; carbon, 80 v e r s u s 700; silicon, 100 v e r s u s 800; and copper,
100 v e r s u s 500, for Nivac and A-nickel, respectively. Estimation of the
a v e r a g e g r a i n size was made using the ASTM method designated E91-51T
(ASTM Standards 1952, P a r t 2, Nonferrous Metals). In this method,
m i c r o g r a p h s (magnification lOOX) of polished and etched samples a r e c o m p a r e d with m i c r o g r a p h s of a standard grain size s e r i e s . By this method,
it was d e t e r m i n e d that the average g r a i n size of the A-nickel was 0.11 m m
and that of the Nivac nickel was 0.03 m m . It is possible, therefore, that
the higher initial reactivity of the Nivac nickel could be due to the s m a l l
g r a i n size of the Nivac nickel and the consequent g r e a t e r grain-boundary
area.
A c o m p a r i s o n of the r a t e constants at various t e m p e r a t u r e s could
not be made for the A-nickel because of a change in the order of the r e action with t e m p e r a t u r e . This variation is shown in the log-log plots of
F i g u r e 15. At 400 and 500 C, the reaction appears to follow a logarithmic
r a t e law; at 600 C the r e a c t i o n approaches a parabolic r a t e law behavior.
This change in o r d e r was also noted by Steunenberg et al.(l5) in a previous
study of the kinetics of the nickel-fluorine reaction. The r e s u l t s obtained
in that work and in the p r e s e n t study a r e in good agreement, as is shown
in Table 2, in which the nickel fluoride scale thicknesses formed after a
reaction time of 1000 min at various t e m p e r a t u r e s a r e compared. In the
previous study by Steunenberg, A-nickel and c o m m e r c i a l tank fluorine of
g r e a t e r than 99 p e r c e n t purity were used.
F i g u r e 15
THE FLUORINATION OF A-NICKEL IN THE
TEMPERATURE RANGE FROM 400 TO 600 C
lOOO:

100

g
X,

10

i
1

10

100
TIME mirutes

1000

22

Table 2
NICKEL FLUORIDE SCALE THICKNESSES AFTER
1000 MIN OF REACTION TIME FOR A-NICKEL
Nickel Fluoride Scale T h i c k n e s s , A
Temperature
(C)

This Study

Steunenberg et al.( 15)

400
500
600

4,400
8,200
29,000

3.800
9,200
30,000

G a s - m e t a l r e a c t i o n s in which the r a t e s a r e controlled by a diffusion

p r o c e s s and a r e dependent on the t h i c k n e s s of the s c a l e f o r m e d s o m e t i m e s
show a p r e s s u r e dependence of a fractional o r d e r . Two e x p e r i m e n t s at each
of the following p r e s s u r e s of fluorine: 100, 350, and 700 m m Hg, w e r e made
at 500 C with Nivac nickel. Ultimate fluoride scale t h i c k n e s s e s obtained in
these experimients after 1500 to 2000 m i n of reaction t i m e w e r e a p p r o x i m a t e l y 17,000 A. The r e s u l t s of these reactions did not indicate a p r e s s u r e
dependence of the r e a c t i o n r a t e beyond the reproducibility of the data, a p p r o x i m a t e l y 10 p e r c e n t . P a r a b o l i c r a t e constants obtained from these data
a r e l i s t e d in Table 3, along with the a v e r a g e values at e a c h p r e s s u r e and the
a v e r a g e of the six r a t e c o n s t a n t s . It is a p p a r e n t from t h e s e r a t e constants
that the effect of p r e s s u r e on the r e a c t i o n over the r a n g e covered in this
work m u s t be l e s s than the magnitude of the deviation between r u n s .
Table 3
PARABOLIC RATE CONSTANTS FOR THE NICKEL-FLUORINE
REACTION AT 500 C AND FLUORINE PRESSURES O F
100, 350, AND 700 m m
Material:

Nivac nickel, 99.92%

F l u o r i n e , 99.93%
Final Scale T h i c k n e s s : ~1.7 x 10* A
P a r a b o l i c Rate Constants

Pressure
(mm)

(Mg F a / sq c m ) y m i n

Average Values

700
700

461
387

424 37

350
350

370
322

346 23

100
100

355
438

396 41

Average of 6 Constants = 388 4 0

23

Work p e r f o r m e d at the Gaseous Diffusion Plant at Oak Ridge by

Hale and coworkers(2) showed the r a t e for the nickel-fluorine reaction to
be p r e s s u r e dependent in the c a s e of s a m p l e s having initial nickel fluoride
s c a l e s of about 2.5 x 10^ A in t h i c k n e s s . The data w e r e used to derive the
constants in the following equation:
dx/dt = kp"^
in which dx/dt is the r a t e of growth of the fluoride scale, k is the r a t e constant, and p is the p r e s s u r e . F r o m the slope of a log-log plot of dx/dt
v e r s u s p for their data at 600 C, a value of n of 0.87 was obtained.
These m e a s u r e m e n t s w e r e r e p e a t e d by us with both A-nickel and
Nivac nickel s a m p l e s having initial nickel fluoride s c a l e s of about
2.5 X 10^ A in t h i c k n e s s . Our data along with values obtained from the Oak
Ridge data by interpolation a r e listed in Table 4. The data obtained for
A-nickel a r e plotted in F i g u r e 16. F r o m the data listed in Table 4, it can
be seen that our r e s u l t s for A-nickel compare closely with those obtained
at Oak Ridge. However, the Nivac nickel r e s u l t s a r e higher than those obtained for A-nickel. In F i g u r e 17, the rate of change in the thickness of the
film is plotted v e r s u s the p r e s s u r e of fluorine in a t m o s p h e r e s as a log-log
plot of the data from this study for Nivac nickel and for interpolated points
obtained from the Oak Ridge work. F r o m the slopes of these c u r v e s , a
value of n of 0.55 was obtained for this work and a value of n of 0.87 was
obtained for the Oak Ridge work.
Table 4
THE E F F E C T O F PRESSURE ON THE RATE OF BUILDUP
OF A NICKEL FLUORIDE SCALE AT 600 C
Initial Scale T h i c k n e s s : ~2.5 x 10^ A
Equation:
dx/dt = kp"Rate of I n c r e a s e of Scale T h i c k n e s s ,
d x / d t , {jig Fg/sq c m ) / m i n
This Study
Pressure
(atm)

Nivac

A-Nickel

0.96
0.46
0.13

1.20
0.78
0.11

0.13
0.082
0.038

Oak Ridge, A-Nickel(2)

0.17
0.085
0.030

24

F i g u r e 16
PRESSURE DEPENDENCE OF NICKEL-FLUORINE REACTION
Temperature:
600 C
Initial NiFg
Scale Thickness: ~2.5 x 10^ A

200

300
TIME, minutes

F i g u r e 17
RATE OF CHANGE OF SCALE THICKNESS AS A
FUNCTION OF FLUORINE PRESSURE

T e m p e r a t u r e : 600 C
Initial Scale
Thickness:
2.5 x 10^ A
Equation
log dx/dt = log k + n log p
O THIS STUDY
A OAK RIDGE AECD-4292

I
PRESSURE FLUORINE, olm

25

IV.

SUMMARY

Evidence obtained from two e x p e r i m e n t a l approaches has been

p r e s e n t e d for the m e c h a n i s m of the nickel-fluorine reaction. In one a p p r o a c h the isotope nickel-63 was used as a s e l f - m a r k e r , and the d i s t r i bution of the beta activity of the nickel-63 in the scale indicated the
s p e c i e s , nickel or fluorine, that m i g r a t e d during the reaction. In the
second or impinging scale technique, the c h a r a c t e r of the interface formed
when s c a l e s from opposing nickel s u r f a c e s a r e made to grow against one
another indicated the m i g r a t i n g s p e c i e s . The validity of the miethod was
checked by performing s i m i l a r e x p e r i m e n t s with the nickel-oxygen s y s t e m , a s y s t e m for which the r e a c t i o n m e c h a n i s m is known. In this s y s t e m ,
the reaction p r o c e e d s via m i g r a t i o n of nickel ions through the oxide scale
to the o x i d e - s c a l e interface.
In the isotopic t r a c e r e x p e r i m e n t s , nickel-63 was plated on the s u r faces of nickel coupons which w e r e then fluorinated or oxidized. The r e acted s p e c i m e n s w e r e then mounted in Bakelite and sectioned n o r m a l to
the surface of the s c a l e . An a u t o r a d i o g r a p h was then taken and, after
development, was mounted on a m i c r o s c o p e slide. The autoradiograph
r e p l i c a t e d the surface of the speciinen so that an unambiguous identification of the m e t a l - s c a l e and s c a l e - g a s interfaces could be m a d e . In the
nickel-fluorine e x p e r i m e n t s , the nickel-63 activity was found concentrated
at the fluoride s c a l e - f l u o r i n e interface, thus indicating that the reaction
miechanism involved the m i g r a t i o n of the fluorine through the nickel fluoride
scale to the s c a l e - g a s interface. A s i m i l a r experimient with the nickeloxygen s y s t e m showed a distribution of the nickel-63 activity such as would
be expected for a m e c h a n i s m in which nickel m i g r a t e d through the growing
oxide scale to the n i c k e l - n i c k e l oxide interface. The r e s u l t s obtained in
the nickel-oxygen e x p e r i m e n t a r e in a c c o r d with the accepted m e c h a n i s m
for this reaction.
In the impinging scale e x p e r i m e n t s , reaction specimens w e r e p r e p a r e d by welding together two nickel coupons along a common edge, so that
the opposing s u r f a c e s w e r e s e p a r a t e d by only a fraction of a m i l l i m e t e r .
The s p e c i m e n s , after r e a c t i o n , w e r e mounted in Bakelite and sectioned
to expose the s c a l e s held between the opposing nickel faces. If the two opposing s c a l e s a r e fused into a single, continuous s c a l e , m e t a l m i g r a t i o n is
indicated with r e a c t i o n o c c u r r i n g at the s c a l e - g a s interface. If, however,
the two s c a l e s a r e not fused into a single, continuous scale and a definite
interface e x i s t s between t h e m , nonmetal m i g r a t i o n is indicated, with r e a c tion o c c u r r i n g at the s c a l e - m e t a l interface. In the fluoride impingement
e x p e r i m e n t s , the p r e s e n c e of an interface between the two fluoride s c a l e s
indicated the m i g r a t i o n of the nonmetal, fluorine. In the nickel oxide i m pingement e x p e r i m e n t s , the fusion of the two s c a l e s into one continuous
scale indicated m i g r a t i o n of the m e t a l , nickel.

Although these e x p e r i m e n t s showed that the m e c h a n i s m of the n i c k e l fluorine r e a c t i o n involves the m i g r a t i o n of fluorine through the growing
fluoride scale to the m e t a l - s c a l e interface, they did not indicate the mode
of t r a n s p o r t of the fluorine. Two p o s s i b i l i t i e s exist: the fluorine m i g r a t e s
to the m e t a l - s c a l e interface by g r o s s m o v e m e n t through p o r e s and c r a c k s
in the fluoride s c a l e , or by some t r a n s p o r t p r o c e s s through the bulk of the
s c a l e . Since the kinetics of the r e a c t i o n have been shown to follow a p a r a bolic rate law, it is m o r e likely that the m e c h a n i s m involves the t r a n s p o r t
of fluorine through the bulk of the nickel fluoride s c a l e .
The kinetics of the nickel-fluorine r e a c t i o n w e r e m e a s u r e d over the
t e m p e r a t u r e range from 300 to 600 C with Nivac, a high-purity nickel, and
c o m m e r c i a l A-nickel, A m a n o m e t r i c technique was employed and the r e actions w e r e p e r f o r m e d under i s o b a r i c conditions. The kinetics of the
reaction between Nivac nickel and fluorine w e r e found to obey a p a r a b o l i c
rate law, with r e a c t i o n r a t e constants of 9.8, 81.0, 461, and I860 (jJ-gFz/
sq cm Ni) / m i n at 300, 400, 500, and 600 C, r e s p e c t i v e l y . An activation
energy for the reaction of 17 k c a l / m o l e was calculated from the value of
the slope of an A r r h e n i u s plot of the data. C o m p a r i s o n of the t e m p e r a t u r e
dependence of the r a t e constants obtained for the r e a c t i o n between A-nickel
and fluorine with those for the r e a c t i o n between Nivac nickel and fluorine
could not be m a d e as the r a t e law compliance in the c a s e of A-nickel changed
with t e m p e r a t u r e , from l o g a r i t h m i c at 400 and 500 C to p a r a b o l i c at 600 C.
The r a t e of r e a c t i o n w a s , however, higher for Nivac than it was for A-nickel.
A s m a l l e r c r y s t a l g r a i n size for the Nivac nickel might account for its
higher r e a c t i v i t y . The p a r a b o l i c r e a c t i o n r a t e constants for the Nivac
nickel did not show a p r e s s u r e dependence g r e a t e r than the uncertainty for
an individual constant, which was 10 p e r c e n t , over the p r e s s u r e range
from 100 to 700 m m of Hg. However, for s a m p l e s having an initial fluoride scale of about 10^ A in thickness the r a t e s obtained w e r e found to be
dependent on a fractional power of the p r e s s u r e of fluorine. The reaction
r a t e of Nivac nickel was found to be dependent on the 0.55 power of the
p r e s s u r e , w h e r e a s that for A-nickel was about 0.87 power of the p r e s s u r e
which was confirmatory of the p r e s s u r e dependence found for A-nickel by
w o r k e r s at Oak Ridge,(2)

V.

ACKNOWLEDGMENTS

The a u t h o r s wish to axknowledge the helpful suggestions and advice

given during the c o u r s e of this work of J. G Schnizlein, L. Leibowitz, and
R. K. Steunenberg. In p a r t i c u l a r we wish to thank M, D. Adams for his
considerable advice and a s s i s t a n c e in the autoradiographic p r o c e s s .

VI.

BIBLIOGRAPHY

1. Steindler, M. J., and Vogel, R. C , Corrosion of M a t e r i a l s in the

P r e s e n c e of Fluorine at Elevated T e m p e r a t u r e s , ANL-5662
(Jan 1957).
2. Hale, C. F . , et a l . , High T e m p e r a t u r e Corrosion Study, Interixn
Report for the P e r i o d November 1958 through May 1959, AECD-4292
(July 28, 1959).
3. J a c k s o n , R, B., C o r r o s i o n of Metals and Alloys by F l u o r i n e ,
NP-8845 (I960).
4. White, E. L., and Fink, F . W., M a t e r i a l s of Construction for Handling
F l u o r i n e , P r o c e e d i n g s of the P r o p e l l a n t T h e r m o d y n a m i c s and
Handling Conference, Ohio State E x p e r i m e n t a l Station Special
Report 12 (June I960).
5. Wagner, C , Theory of the Tarnishing P r o c e s s , Z. physik. Chem.,
B21, 25 (1933T
6. Gulbransen, E. A., and Andrews, K. F . , High T e m p e r a t u r e Oxidation
of High P u r i t y Nickel between 750 and 1050C, J. E l e c t r o c h e m . S o c ,
104, 451 (1957).
7. O'Keefe, M, O., and M o o r e , W. J., Diffusion of Oxygen in Single
C r y s t a l s of Nickel Oxide, J, P h y s . Chem., 65, 1438 (1961).
8

Bardeen, J,, B r a t t a m , W. H., and Schockley, W., Investigation of

Oxidation of Copper by Use of Radioactive Cu T r a c e r , J. Chem. P h y s .
14, 714 (1946).

9. Castellan, G. W., and Moore, W. J., Diffusion of Radioactive Copper

During Oxidation of Copper Foil, J. Chem. P h y s . , 17, 41 (1949).
10. Schnizlein, J. G., et a l . , Identification of the Diffusing Species in
Uranium Oxidation. J. E l e c t r o c h e m . S o c , 107, 783 (i960).
11. A r m s t r o n g , G. T., and J e s s u p , R, S., Combustion C a l o r i m e t r y with
F l u o r i n e : Constant P r e s s u r e F l a m e C a l o r i m e t r y , J. R e s e a r c h , 64A,
49 (I960).
12. Gomberg, H. J-5_t_^. J High Resolution Autoradiography for Study of
Grain Boundaries in M e t a l s , P r o j e c t 2029, Univ. of Michigan
(Feb 1954),

28

13. Birchenall, C. E., Kinetics of F o r m a t i o n of P o r o u s or P a r t i a l l y D e tached S c a l e s , J. E l e c t r o c h e m . S o c , 103 619 (1956).

14. V e r m i l y e a , D, A., On the Mechanism of the Oxidation of Metals, Acta
Met,, 5, 492 (1957).
15. Steunenberg, R. K., Seiden, L., and Griffin, H., Chemiical Engineering
Division S u m m a r y Report, ANL-5924 (1958).