Vol. 120, No.

4 X - R A Y S T U D Y OF C u 3 0 Z n A L L O Y 475

thickness of the layer at steady state is on the order of sented at the Miami Beach Meeting of the Society, Oct.
10 -8 cm. Since the polarization conditions are such 8-13, 1972.
that steady-state simultaneous dissolution is e v e n t u -
ally obtained, it is deduced that a Cu-rich surface layer A n y discussion of this paper will appear in a Dis-
cussion Section to be published in the December 1973
is a necessary condition for simultaneous dissolution JOURNAL.
of Cu30Zn. The oxygen K b a n d spectra show that the
a m o u n t of b o u n d oxygen on the surface decreases d u r - REFERENCES
ing the first dissolution period and then holds con- 1. H. W. Pickering and C. Wagner, This Journal, 114,
stant d u r i n g subsequent dissolution periods at E 698 (1967).
0.24V, and that this oxygen is b o u n d to zinc ions. 2. H. W. Pickering, ibid., 115, 143 (1968) ; 117, 8 (1970).
These data show the utility of soft x - r a y spectros- 3. H. W. Pickering, ibid., 115, 690 (1968).
copy for the investigation of alloying effects which 4. C. Wagner, ibid., 116, 343 (1969).
occur very near the surface. 5. H. W. Pickering and P. J. Byrne, ibid., 116, 1492
The Cu LILm a n d Zn LILm b a n d spectra show that (1969).
the usual mechanical polishing methods i n v o l v i n g 6. H. W. Pickering and P. J. Byrne, To be submitted
to This Journal.
aqueous suspensions of a l u m i n a leave the surface of 7. J. E. Holliday, in "Techniques of Metals Research,"
Cu30Zn alloy enriched in copper. Dry mechanical Vol. 3, P a r t I, Chap. 9, R. F. Bunshah, Editor,
polishing methods are, therefore, recommended for the J o h n Wiley & Sons, Inc., New York (1970).
a t t a i n m e n t of a more n e a r l y u n i f o r m composition 8. J. Clift, C. Curry, and B. J. Thompson, Phil. Mag.,
b e t w e e n the b u l k and surface. 8, 593, 639 (1963).
A model of simultaneous dissolution is presented. It 9. J. E. Holliday, "Advances in X - r a y Analysis," Vol.
shows how zinc m a y initially be dissolved preferen- 14, p. 243, C. S. Barrett, J. B. Newkirk, and
C. O. Rund, Editors, P l e n u m Press, New York
tially. Then, simultaneous dissolution occurs in the (1971).
presence of a Cu-rich alloy surface layer. 10. J. E. Holliday, U n p u b l i s h e d data.
11. J. E. Holliday, in "Soft X - r a y Band Spectra and
Acknowledgments Electronic S t r u c t u r e of Metals and Materials,"
We gratefully acknowledge the contributions of p. 101, D. J. Fabian, Editor, Academic Press, New
P. J. B y r n e who p r e p a r e d a n d anodicaUy polarized York (1968).
the specimens, and of W. A. Hester who assisted with 12. S. Barnartt, This Journal, 119, 812 (1972).
the soft x - r a y investigations, and the helpful com- 13. R. P. F r a n k e n t h a l and H. W. Pickering, ibid., 119,
ments of Professor Carl W a g n e r of the M a x - P l a n c k - 1304 (1972).
I n s t i t u t ffir Biophysikalische Chemie. I4. C. Wagner, ibid., 103, 571 (1956).
15. J. D. Harrison and C. Wagner, Acta Met., 7, 722
Manuscript submitted May 16, 1972; revised m a n u - (1959).
script received Nov. 22, 1972. This was P a p e r 43 pre- 16. C. Wagner, P r i v a t e communication.

Surface Characterization of Sensitized

and Activated Teflon
N. Feldstein* and J. A. Weiner
RCA Corporation, David Sarno~ Research Center, Princeton, New Jersey 08540

ABSTRACT
A tin sensitizer solution has been developed which is useful with hydro-
phobic surfaces. Based on radiochemical tracer adsorption m e a s u r e m e n t s and
c o n v e n t i o n a l analytical techniques, a chemical characterization of the surface
was made following the sensitization and activation steps. Q u a n t i t a t i v e results
r e l a t i n g to the surface concentrations of active components [tin (II), t i n ( I V ) ,
and palladium] have been established. The surface concentration ratio of
t i n ( I I ) and t i n ( I V ) was found to be about 3: 1. It was also d e m o n s t r a t e d that
the t i n ( I I ) - p a l l a d i u m (II) redox reaction is of low efficiency.

In the plating of dielectric substrates, a p r e t r e a t m e n t place d u r i n g the sensitization a n d activation sequence:

of the substrate is essential in order to effectively
deposit metals b y the electroless plating technique. Of
the various procedures used commercially in meeting
the above requirements, a two-step immersion se-
quence in acidic stannous chloride solution followed
b y a n acidic p a l l a d i u m chloride solution is commonly
used. I n general, the first bath is referred to as the
"sensitizer" solution while the second solution is the
"activator." The net result of this sequence is the
formation of finely divided palladium nuclei which
initiate the autocatalytic plating process (1, 2). The
formation of the p a l l a d i u m metal nuclei has been pro-
posed to be due to a redox reaction (3-5) taking place
between the stannous ions adsorbed on the surface
and the p a l l a d i u m ions in the activating solution.
The following simplified reactions p r o b a b l y account
for some of the chemical and physical changes taking
* Electrochemical Society Active Member.
K e y w o r d s : sensitizer, electroless p l a t i n g , t i n - l l 3 .
1. Sensitization through stannous adsorption
S* ~ S n +~ (aq) ~ S* 9 S n +2 (ad)
2. Activation through a galvanic replacement
S* 9 S n +2 (ad) ~- Pd +2 (aq) --> S* 9 (ad) ~ Sn +4
where S* refers to the dielectric substrate, and (ad)
refers to an adsorbed state. Although the above proc-
ess is widely used commercially, little data has been
reported as to the efficiency of the reaction and the role
of the substrate i n such reaction.
I n recent publications (6-12) it has been d e m o n -
strated that the effectiveness of conventional tin sensi-
tizer solutions (SnC12/HC1) m a y be altered through
proper bath modification. Specifically, the incorpora-
tion of aged stannic chloride solutions was found to
provide the i m p r o v e m e n t s in performance. During the
aging process, a colloidal compound of t i n ( I V ) was

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 476 J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
formed. T h e colloidal c o m p o u n d is believed to be
~-stannic acid. It was also found (6) that th e aged
stannic chloride solution m a y be either added to con-
v e n t i o n a l tin sensitizers or used in a separate step prior
to the i m m e r s i o n in c o n v e n t i o n a l tin sensitizers. In
either case, identical results w e r e obtained, both w i t h
respect to the u n i f o r m i t y of metallic coverage, and by
an e x a m i n a t i o n of the r e s u lt in g surface by contact
angle m e a s u r e m e n t s (10). This i m p r o v e m e n t was of
special significance in the case of hydrophobic sub-
strates. Based on the t e n d e n c y for the interaction
b e t w e e n t i n ( I I ) and t i n ( I V ) , a m o d e l has been pro-
posed (11) wh i c h accounts for the m e c h a n i s m of
sensitization using t h e i m p r o v e d sensitizer. In the p r o -
posed m o d el (11), it was suggested that the sensitiza-
tion process is a t w o - s t e p sequence of adsorption of
the aged t i n ( I V ) component, followed by the adsorp-
tion of t h e t i n ( I I ) component. The adsorbed t i n ( I V )
component provides a path for t h e adsorption of
t i n ( I I ) . Th e n e w path is based on the chemical i n t e r -
action of t i n ( I I ) and t i n ( I V ) (11). This sequence
takes place w h e t h e r the aged t i n ( I V ) and t i n ( I I ) are
present t o g e t h e r or are used separately.
Th e choice of Teflon substrates was m a d e in v i e w
of its great degree of h y d r o p h o b i c i t y (10). It is also
b e l i e v e d that the results of the c u r r e n t investigation
w o u l d be applicable to other hydrophobic substrates
(e.g., photoresists) as was d e m o n s t r a t e d in the p r e -
vious w o r k on contact angle m e a s u r e m e n t s (10).
I n t h e c u r r e n t work, analytical e x a m i n a t i o n of the
surface u n d e r v a r i e d conditions was undertaken. This
w o r k was carried out to p r o v i d e verification of the
proposed mechanisms (11) and to establish some q u a n -
titative values r e l a t e d to the concentrations of active
components on t h e t r e a t e d surfaces in th e course of
t he sensitization and activation sequence.
Experimental Procedures
Tracer soIutions.--Preparation and calibration.--The
t r a c e r ( t i n - l l 3 ) solution of SnC14 was obtained from
A m e r s h a m / S e a r l e Corporation, Chicago, Illinois. The
supplier's specification for this m a t e r i a l was: chemical
form, SnC14 in 6.3N HC1; volume, 2.1 ml; and solids
content, 0.181 m g S n / m l .
The t r a c e r solution (2.1 ml) was t r a n s f e r r e d to a
100 m l v o l u m e t r i c flask using a freshly p r e p a r e d 0.51M
SnCla solution as the t r a n s f e r agent. A f t e r bringing to
100 ml volume, the final concentration was 0.50M
SnC14. No appreciable effect on solution characteristics
was e n c o u n t e r e d due to the slight addition of acid.
This solution was a ll o w e d to age for about one w e e k
before use.
Two milliliters of the SnC14 tracer stock solution
w e r e diluted to 100 ml. Duplicate 2 m l aliquots w e r e
removed, placed into individual 1 d r a m s c r e w - t o p glass
vials and counted in a 2 • 2 in. NaI (T1) w e l l - t y p e
crystal coupled to a m u l t i - c h a n n e l analyzer. The a v e r -
age count rate of the two standards was adjusted by
the ap p r o p r i at e dilution factor to d e t e r m i n e the a c t i v -
ity of the stock solution. It was found that the activity
of the 100 m l tagged stock solution was 6.50 • 10e
c o u n t s / m i n / m l . As the stock solution was 0.50M w i t h
respect to the tin (IV), th e e q u i v a l e n t c o u n t s / m i n / m o l e
of t i n ( I V ) is 1.3 • 1010.
The t r a c e r ( t i n - l l 3 ) solution of SnC12 was obtained
f r o m t h e same supplier as above. The supplier's speci-
fication of this m a t e r i a l was: chemical form, SnC12 in
6N HCI; volume, 0.38 ml; and solids content, 1.32 m g
Sn/ml.
The tracer solution was t r a n s f e r r e d to a 25 ml
v o l u m e t r i c flask and b r o u g h t to v o l u m e with 0.47M
HC1. One milliliter of this stock solution was added to
a 50 m l portion of SnC12/HC1 solution for each 0.065
m o l e / l i t e r SnC12 present in th e 50 ml portion. The
hydrochloric acid was held fixed at 0.47 molar.
A t ech n i q u e similar to that described for the tin (IV)
tracer calibration was used to d e t e r m i n e the activity
of the 25 m l stock solution. An activity of 1.17 • 107
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April 1973
c o u n t s / m i n / m l was found. This activity level corre-
sponds to 3.6 • 109 c o u n t s / m i n / m o l e of t i n ( I I ) .
Substrate preparation and treatment.--The sub-
strates used t h r o u g h o u t the r ad i o ch em i cal m e a s u r e -
m en t s w e r e Teflon rods 4 • 0.65 cm. The rods w e r e
cleaned in a m i l d alkaline soap solution, rinsed well
in deionized water, and t h e n v a p o r degreased with
F r e o n TF| Th e rods w e r e i m m e r s e d to a constant
d ep t h of 2 cm in a v o l u m e of 50 m l of the sensitizer
solution. This constant depth i m m er si o n was done so
that counting rates could be correlated to a solution
of k n o w n t i n - l l 3 activity, w h i ch had a height of 2 cm,
in order to p r o v i d e identical counting geometries (area
o f 4 . 5 c m 2) in all cases.
Sample counting.--Counting was done on a P a c k a r d
Model 116 m u l t i c h a n n e l analyzer in channels 1 through
49 (10 to 490 keV). B a c k g r o u n d radiations w e r e low
and subtracted from the m e a s u r e d values. Each sample
was counted for 30 rain, and the results are presented
on a c o u n t / m i n basis. P r i o r to counting, the sensitized
samples w e r e stored for 24 hr to allow for a complete
i n g r o w t h of t h e In T M d a u g h t e r f r o m the deposited
Sn 113, as well as to allow the decay of any co-deposited
In T M . Counting of the same samples i m m e d i a t e l y
after the sensitization step showed no In T M peak. The
following decay scheme (13) is p r o v i d e d r e p r e s e n t i n g
the radiochemical characteristics of Sn 113.
IT EC
S n 113 ) Sn TM )
tl/2 = 118 days tl/2 = 20 rain
IT 9
In TM ) In 113
t~/2 = 100 m i n
w h e r e EC = electron capture: a m o d e of decay i n v o l v -
ing cap t u r e of an orbital electron by its nucleus; IT =
isomeric transition: t h e decay of a nuclide to an iso-
meric nuclide by g a m m a radiation a n d / o r internal
conversion electron transition; and 7 = g a m m a radia-
tion of In T M ~ In 113 w i t h a p e a k at 392 keV. In all
counting experiments, at least two runs w e r e m a d e per
composition used. The duplicate runs showed good
agreement, w e l l w i t h i n •
Chemicals and solution.--All chemicals used
t h r o u g h o u t w e r e r e a g e n t grade; the hydrochloric and
nitric acids used w e r e electronic grade. The w a t e r used
was deionized and then distilled.
Etching and analysis oS surJace concentrations.--In
this phase of the investigation, Teflon spheres w e r e
used. The spheres used w e r e 0.094 • 0.001 in. in d i a m -
eter and supplied by Orange Products, Inc., Chatham,
N ew Jersey. In all cases 2000 spheres w e r e used, pro-
viding a surface area of about 360 cm 2. F o l l o w i n g the
cleaning p r o c e d u r e described above, these substrates
w e r e sensitized and activated in a s t a n d a r d fashion.
F o r estimating the p a l l a d i u m surface concentration,
etching was done in both concentrated HC1 and in 1:1
HC1/HNO3. A colorimetric t ech n i q u e (14) was e m -
ployed in estimating the r e c l a i m e d palladium. In order
to estimate the surface chloride concentration fol l ow -
ing the sensitization step, t h e sensitized surfaces w e r e
etched in concentrated nitric acid, and the chloride
was d e t e r m i n e d by n e p h e l o m e t r y .
Results and Discussion
In investigating the interaction b e t w e e n tin (II) and
t i n ( I V ) , B r o w n e et aI. (15) studied the kinetics of
exchange using a radiochemicaI tracer technique. The
t i n ( I I ) and t i n ( I V ) w e r e separated by the selective
precipitation of Cs~SnC16 by the addition of a CsC]
solution. This technique, however, is applicable only
in high concentrations of hydrochloric acid and is not
w i t h i n the range of typical sensitizing solutions. In
10.0F hydrochloric acid, t h e authors (15) found that
the rate of t h e r m a l homogeneous e x c h a n g e reaction
( b e t w e e n 0 ~ and 25~ is g i v en by
 Vol. 120, No. 4 S U R F A C E C H A R A C T E R I Z A T I O N OF T E F L O N 477

R = (Sn II) (Sn IV) • 4.5 • 107
X exp (--IO,800/RT) liter mole -1 m i n - j
F u r t h e r m o r e , at 25~ the rate constants in 9.0, 10.0,
and 11.0F hydrochloric acid w e r e found to be 0.38,
0.55, and 0.73 liter m o l e -1 m i n -1, respectively.
In v i e w of these findings (15), and the lack of
kno wl ed g e of the e x c h a n g e rate for solutions h a v i n g
less t h a n 1.0F hydrochloric acid (typical acid concen-
trations present in sensitizer formulations), the sensi-
tization sequence for the c u r r e n t w o r k was modified
to provide additional information. The o v e r - a l l sensi-
tization process was c a r r i e d out in two consecutive
steps (6, 10), each followed by deionized w a t e r rinsing
(at r o o m t e m p e r a t u r e for 1 m i n ) : (i) i m m e r s i o n in
aged stannic chloride solution w i t h added sodium
chloride and (ii) i m m e r s i o n in c o n v e n t i o n a l sensitizer
(SnC12/HC1). This approach was previously found (6)
to give e q u i v a l e n t results in comparison to a sensitiza-
tion process in w h i c h the stannous and stannic com-
ponents coexist in the same media. By adopting this
procedure, the p r o b l e m of homogenous exchange be-
t w e e n t i n ( I I ) and t i n ( I V ) was eliminated. The in-
corporation of sodium chloride was m a d e in v i e w of
the f u r t h e r i m p r o v e m e n t in the w e t t i n g of h y d r o -
phobic surfaces as d e m o n s t r a t e d p r e v i o u s l y (6, 10).
Table I provides the results of t h e radiochemical
measurements. As stated previously, these values cor-
respond to t h e a v e r a g e of duplicate runs. In Table IA,
the effect is d e m o n s t r a t e d of v a r i e d concentration of
aged stannic chloride on the surface concentration
adsorbed. E x a m i n a t i o n of the results r e v e a ls no m a j o r
variations although t h e stannic concentration is v a r i e d
over a five-fold concentration range. Table IA indicates
that the adsorbed stannic species (~-stannic acid) was
adsorbed onto the Teflon surface to a final surface con-
centration which was essentially in d e p e n d e n t of bulk
concentration. F r o m the values of Table IA, an a v e r a g e
surface activity of 521 c o u n t s / m i n was obtained. This
va l u e corresponds to a stannic activity of 4.0 X 10 -2
# m o l e / s u b s t r a t e or 0.89 • 10 -2 ~,mole/cm 2 tin (IV).
Table IB shows t h e net surface activity after i m -
mersion in a fixed stannous c h l o r i d e / h y d r o c h l o r i c
acid solution for substrates w h ic h w e r e previously
i m m e r s e d in v a r i e d concentrations of aged stannic
chloride solutions. Once again, little change is noted
as the stannic concentration was v a r i e d over a tenfold
range. O v e r this range, an a v e r a g e v a l u e of 419 -+ 9
c o u n t s / m i n was found.
Based on the a v e r a g e results of Tables IA and IB,
t h e r e is about a 20% loss in surface activity of tin (IV)
following the i m m e r s i o n in stannous c h l o r i d e / h y d r o -
chloric acid solution.
In order to d e t e r m i n e the effect(s) associated w i t h
varied i m m e r s i o n times in the aged stannic chloride
Table I. Radiochemical adsorption measurements
A g e d SnCI~ s o l u t i o n * SnCI2 s o l u t i o n * *
Concen- Concen-
tration Immer- tration Immer-
(moles/ sion (moles/ sion
Expe- liter time liter time
Counts/rain
riment x I00) (min) x I0) (min)
Sn(IV)
solution, t h e results of TabIe IC are provided. F r o m
t h e values of Table IC, it appears that for i m m e r s i o n
times of about 1 m i n or g r e a t e r in SnC14 solution, the
surface activity of t i n ( I V ) is constant at a value of
about 410 counts/min. This v al u e is in ex cel l en t a g r e e -
m e n t with t h e a v e r a g e results of Table IB (419 __ 9
counts/min).
In Tab l e ID, the net surface activity of t i n ( I V ) is
shown following an i m m e r s i o n in acidic stannous
chloride solutions of fixed hydrochloric acid content,
but v a r i a b l e stannous chloride contents. O v e r a f our -
fold concentration range of tin (II), an a v e r a g e va l ue
of 381 ___ 34 c o u n t s / m i n was obtained, in good a g r e e -
m e n t w i t h the a v e r a g e s of Tables IB and IC. This
result suggests that the fraction of surface m a t e r i a l
[tin ( I V ) ] desorbed during a 1-min i m m e r s i o n in acidic
stannous solution is i n d e p e n d e n t of the stannous con-
tent of the solution.
It is interesting to note that a 1-min i m m e r s i o n in
a solution containing 0.47M HC1 (without SnC12)
resulted in a surface activity [for t i n ( I V ) ] of about
200 counts/min. In fact, d e - w e t t i n g of the Teflon sur-
face takes place in the hydrochloric acid w i t h i n a few
minutes. By contrast, i m m e r s i o n in the same h y d r o -
chloric acid m ed i a w i t h SnC12 (e.g., 0.13M) did not
produce any d e - w e t t i n g of t h e surface after several
hours.
In an o t h er ex p er i m en t , the sequence of immersion
and timing w e r e identical, but tagged stannous chlo-
ride solutions w e r e e m p l o y e d r a t h e r than tagged
stannic solution. As seen f r o m the results of Table IE,
the surface activity of the stannous ion was inde-
p en d en t of the bulk concentration used and had an
a v e r a g e value of 314 __ 19. This corresponds to a sur-
face co n cen t r at i o n of 8.9 X 10 -2 ~ m o l e / s u b s t r a t e or
2.0 X 10 -2 # m o l e / c m 2 of t i n ( I I ) . It should also be
noted that e x t e n d e d i m m e r s i o n (15 m i n in the acidic
stannous chloride solution) did not change t h e sur-
face concentration of the adsorbed stannous com-
ponent. F r o m the a v e r a g e values of Tables IB, IC, and
ID, a m e a n surface activity of 387 ___ 29 was found for
the t i n ( I V ) after brief i m m e r s i o n (1 rain) in acidic
t i n ( I I ) solutions. F r o m these results, the ratio of
tin (IV) to tin (II) was a p p r o x i m a t e l y 1: 3.
In Fig. 1 the net surface activity for t i n ( I V ) as a
function of i m m er si o n t i m e in a SnC12/HC1 solution
is shown. A l t h o u g h t h er e was an initial decrease in
the surface concentration of tin (IV), after about 5 mi n
an e q u i l i b r i u m v al u e was achieved, in the range of
350 __ 25 c o u n t s / m i n / s u b s t r a t e .
This slight desorption of t h e t i n ( I V ) m a y be due
to either of the following factors operating singly or
in combination: (i) desorption a n d / o r dissolution of
the p-stannic oxide in the acid m ed i a (ii) desorption
due to the r e p l a c e m e n t of adsorbed stannic co m pone nt
by t h e stannous ion. Based on the c u r r e n t results it
w o u l d seem that the possible r e p l a c e m e n t of adsorbed
t i n ( I V ) by t i n ( I I ) does not take place to any a p p r e -
ciable extent; instead, the desorption of t i n ( I V ) is
500
i
Sn(II)

A 0.50 1.0 -- -- 564

1,O 1.O -- -- 520
-- 40
2.5 1.0 -- ~ 480 Z U.I
B 0.50 1.0 1.3 1.0 415 -- -- k-
2.5 1.0 1.3 1.0 409 u_ Z
5.0 1.0 1.3 1.0 433 --
C 2.5 0.25 1,3 1.0 347 --
2.5 1.0 1.3 1.0 408
2.5 5.0 1.3 1.0 411 ~ 30
D 2.5 1.0 0.65 1.0 360 --
2.5 1.0 1.3 1.0 409 -- c- 2
2.5 1.O 1.9 1.O 304
2.5 1.0 2,6 1.O 372 --
E 2.5 1.0 1,3 1.0 -- 305
2.5 1.0 1.9 1.0 -- 351 z 200 I I l
2.5 1.0 2.6 1.0 -- 300 0 50 I0.0 15.0 200
2.5 1.0 1.3 15.0 -- 298 IMMERSION TIME IN STANNOUS SOLUTION (MINUTES)

* A l l s o l u t i o n s c o n t a i n e d 3 M NaC1.
Fig. I. Surface activity of tin(IV) vs. immersion time in stannous
** A l l s o l u t i o n s c o n t a i n e d 4.8 x 1O-IM HC1. solution.

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 478 J. E l e c t r o c h e m . Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
probably due to the acidic n a t u r e of the media and the
chloride present. Yet it should be a p p a r e n t that in a
SnC12/HC1 solution an e q u i l i b r i u m state is reached
after which no f u r t h e r desorption of the adsorbed
t i n ( I V ) component takes place. This stabilization of
the surface suggests that either a highly preferred
configuration is established comprised of t i n ( I I ) and
t i n ( I V ) , or a subsequent reaction on the surface might
have taken place forming a product which is insoluble
in the media. I n this preferred configuration there is
a fixed molar ratio b e t w e e n the stannous and the
stannic components. Hence, at equilibrium, which is
established (Fig. 1) after about 5.0 rain of immersion,
the following are the surface concentrations for the
tin components
T i n ( I I ) -- 20 • 10-3 ~mole/cm 2
or 1.2 • 10TMa t o m s / c m 2
Tin (IV) -- 6.0 • 10-3 ~mole/cm 2
or 0.36 • l0 TMa t o m s / c m 2
This corresponds to a ratio of a b o u t 1 t i n ( I V ) to 3.3
t i n ( I I ) existing in the mixed adsorbed layer. This
configuration is quite stable and does not seem to
change over a period of several hours.
Table II provides a s u m m a r y of the changes in the
surface concentrations of tin (IV) at each stage i n the
cycle.
Although in the c u r r e n t work the m e a s u r e m e n t s
were obtained using the aforementioned technique of
consecutive immersion i n stannic a n d stannous solu-
tions, one e x p e r i m e n t was conducted using a mixed
solution of t i n ( I I ) and tin (IV). The solution used was
composed of 4.7 • 10-1M HC1, 1.3 • 10-1M SnC12, and
SnC14 varied from 1.5 • 10 -3 to 1.5 • 10-1M. Tagged
SnC14 was incorporated into a O.5M SnC14 stock solu-
tion which was aged and then used to prepare the
mixed tin (II) - t i n (IV) solutions.
Radiochemical m e a s u r e m e n t s revealed a surface
concentration which was i n d e p e n d e n t of the b u l k con-
centration of tin (IV). The surface concentration found
was a p p r o x i m a t e l y 4 • 10 -3 ~mole/cm 2 t i n ( I V ) . It is
interesting to note that this value agrees fairly well
with the surface concentration of tin (IV) found u n d e r
e q u i l i b r i u m conditions (6 • 10 -3 ~mole/cm 2) using
the two-step sequence. This m a y indicate that little
homogenous exchange b e t w e e n t i n ( I I ) and t i n ( I V )
takes place u n d e r the conditions employed. This con-
clusion is consistent with the reported (15) t r e n d of
a lower homogenous rate of exchange with decreased
acidity. Also, these results reinforce the previous pro-
posal (11) that an identical o v e r - a l l m e c h a n i s m takes
place regardless of w h e t h e r the aged stannic com-
p o n e n t is used with conventional sensitizers or is used
as a separate i m m e r s i o n step prior to conventional
sensitization.
F r o m the e q u i l i b r i u m concentration data for tin (II)
and t i n ( I V ) , it would seem that both the adsorbed
t i n ( H ) as well as t h e t i n ( I V ) colloid m u s t be of
several monolayers in thickness, since a monolayer is
generally 1015 a t o m s / c m 2.
It was also found that the surface activity (tin ( I I ) )
of sensitized Teflon was not changed by subsequent
Table II. Net radiochemJcal adsorption after each step*
in the cycle
Average counts/min
Step f o r t i n (IV)
After immersion in aged stannic solution** 521
A f t e r i m m e r s i o n in stannous solution*** 419
After l-rain immersion in palladium chloride 413
s o l u t i o n (2.8 • 10-~M PdCl~ a n d 6 • 1 0 ~ M
HC1)
* I n a l l cases, l - r a i n i m m e r s i o n t i m e w a s u s e d .
** A v e r a g e o f r e s u l t s o f T a b l e I A .
*** A v e r a g e o f r e s u l t s o f T a b l e IB.
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A p r i l 1973
immersion in a PdC12 solution (1.0 g/1 PdC12 ~ 1.O
ml/1 conc HC1). This t r e n d was demonstrated
using different types of sensitization [one using com-
bined t i n ( I I ) and t i n ( I V ) a n d the other using t i n ( I V )
followed by t i n ( I I ) ] procedures. The per cent change
in surface activity of t i n ( I I ) was below 5%, well
within the accepted 90% confidence level.
Analysis for the chloride content following the
sensitization sequence revealed a chloride level of less
t h a n 3 • 10 -2 ~mole/cm 2. This upper limit is due to
the limitation in the nephelometric method of analysis
used. Based on this result, the actual role of the chlo-
ride ions in the sensitized film is not understood and
requires additional investigation. However, its use in
the media has provided i m p r o v e d wetting performance
(10).
Etching and analysis of the p a l l a d i u m following the
activation step has resulted i n surface concentrations
in the range of about 2 • 10 -3 to 4.5 • 10 -3 #mole/
cm 2. These values correspond to about 10-25% of the
surface concentration of t i n ( I I ) . It would thus seem
that the proposed redox exchange reaction between
tin (II) and Pd (II) takes place only to a limited extent.
This observation, while it m a y be puzzling at first, is
not surprising since the sensitized surface [composed
of t i n ( I V ) and t i n ( I I ) ] was shown to be a highly pre-
ferred configuration which does not change with time.
It should be pointed out that the extent of oxidation-
reduction observed for the present system does not
necessarily apply to other sensitizer media. I n fact,
Cohen et al. (4, 5) have suggested that in conventional
sensitizers there is a complete exchange between
t i n ( I I ) and P d ( I I ) using K a p t o n as the substrate.
More recently, P. F. J. v.d. Boom et at. (16) have
shown that no replacement of t i n ( I I ) b y P d ( I I ) takes
place using soda-lime glass as the substrate.
Conclusions
The present investigation, using radioactive t i n - i f 3 ,
has provided q u a n t i t a t i v e results for the adsorption of
aged t i n ( I V ) a n d t i n ( I f ) , the findings of which sup-
port the proposed model for this system (11). More-
over, it has been demonstrated that prior to the activa-
tion step, the surface concentration ratio of t i n ( I I ) to
t i n ( I V ) is about 3: I. Although the exact surface con-
figuration and b o n d i n g is not known, the resulting
sensitized film is highly stable, p r o b a b l y due to the
chemical interaction of the aged stannic component
with the stannous ions. As was found previously (i0),
the aged stannic component m a y be used as a distinct
immersion step prior to the i m m e r s i o n in conventional
sensitizers or be combined with the c o n v e n t i o n a l sensi-
tizer into one solution. I n either case, the surface con-
centration for the aged t i n ( I V ) component was found
to be n e a r l y the same.
F r o m a practical consideration of the c u r r e n t sys-
tem, it has been demonstrated that the surface concen-
t r a t i o n of active components is fairly i n d e p e n d e n t of
variations i n i m m e r s i o n times, concentrations of aged
t i n ( I V ) , and concentrations of t i n ( I I ) . This permits
industrial processes to be operated with wide m a r g i n s
in sensitizer m a k e - u p .
It would also seem doubtful w h e t h e r the redox reac-
tion b e t w e e n t i n ( I f ) and p a l l a d i u m ( I f ) does occur.
As there has not been a significant decrease in surface
activity (using tagged t i n ( I I ) ) after the activation
step, it is possible that either (i) the redox reaction
does not take place and the palladium is adsorbed in
a n ionic state, or ({i) the redox reaction takes place
resulting in tin (IV) which is insoluble in the activator
solution. Moreover, if the redox reaction does take
place, its efficiency is, at best, 25%.
I n view of the wide range of per cent efficiencies
reported for the t i n ( I f ) / p a l l a d i u m ( I f ) redox reaction,
future work in this field should provide greater con-
sideration of the sensitization system and the role
played by the substrate. It is believed that future i m -
provements in the sensitization of dielectric substrates
 VoI. 120, No. 4 SURFACE CHARACTERIZATION OF TEFLON 479

will f u r t h e r result in i m p r o v e d p r o p e r t i e s of thin films 4. R. L. Cohen, J. F. D'Amico, and K. W. West, This

deposited b y chemical p l a t i n g techniques.
Acknowledgments
The w r i t e r s wish to t h a n k P. B l u m b e r g a n d R. J.
L a g o m a r s i n o of L e D o u x and C o m p a n y for t h e i r assist-
ance in the r a d i o c h e m i c a l measurements, B. L. Goydish
for technical assistance in the p a l l a d i u m analysis, and
G. L. S c h n a b l e and R. W i l l i a m s for useful suggestions
and the r e v i e w i n g of this manuscript.
M a n u s c r i p t s u b m i t t e d J u n e 15, 1972; revised m a n u -
script received Nov. 30, 1972. This w a s P a p e r 218
p r e s e n t e d at the Miami Beach, Florida, Meeting of the
Society, Oct. 8-13, 1972.
A n y discussion of this p a p e r will a p p e a r in a Dis-
cussion Section to be p u b l i s h e d in the D e c e m b e r 1973
JOURNAL.
REFERENCES
1. J. P. M a r t o n and M. Schlesinger, This Journal, 115,
16, (1968).
2. R. Sard, ibid., 117, 864 (1970).
3. W. Goldie, "Metallic Coatings of Plastics," Vol. 1,
Chap. 5, Electrochemical Publications Limited,
H a t c h End, Middlesex, E n g l a n d (1968).
Journal, 118, 2042 (1971).
5. R. L. Cohen and K. W. West, ibid., 119, 433 (1972).
6. N. F e l d s t e i n a n d J. A. Weiner, Plating, 59, 140
(1972).
7. Staff Editor, Chem. Eng. News, Feb. 21, p. 17
(1972).
8. Staff Editor, Elec. Packaging and Production, 12,
16, A p r i l (1972).
9. Staff Editor, Ind. Finishing, p. 112, M a y (1972).
10. N. F e l d s t e i n and J. A. Weiner, This Journal, 119,
668 (1972).
11. N. Feldstein, J. A. Weiner, and G. L. Schnable,
ibid., 119 1486 (1972).
12. N. F e l d s t e i n and T. S. Lancsek, U.S. Pat. 3,667,527,
issued M a y 30, 1972.
13. U.S. D e p a r t m e n t of Health, Education and Welfare,
Public H e a l t h Services, "Radiological Health
Handbook," 1960 edition, p. 311.
14. K. L. Cheng and B. L. Goydish, Microchem. J., 10,
158 (1966).
15. C. I. Browne, R. P. Craig, and N. Davidson, J. Am.
Chem. Soc., 73, 1946 (1951).
16. P. F. J. v.d. Boom a n d C. H. deMinjer, P r i v a t e com-
m u n i c a t i o n (1972).

The Influence of Anions on the Structure

of Porous Anodic Films Grown
in Alkaline Electrolytes
P. Neufeld and H. O. Ali
Polytechnic o] the South Bank, London S E 1 0 A A , England

ABSTRACT
Porous, anodic A1203 films have b e e n g r o w n in a v a r i e t y of a l k a l i n e
electrolytes. A t e l e v a t e d t e m p e r a t u r e s film g r o w t h b e y o n d the n o r m a l b a r r i e r
thickness and the d e v e l o p m e n t of a w e l l - d e f i n e d pore structure is not u n -
common, but only b o r a t e solutions have been found to support the g r o w t h
of films of a thickness c o m p a r a b l e to c o m m e r c i a l acid anodizing processes.
A transition from porous film g r o w t h to electropolishing has been observed
in the case of c i t r a t e solutions.
The significance of the results is discussed in relation to p r e s e n t theories
of acid anodizing.

Some e l e c t r o l y t e solutions such as a m m o n i u m t a r - h y d r a t i o n a n d lowering of resistance for films grown

t r a t e and boric a c i d - b o r a x m i x t u r e s support the
g r o w t h of thin b a r r i e r films of anodic oxide on a l u -
minum. Others, such as sulfuric and chromic acids
support the g r o w t h of thick, porous films, w h i l e elec-
tropolishing m a y occur in others such as phosphoric
a c i d - b u t y l alcohol (1). T h e simplest classification of
these electrolytes has been in t e r m s of their solvent
ability, b a r r i e r electrolytes having t h e least dissolving
p o w e r on the oxide film. It has long been evident that
solubility a l o n e does not e x p l a i n all the variations of
b e h a v i o r shown b y anodized aluminum, and the n a t u r e
of the anions p r e s e n t has been shown to be i m p o r t a n t
a s w e l l as the pH. Kissin (2) a n d M u r p h y (3) sug-
gested t h a t only d i - or t r i v a l e n t acids would s u p p o r t
porous film growth, t h o u g h evidence for the g r o w t h
of such films in sulfamic acid (NH2 SO3H) is found in
the w o r k of La Vecchia (4).
The g r o w t h of t h i c k porous A1203 anodic films has
t r a d i t i o n a l l y a l w a y s been c a r r i e d out in acid e l e c t r o -
lytes. Thus theories of film g r o w t h have assigned i m -
portance to t h e role of the h y d r o g e n ion. H o a r and
Y a h a l o m (5) suggested t h a t p r o t o n e n t r y against the
field could reduce the film resistance and l e a d to in-
creased c u r r e n t flow, J o u l e heating, and pore i n i t i a -
tion. B r o c k and Wood (6), however, r e p o r t e d h e a v y
Key words: aluminum, anodizing, alkaline, anions.
in a l k a l i n e - t a r t r a t e solutions. These ideas m a y be
h a r m o n i z e d to some e x t e n t b y considering, as did
O ' S u l l i v a n and Wood (7), t h a t mobile protons in the
film w o u l d be l i k e l y to be included in O H - ions. Thus
s t r u c t u r a l modifications due to proton e n t r y in acid
electrolytes m a y not s u b s t a n t i a l l y differ from those
produced b y h y d r o x y l a t i o n in alkalies.
Recent w o r k b y Leach and Neufeld (8) and Neufeld
and A l l (9, 10) has shown t h a t thick, porous, anodic
films m a y be grown in hot a l k a l i n e solutions contain-
ing b o r a t e ions. Heating is essential; if the dissolving
p o w e r of the electrolyte is increased s i m p l y b y raising
the pH, pitting a t t a c k is induced. Active p a r t i c i p a t i o n
b y the anions in the anodizing electrolyte is thus a m a -
jor factor in t h e g r o w t h of porous films in alkaline
electrolytes. The present w o r k describes a s t u d y of the
effect of a v a r i e t y of anions in porous anodic A120
g r o w t h in a l k a l i n e solutions at t e m p e r a t u r e s above
ambient.
Experimental Techniques
MateriaL--The m a t e r i a l used was 99.99% p u r i t y
a l u m i n u m sheet, about 0.3 m m thick. F l a g - s h a p e d
specimens w e r e cut, 1 cm 2 in size, w i t h a long n a r r o w
"flag pole" w h i c h was used for h a n d l i n g a n d m a k i n g
electrical contact.

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