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Corrosion Science, 1972, Vol. 12, pp. 113 to 120. Pergamon Press.

Printed in Great Britain

ELECTROPOLISHING OF COPPER AND COPPER-BASED


ALLOYS IN ORTHO-PHOSPHORIC ACID*

D. R. GABE
Department of Metallurgy, The University, Sheffield

Abstract--The behaviour of copper, a single-phase brass and a duplex aluminium bronze, during
electropolishing in orthophosphoric acid has been examined in terms of polarization curves and the
effects of temp. and acid concentration. A change in mechanism of electropolishing was apparent at
about 37°C; below this temp. an activation energy of 5.9 kcal/mole was found while above it was
4.2 kcal/mole. The copper alloys were satisfactorily electropolished in similar solutions to those used
for pure copper, but at high overpotentials the duplex bronze was subject to dealuminification of the
second (y~) phase.
R6sum& On a examin6 le comportement de cuivre, d'un laiton h une phase et d'un bronze ~t
l'aluminium lors de polissage 61ectrochimique dans l'acide orthophosphorique. Les effets de la tem-
p6rature et de la concentration en acide ont 6t6 examin6s au moyen de courbes de polarisation. Une
modification du m6canisme de polissage apparait h 37°C; on a trouv6 une 6nergie d'activation de
5,9 kcal/mole en dessous de 37°C et de 4,2 kcal/mole au-dessus de 37°C. Les alliages cuivreux sont
polis correctement darts des solutions semblables h celles utilis6es pour le cuivre pur, mais ~t des
surtensions 61ev~s la seconde phase ('f~) du bronze d'aluminium s'est d6salumin6e.
Zusammenfassung--DasVerhalten yon Kupfer, einem Einphasenmessing und einer Duplexaluminium-
bronze wahrend des Elektropolierens in Orthophosphorsiiure wurde zwecks Gewinnung yon
Polarisationskurven und der Feststellung der Einfliisse yon Temperatur und Siiurekonzentration
untersucht. Bei etwa 37°C trat eine ~nderung des Mechanismus des Elektropolierens in Erscheinung;
unterhalb dieser Temperatur wurde eine Aktivierungsenergie yon 5,9 kcal/Mol gefunden, wiihrend
sie dartiber 4,2 kcal/Mol betrug. Die Kupferlegierungen liessen sich in fihnlichen L6sungen wie den
fiir reines Kupfer verwendeten zufriedenstellend elektropolieren, aber bei hohen Obersparmungen
war die Duplexbronze der Entaluminisierungder zweiten (Y2) Phase unterworfen.

INTRODUCTION
ORTHO-VHOSVHORICacid is widely used for the electropolishing of copper a n d c o p p e r -
based alloys 1,2 and since its original development 3,4 the polarization characteristics
have received considerable attention. 5-10 A d d i t i o n a l factors which have been examined
in recent years include the effects of solution flow n-13 a n d heat transfer 1. although
little has been reported o n the effects of alloying elements. The m e c h a n i s m o f electro-
polishing has been of considerable interest, owing to the peculiar properties of
phosphoric acid in n o t only p r o m o t i n g passivity a n d thereby film-controlled dis-
solution, b u t also p r o m o t i n g solution diffusion-control in view of its viscosity. These
factors have all received consideration in the development of a theory for electro-
polishing.a, 16-21
Nevertheless, some discrepancies in the polarization data exist a n d a n attempt
has been made to c o m p a r e these results a n d show how they relate to data for some
c o p p e r - b a s e d alloys. The basis o f the investigation has been the r e c o m m e n d a t i o n that
o p t i m u m metallographic electropolishing m a y be achieved in solutions c o n t a i n i n g
60-70% v/v ortho-phosphoric acid (8.7-10M) at temp. within the range 15-25°C 1,~
*Manuscript received 5 April 1971 ; in revised form 21 July 1971.
113
114 D . R . GABE

and the assertion that brightening only occurs for concentrations above about
36% (5.3M). 5

EXPERIMENTAL
Samples of O.F.H.C. copper strip, cold-rolled and annealed, were degreased and
pickled in 50% nitric acid prior to electropolishing in ortho-phosphoric acid solutions.
The basic solution used was 67% v/v (10M) although the effect of concentration was
examined at 24°C and the effect of temp. examined over the range 4-75°C. Potentio-
dynamic polarization measurements were made with an Amel potentiostat using a
scanning speed of 133 mV/min and a copper reference electrode. The anode was held
vertically such that convection currents could develop naturally without significant
restriction and the cathode was a cylindrical sheet surrounding anode and again
vertical. The effect of stirring was examined by using a small electromagnetic stirrer
at the bottom of the cell which was rotated quite slowly (e.g. 30-60 rev/min).
In addition to the "pure" copper mentioned above, two other alloys were examined
- - a single-phase 71 Cu-29 Zn u-brass and a duplex 9 AI-91 Cu aluminium bronze
--and their electropolishing characteristics examined. Both alloys had been rolled
and annealed, the latter having a relatively large grain size with the second (72) phase
present essentially as a massive grain boundary precipitate.

RESULTS
Effects of temp. variation
Potentiodynamic polarization curves were measured for a range of temps. (4-75°C
under conditions of no specific agitation, although it was clear that at the higher
temps, some thermal convection was developing. The critical electropolishing or
bdghteuing potential was apparent at about 250 mV over-potential for the lower
temps, rising to almost 400 mV at 75°C (Fig. 1). The polishing current, i,o~, increased

i i , i . . . . i
,, /

l t J I ~ l - -

o 1500 P

o ",,i Ii/ ,0 e
5oo \ ",,,k 'k:,...?,,
" ~ x.,, ,,. "\

I = I r I I = I
20 50 i00
c.d., ' mA/cm 2

FIG. I. Anodic polarization curves for copper in 67% ortho-phosphoric acid at


various temps.
Electropolishing of copper and copper-based alloys 115

with temp. as shown in Fig. 2 where some earlier data of Honeycombe and Hughan s
in 36.5 % (SM) phosphoric acid has been included for comparison. The effect of stirring
was analogous to an increase in temp.; for example, in 67% (10M) acid at 22°C,
Ecrit might be raised from 260 mV to 430 mV over-potential and ipol raised from 18 to
66 mA/cm ~.

J I l I I I

80 ×

7O

;e N
./
- 50 0 ×

•c~
- 40

30

20 o ×°. i nvesfigation
-:~>/
x IO M acid
o-
to :<'<~" o Honeycombe andHugha~
5.3 M acid

] I r l 1 I I
tO 20 30 40 .50 60 70

Temperature, °C
FiG. 2. Relation of polishing current to temp. in 67% orthophosphoric acid.

J • l ' , , ', j ]


3 o~
2o00

> 1500
E
Jsoo

R iooo
£
O
I000

500

500

.L r f f , , , ,I f
20 50 lO0 20O

c.d,, mA/¢m a

FIG. 3. Anodic polarization curves for copper in ortho-phosphoric acid at various


concentrations (22°C).
116 D.R.. GABE

Effects of acid concentration


A decrease in concentration of ortho-phosphoric acid had little effect on the value
of Ecrit but the polishing c.d. increased markedly (Fig. 3). If the values of ipoI are
plotted against acid concentration (Fig. 4) it may be seen that a maximum occurs at
about 20% (3M), polishing only being satisfactory on the high-concentration side of
this peak. If other data is included it may be seen that the general shape and maximum
position, which could be affected by the experimental procedure and materials, show
some discrepancy. The line shift of Fig. 2 can now be clearly placed in context.
Acid concentration, % V/V
5 I0 20 30 44950 70
/-%
180 × This investigation / k

• HoarandRothwell
s
/ /
/ \\ /
,4o li / \ht.~
,~o ! /× •
..oo / I/d .;,.
, y -\\ \
.o / ! .,.
;~ so I I ,, \

I r I i I I I I I I I 1 1 I I I I i I
0'1 I0
[ "0
Acid concentration, M
FIG. 4. Relation of polishing current to acid concentration at 22°C.

Effects of alloy composition


Polarization curves in orthophosphoric at 23°C were obtained for the two copper
alloys at three concentrations (Fig. 5) and are directly comparable with the data of
Fig. 3. The curves are clearly very similar in the case of 70/30 brass although it may
be noticed that the breakdown of polishing "passivity" takes place at about 150 mV
lower-potential when compared with copper. In the case of the duplex aluminium
bronze a two-stage polishing "plateau" is apparent, each stage clearly associated with
one of the phases. With increasing temp. (Fig. 6), the secondary polishing region
becomes less significant but may still be detected at 50°C.
At high over-potentials (Ets > 1800 mV) the aluminium bronze is subject to
dealuminification which can be associated with the second phase (72), being pre-
ferentially dissolved yielding, after a length of time, a porous copper-like appearance.
Potentiodynamic cycling reveals that irreversibility occurs only when over-potentials
above about 1500 mV are exceeded (Fig. 7).
Good metallographic polishes are achieved for both alloys at over-potentials of
400-700 mV and temps, below about 40°C, and the black-film characteristics are
similar to those observed for pure copper.
Electropolishing of copper and copper-based alloys 117

I ' ' ' ' I I

-- 2 9 Z n : 71Cu ~---,., 5 0 % . : ' = *,


A,:~,cu .zo, (X.-'7:~'Z.>"
200o

> 1500
E
-2 1500
O

N 10~
//I /" o

o
,, <;.*':;;'" I000 Q.
o
c

/
500 / ,.'.~ __
..',~-. . . . . . . . . . . .
500
l i , I , i ~ i I I
20 50 I00 200
c.d., m A / c m 2

FIG. 5. Anodic polarization curves for 71 Cu-29 Zn and 9 AI-91 Cu alloys at three
acid concentrations.

i i ' 71Cu
' ' '1 I ' i .... i
- - 2 9 Zn:
sJ/ ' / $1 ..S~30~
,

.... 9AI: 91 Cu /'" .i/~.-" ./~ 2000

>
.E

1500
2
~ioool- II i ~I
o

I/
...< I -
1000 g
o
rl

,, \ ,,
500

2 5 I0 20 50 I00
c.d., m A / c m 2

FIG. 6. Anodic polarization curves for 71 Cu-29 Zn and 9 AI-91 Cu alloys in 67%
orthophosphoric acid at various temps.
118 D.K. GABE

l,,J i i ,~l 1 i ,,j L ;''I

1500

5co C~,
o
~ I000

& o
!000

0
5OO

5OO

•' 7 I0 20 30

c.d., mAlcm 2

FIG. 7. Anodic potentiodynamic curves for the 9 AI-91 Cu alloy in 67% ortho-
phosphoric acid at 25°C.

DISCUSSION
Electropolishing is usually attributed to the formation of a surface film or a
diffusion layer at the electrode surface such that dissolution is a "randomized"
process and preferential etching is suppressed. Clearly the form of the film is important
otherwise true passivation may take place--in Fig. 4 concentrations below 2M cause
low c.ds. but this is due to passive phosphating films and not electropolishing films.
Electropolishing continues to take place on alloys as well as pure metals in essentially
the same manner, although if a second phase appears, having its own well-defined
electrochemical characteristics, preferential dissolution may take place within an
apparently polishing film condition.
The difficulties of examining the role of either surface films or diffusion layers in
the mechanism of electropolishing are obvious although impedance measurements s
or ellipsometry22 have been used. However, if activation energies are determined
for the process over a range of temp. some indications of mechanism may be obtained.
Assuming an Arrhenius-type relation* the data of Fig. 2 has been replotted as log i
against 1/T (Fig. 8) and it may be seen that two lines result with a transition at about
37°C. The data of Honeycombe and Hughan 5 is insufficient to establish a transition
temp. although a change in slope may be perceived. However, data of Hoar and
Rothwel112 can be compared; by taking relatively few values around the transition
temp. they obtained a spurious activation energy value, although with hindsight, the
change in slope may be discerned. From the data presented here values of the activa-
tion energy may be found to be 5.9 kcal/mole below 37°C and 4.2 kcal/mole above
37°C compared with the earlier values x2 of 3.4-3-6 kcal/mole.
These two values, together with the appearance of a transition, seem to be distinc-
tive, although it is not possible to be dogmatic about possible mechanisms in view
of the similarity of the values. At low temps, the viscosity of the ortho-phosphoric
acid solutions is readily apparent and electropolishing at lower over-potentials is
*ipoj = A exp (-- Q/RT) where Q is the activation energy and T the absolute temp.
Electropolishing of copper and copper-based alloys 119

Temperature, °C
70 60 50 40 30 20 to

22 ~ k cal/m

2 0 I~

~ ~--~ ~ Q=34 k cal/m

,6 ""3,
±':× ~ . ~ .....
i \\ .
o; z' Copper This ~ "
o 14 -I- 29Zn:71Cu J investigation " - ~ \

AIm Hoar and Rothwell ~'" "~ "~K.


[.2 "~,
o Honeycombe and Hughan Q = 5.9 k cal/m "~
io >:';%,,

o 28 L330 5~32 O'34 O'36


Reciprocal temperolure, °K'x IO 2

FIG. 8. "Arrhenius" activation energy plot for copper in 67% ortho-pbosphoric acid.

accompanied by a black film (see Refs. 9, 12); at higher temps, the viscosity, is less
apparent, thermal convection currents may be observed and the black film stage
tends to be less important. Circumstantial evidence, therefore, suggests that at lower
temps, electropolishing may be diffusion-layer controlled while at higher temps, it may
be surface-film controlled. (It may be noted that data for the single-phase brass fits
the same pattern of behaviour).
When the behaviour of the aluminium-bronze is compared to that for copper it
is clear that the breakdown of the "secondary plateau", which might be expected
to be due to copper dissolution, is in fact due to preferential dissolution of the second
phase 3'2 leading to dealuminification. The presence of about 8 % aluminium in the
primary solid solution (~) therefore appears to have ennobled the matrix phase
sufficiently to avoid dissolution at these potentials (En ~ 1850 mV). Rowlands 2a has
shown that the Y, phase is markedly anodic with respect to et in sea-water (a difference
in corrosion potential of about 300 mV) and practical experience indicates that
corrosive attack of this type will occur in acid solutions. 24 An adequate metallographic
electropolish is nevertheless achieved at conditions recommended for copper but
clearly the low potential range, associated with black film polishing, is preferable
otherwise selective attack of the second phase may take place.

Acknowledgement--The author is indebted to Professor G. W. Greenwood for making laboratory


facilities available and to various colleagues for helpful discussion.

REFERENCES
1. P. A. JACQUET,Met. Rev. 1, 157 (1956).
2. W. J. M. TEGART,Electrolytic Polishing of Metals and Alloys, 2nd Ed. Pergamon (1959).
3. P. A. JACQ~T, C.R. Acad. Sci. 201, 1473 (1935).
4. P. A. JACQUET,Trans. electrochem. Sac. 69, 629 (1936).
120 D . R . GABE

5. R. W. K. HONEYCOMBEand R. R. HUGHAN, J. Counc. Sci. Ind. Res. Aust. 20, 297 (1947).
6. A. I-I.tcKtaNG and J. K. H[GGINS, Trans. Inst. Met. Fin. 29, 274 0953).
7. K. F. LORKrNG, J. electrochem. Soc. 102, 479 (1955).
8. M. COLE and T. P. HOAR, Proc. 8th CITCE 1956. Butterworths 0958).
9. K. F. LORKING, Electrochim. Acta 7, 101 0962).
10. F. H. GILES and J. H. BARTLETT,J. electrochem. Soc. 108, 266 (1961).
11. H. F. WALTON,J. electrochem. Soc. 97, 2,19 (1950).
12. T. P. HOAR and G. P. ROTHWELL, Electrochim. Acta 9, 135 0964).
13. E. S. VARENKO et al., Prof. Met. 6, 106 (1970).
14. D. T. PORTER, M. DONIMIRSKA and R. WALL, Corros. Sci. 8, 833 (1968).
15. T. P. HOAR and J. A. S. MOWAT, Nature 165, 64 (1950).
16. T. P. HOAR and T. W. FARTHING, Nattire 169, 324 0952).
17. I. EDWARDS, 3". electrochem. Soc. 100, 189C, 223C (1953).
18. C. WAGNER,J. electrochem. Soc. 101,225 (1954).
19. E. C. WILLIAMS and M. A. BARRETT, J. electrochem. Soc. 103, 363 (1956).
20. T. P. HOAR, Modern Aspects t~f Electrochemistry (Ed. BOCKmS) 2, 262. Buttcrworths, London
(1959).
21a. T. P. HoAR, D. C. MEARS and G. P. ROTHWELL, Corro~. Sci. 5, 279 (1965).
21b. T. P. HOAR, Corros. Sci. 7, 341 (1967).
22. M. NOVAK, A. K. N. REDDY and H. WROBLOWA,J. electrochem. Soc. 117, 733 (1970).
23. J. C. ROWLANDS, Corros. Sci. 2, 89 (1962).
24. "Aluminium Bronze", Copper Devel. Assoc. Pub. 31.