Electrochemic~corrosionof me~c

biomaterials
Centre Belge d’Etude de la Corrosion, CEBELCOB, Avenue Paul Heger, Grille 2, 1050-Brussels, Belgium

This paper was given as a Keynote presentation at the conference BIOINTERACTIONS 84,
London, 4-6 January 1984.

Methods of electrochemical the~o~namics (electrode potential-ptl equilib~um diagrams) and electrochemical

kinetics (polarization curves) may help to understand and predict the corrosion behaviour of metals and alloys in
the presence of body fluids.
A short review of the literature is given concerning some applications of such methods, both in vitro and in
viva, relating to surgical implants (stainless steels, chromiu~cobal~molybdenum alloys titanium and titanium
alloys) and to dental alloys (si~e~ti~copper amalgams sifver-base and gold-base casting alloys, nicke~base
casting alloys).
Attention is dmwn to the necessity of more basic research on crevice- and fretting corrosion of surgical
implant materials and dental alloys, and to the toxicity of corrosion products. A perfect understanding of the exact
significance of electrode-potentials is essential for the success of such a task

Keywords: ~~pia~~ materials, dental alloys. coirosion, irnrn~Ri~, passivity, elect~ockami~at tasting methods

An International Symposium on Corrosion and Degrada-
tion of ~m~iant Materials, was held in Kansas City, Mon-
tana on 22-23 May 1978, under sponsorship of the
American Society for Testing and Materials ASTM’. On
the occasion of this Symposium, an excellent report on
Fundamental Aspects of the Corrosion of Metallic
implants, has been presented by Kruge?. As stated in this
report, ‘the corrosion of metals in the aqueous environ-
ments of body fluids involves the setting-up of elec-
trochemical corrosion cells. The corrosion produced by
these cells is controlled by thermodynamic and kinetic
factors. The thermodynamic factors determine the corro-
sion tendencies; the kinetic factors determine the rate’.
The reader is advised to read with great attention
this report of Kruger, as well as other reports published in
the Proceedings of this Symposium. In the present lec-
ture, some additional comments will be presented, with
special consideration to the electrochemical processes
occurring when metals and alloys are in contact with
physiological environments which exist in orthopaedic
practice and in dentistry.
rechts3, p.256, of the values of rH and r0 of aqueous
solutions*.
Figure 2 shows the conditions of the~odynamic
stability of water under a pressure of 1 atm.; below line a,
water may be reduced with evolution of hydrogen; above
line 6, water may be oxidized with evolution of oxygen.
Figure 3 shows the acid, alkaline, oxidizing and
reducing media.
Figure 4 (4, pp. 76-79) shows, according to some
assumptions+, for43 metals and metalloids, the theoreti-
cal conditions of immunity (where the metal or metalloid
is thermodynamically stable), of passivation (where its
stable form is a given oxide, which may be protective or
not protective), and of corrosion (where its stable form is
dissolved in water, or gaseous).
Figure 5 shows, among the 43 elements listed in
Figure 4, 21 metals which may be immune or passivated
at the pH’s to be considered for surgical implants: accord-
ing to Laing5pp.203,normally pH 7.4; pH 5.6 after surgery,
and pH 9.0 in case of infection. These metals are gold,
.iridium, platinum, rhodium, ruthenium, palladium, mer-

*rH = - log ug, and r0 = - log po,, where pns and poz are the equili-
brium partial pressures in hydrogen and oxygen.
ELECTROCHEMICAL THERMODYNAMICS ‘It is assumed that corrosion of a metal occurs when the solubilityof its
OF METALLIC CORROSION dissolved form exceeds 1 0V6 mole per litre, or if the equilibrium pre-
ssure of its gaseous form exceeds 1 OW6 atm. These diagrams may be
Figure I shows the potential-pH equilibrium diagram for valid only in the absence of substanc~sforming soluble complexes with
water at 25°C with indication, as was done by M. Huyb- the considered elements: e.g. ammonia for Cu, chloride for Cr.

0 1984 Butterworth Et Co (Publishers) Ltd. 0142-9812/84/050122-13 $03.00

122 Biomaterials 1984, Vol5 May

 Metallic corrosion: M. Pourbaix

-2 0 2 4 6 6 IO 12 14 16
l,SO 1 2 345678 9 IO 11 12 13 14 136
I,4 ---__ I,4

region of water at 1 ?-Q.

-0,&i_
iiberot/on of hydrogen and
-Cl,6 - 1,2 - o/ka/i2atr’0ll

-0,0
-Vj- , , , , , , , , j
-1 ___ -___pI-l
k- -2 0 2 4 6 8 10 12 14 16
-I,21 J-1,z Figure 2 Domain of thermodynamic stabihtv of water under 1 atm
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
P” pressure at 25’C.

Figure 1 rH and r0 of aqueous solutrons

-2 0 2 4 6 6 10 I2 14 16

oxidizing and
cury, silver, osmium, copper, tin, indium, gallium, tan- oikoline medkm
talum, niobium, chromium, zirconium, aluminium, hafnium,
titanium, beryllium. In fact these 21 metals are those ---I
which are resistant to pure water. 1
For 4 of these metals (aluminium, copper, and pro-
I
bably indium and tin), the oxides which make them
passive in the presence of pure water are not sufficiently
protective if chlorides are present, probably due to the for-
mation of soluble chloro-complexes or of insoluble basic
chlorides. Most of the fluids existing in our body (such as
‘.
blood, plasma and lymph) have a chloride content (and .- ’ ._
pH) somewhat similar to that of sea water (about 5 to ---.
reducing and
20 g/l and pH about 8). The metals which may be con-
- 1,2 acidic medium alkaline medium
sidered for implants are thus just the same as those which
t
resist perfectly to sea water, with the exception of those
which poison the human body (mercury, gallium?, haf- -I+ , , , ,
nium?). As a result of this, the 13 following metals may -2 0 2 4 6 8 10 12 14 16
theoretically be considered for use as surgical implants
Figure 3 Aod, alkaline, oxidizing and reducing media.
and dental alloys:

8 noble metals, which keep a really metallic alloys. Tables 7 and2 give lists of metals and alloys which
surface: Au, Ir, Pt. Rh, Ru, Pd, Ag, OS are in fact used for such purposes. One sees that:

5 passive metals, which are covered by a layer of Au, Pt. Pd and Ag are commonly used in dental
protective oxide: Ti. Ta. Nb, Zr, Cr. alloys, together with Sn and Cu,

These are thus the basic elements of surgical and dental Cr (together with Fe, Ni and MO) and Ti (together

Table 1 Some alloys used for surgical implants

Fe Cr Ni MO C Mll Si co P S

;a) Stainless steels

AISI 31 6L6 bal 17.33 13.69 2.34 0.017 1.73 0.65 - 0.023 0.027
AISI 316L-CW’ bal 17.4 13.8 2.14 0.026 1.62 0.57 ? 0.020 0.002
AISI 304L’ bal 18.10 10.30 0.32 0.020 1.40 0.41 - 0.032 0.013
TRIP steel 4Mo.l %CW8 bal 12.5 7.27 3.88 0.29 0.011 0.05 ? 0.008 0.002

Lb)Chromium-cobalt-molybdenum
alloy
Vltalllum8 0.18 27.4 0.29 5.10 0.20 0.85 0.80 bal , ?

Fe C Al V 0 N H Ti

:c) Titanium alloy6

Ti.6Al.4V 0.15 0.013 6.20 4.05 0.13 0.011 0.0058 bal

Biomaterials 1984, Vol 5 May 123

Metallic corrosion: M. Pourbaix

Table 2. Some dentaf alloys

Ni Cr MO Mn Al Si Others

a) Nickef-chromium alloys’ o
I A Ducinox 65 22 - - - ? Fe, B, C
B Howmedica Ill 68.3 20 4.5 1.2 <O.Ol 2.5 Cu. Sn, 6
Ceramalloy 70 20 5.6 - - - Fe, Ti, C
II C Ticon 70 16 5 4 2.6 0.8 Fe, Be, C
D Victory 70 18 11 - - Fe
E Wiron S 70 16 4.8 3.5 4 0.8 6
Wiron 77 70 76 4.8 3.5 4 0.8 Nb
Ill F Gemini II 80 12 2 - 3 0.18 Be
G Jelbon 69.5 13.2 4.3 5.3 3.3 4.3 Fe
H Microbond NP.2 67.9 12.1 6.8 0.15 - 0.65 Fe, Ga7.3
I Ultratek 80.5 11.4 2 0.02 2.2 - Be, Cu, Co
Experimental I bal 10-16 IO-15 o-1 Gl.5 O-l -
IV J Phenix 81.5 11.7 - 0.05 - 6.3 Fe, Co
K Ryco AR.1 71.6 15.1 - 3 - 3.2 Fe. Cu, Co
V t Experimental II bal 15-20 - 0.2 - - Co1 216, Sn, Nb, La
Experimental Ill bal 15-20 0.7-l 5 0.7-l .5 1.5-3.0 Co1 2-16, Cu

A% Sn CU In Au Pt Pd Zn In+ZN

bJ Amalgams9
n’ 1 70.0 17.0 3.0
2 60.0 27.0 13.0
3 40.0 30.0 30.0
4 71.0 17.0 12.0
5 60.0 22.0 13.0 5.0

c) Silver base allo$

no 6 70.0 ? 25.0 ? 5.0
7 65.0 1 5.0 25.0 ? 5.0
8 45.0 15.0 ? 23.0 ? 1 .o

d) Gold base alloys’

no 9 46.0 8.0 40.0 5.0 ? 1.0
10 35.0 10.0 50.0 3.0 ? 2.0
11 27.0 8.0 60.0 2.0 3.0
12 12.0 10.0 69.0 3.0 3.0 3.0

with Al and V) are commonly used in surgical increasing and decreasing electrode potentials, and
implants and in dental alloys. sometimes mistakenly called ‘hysteresis curves’) deter-
mined potentiokinetically in an aqueous solution. Points A
No mention is made in these tables of Ir, Rh, Ru, OS, Ta,
and B indicate the equilibrium potentials of respectively
Nb and Zr, although some uses ofTa in surgery have been
hydrogen and oxygen under 1 atm. pressure at the con-
reported “ p.2*4. It is likely that, amongst these 7 metals,
sidered temperature and pH (e.g. - 413 and i- 813 and
the cheapest ones Nb and Zr might be of special
$_ 810 mvversus the standard hydrogen electrode she, at
interest.
1 atm., 25”C, and pH 7.0). Point C is the i~~un~~poten-
tial, below which the considered metal or alloy is immune,
and thus thermodynamically uncorrodible.
ELECTROCHEMICAL METHODS FOR STUDYING
Figure 6a denotes a general corrosion (with evolu-
METALLIC CORROSION
tion of hydrogen below potential A, and without such an
evolution above potential A).
Polarization cunres, potentiokinetic and potentiostatic
Figure 66 denotes a perfect behaviour, without any
methods
corrosion, even if the metal or alloy is being used as an
Many electrochemical methods, based notably on pioneer electrolytic anode (above potential B) or cathode (below
works”, “, and making use of the concepts of elec- potential A); in this case the two branches of the polariza-
trochemical affinity and of electrochemical kinetics, are tion curve simply relate to the evolution of O2 (and perhaps
presently available for predicting experimentally the real of 0s and H202) and of H2 on uncorrodible electrode.
corrosion behaviour of metals and alloys. For instance, Figure 6c denotes corrosion in reducing media, with
polarization curves, where the electrode potential E formation, above the passivation potential P, of an oxide
(which may measure the affinity of an electrochemical protective film which makes the metal passive under
reaction) is drawn as a functjon of an electric current I oxidizing conditions.
(which may measure its velocity), when determined in Figure 6d denotes a perfect behaviour under reduc-
stirred and oxygen-free aqueous solutions, may, if correc- ing conditions, but the protective oxide film becomes
tly performed and interpreted, enable a fully reliable pre- damaged, with formation of pits, above the rupture (or pit-
diction of the conditions of corrosion and no-corrosion of ting) potential R; the electrode potential at which, on the
metals and alloys. return scan at decreasing potentials, the electrolysis
Figure 6 shows schematically, as an example, five current reaches value zero, is the protection potential
types of cyclic polarization curves (drawn at successively above which pre-existing pits may grow and below which

124 Biomateriafs 1984, Vol5 May

 Metallic corrosion: M. Pourt

0 7 4 0 7 14 0 7 14

0 7 $4 0 7 14 0 7 t4

0[_!14 0l-J 14 0 Ilg&_T l&PM

Figure 4 Carrosiou, immunify and passiwtion domains ofr netafs and

metalloids, ordered according to their thermodynamrc I,Ob/ fity.

Biomateriafs 1984, Vof 5 May 125

Metallic corrosion: M. Pourbaix

such pits do not grow anymore. The behaviour of such a

metal and alloy is thus completely safe below the ‘protec-
tion potential’.
Figure 6e relates to a metal (or alloy) which suffers
general corrosion under reducing conditions, becomes
passive above the passivation potential P, and suffers pit-
ting above the rupture potential R; as already said for
Figure 6d, the so formed pits still grow between potentials
R and ‘prot’; and do not grow anymore below the protec-
tion potential ‘prot’. The potential range from ‘prot’ to R
may thus be considered as a range of imperfect passivity
and the protection range from ‘prot’ to P is a range of per-
fect passivity (which has a very great practical importan-
ce), where the metal or alloy does not suffer any corrosion,
even if its surface has been previously damaged. Between
the passivation potential P and the immunity potential C,
the passivating film may be dissolved by reduction and
general corrosion occurs. Below the immunity potential C,
the metal or alloy becomes immune and is again
uncorrodible.
As said before, polarization curves such as those
shown in Figure 6 may be drawn, rather quickly, with a
potentiokinetic method (often improperly called ‘poten-
tiodynamic’) where, with the aid of a potentiostat, the
electrode potential is moved continuously upwards or
downwards. More accurate and reliable polarization cur-
ves may be obtained, but more slowly, with a ‘potentio-
static’ method, where the electrode potential is kept
constant at different values during a more or less long
period of time. Such methods, preferably if combined with
chemical analyses and with methods of physical metallurgy,
may usually lead to a perfect solution of corrosion pro-
blems, even when very complex.

Other electrochemical methods

Other electrochemical tests may be useful. Among them,
we note:

Zero-current tests, where the metal is simply

immersed, without stress or under stress, in the
considered solution, with measurement of the
influence of time on its electrode-potential;

Linear polarization tests,

impedance tests,

Potentiostatic tests under stress, as developed by

R.N. Parkins, where strained specimens are kept
immersed until rupture, at given electrode
potentials.
We also mention the rubber band test for crevice corro-
sion, which will be considered in Figure 72 of the
present report

EXPERIMENTAL CONDITIONS OF METALLIC

CORROSION
The equilibrium diagrams shown in Figures 4 and 5 are
based on certain hypotheses. They may be a good guide
for corrosion teaching, research and control, but they
should be used only with full appreciation of their
significance, validity and limitations. Most of them should
be checked and improved experimentally.
For instance, Figures 7a and b14, p.‘3s show theoreti-
cal corrosion-immunity-passivity diagrams for iron at
Figure 5 Metals resisting to corrosion between pH 5.6 and 9.0. 25°C. when assuming respectively that both lepidocrocite

126 Biomaterials 1984, Vol5 May

 Metallic corrosion: M. Pourbaix

P
:-3 - - -.- - -
I$
-.$---_-C
A 7
%- /
$
P

Figure 6 Types of polarization curves

Biomaterials 1984, Vol 5 May 127

Metallic corrosion: M. Pourbaix

d.
Figure 7 Theoretical conditions of corrosion, immunity and passivation of iron, at 25°C: (a) assuming that both yFeOOH and Fe,O, are protective;
fbj assuming that yFeOOH is protective and Fe304 not protective.

yFeOOH and magnetite Fes04 are protective, and that, as and of perfect passivation are the only two where no
shown by many authors14, p.22’, only yFeOOH (very similar danger of corrosion exists.
to maghemite yFez0,) is protective. Experiments conduc- Figures 1Oa to IOd, which should be considered as
ted in stirred oxygen- and chloride-free solutions have led provisional and subject to more or less important mod-
to the polarization curves (of the types given at Figure 6~). ifications, show such areas relating to solutions more con-
shown at Figure 8at4, p.263, which enable to draw the centrate in chloride (1 O- ’ molar, i.e. 3.5 grams Cl per
experimental corrosion-immunity-passivity diagram given litre), for respectively iron, a chromiun+steel AISI 410, a
at Figure 86. One sees that the experimental diagram 86, chromiumnickel steel AISI 304, and a chromium-nickel-
very well fits with the theoretical one 76: the passivity of molybdenum steel AISI 316, with both emerypolished
iron in chloride-free solutions is thus really due to a pro- and electropolished surface conditions. The narrow verti-
tective film of ferric oxide y-FeOOH (or yFe203), and cal area drawn around the middle of these few figures
magnetic Fe304 is not protective. shows the conditions which may occur when the metal is,
Figures 9a and96 give results of similar polarization at zero-current( i.e. without electrolytic or galvanic action),
experiments in solutions containing chloride (1 O- * molar, in contact with a solution of pH 7.4 (which is the normal
i.e. 0.35 g Cl per litre). The polarization curves given on pH of healing wounds). The two vertical areas which are
Figure 9a are, depending on the pH, of the type a, c or d of on both sides of this narrow vertical one show the condi-
Figure 6. It appears that such an amount of chloride does tions which may occur in case of infection (pH 7.4 to 9.0)
not modify markedly the conditions of immunity (where or of haematoma (pH 7.4 to 5.6). The upper part of these
metallic iron Fe isstable), northe’passivation potential’ EP three vertical areas indicates the behaviour of the metal in
(above which a passivating ferric oxide film appears). But the presence of oxygen. The lower part of these areas cor-
above a given’rupture potential’ E,(which depends on the responds to the behaviour of the metal in the absence of
value of the pH), this ferric oxide ceases to be protective oxygen, such as what may occur for instance when the
and pitting corrosion appears. The electrode potential E, access of air is restricted by a particular geometry of the
where, on the return scan of the polarization curve, the structure (under a screw), or due to a deposit of solid cor-
electrolysis current reaches value zero (in oxygen-free rosion products (rust). If the considered metallic structure
solution), is, as already said in section 3 of the present is locally aerated and locally non-aerated, and if the lower
report, the’protection potential against the propagation of part of the pH 7.4 to 9.0 area lies in the triangular corro-
localized corrosion’, above which the pre-existing pits still sion area, localized corrosion may start by differential
develop, and below which these pits do not grow any aeration between, as shown in 1923 by Evans15, more or
more. The polarization curves shown at Figure 9a allow to less passive aerated surfaces where oxygen is being
draw Figure 96 which shows, besides areas of general reduced, and active non-aerated surfaces where the metal
corrosion and of immunity, an area of pitting, an area of corrodes. This corrosion at low electrode-potential leads
imperfectpassivity(where no new pits may be formed, but to the formation of cavities for which Brown has proposed
where pre-existing pits may grow) and an area ofperfect the wording occluded corrosion cells o.c.c.‘~, and inside
passivity (where no new pits may be formed and where which the solution becomes acid as a result of hydrolysis
pre-existing pits may not grow). The regions of immunity phenomena: up to pH 3.8 for iron and carbon steels, and

128 Biomaterials 1984, Vol5 May

 Metallic corrosion: M. Pourbaix

._---__
_----es

77-;

FIgwe 8 Behaviour of MO” in aqueous solutions: (a) polansation curves; (bJ corro~on-. /mmun/ty- and passivatior~ diagrams

much lower for alloy steels containing chromium: about becomes immune, due to some kind of cathodic
1.8 for chromium steels AISI 410, and about zero for protection.
chromium-nickel AlSl 304 and chromium-nickel-molyb- One sees in Figure 10 that alloying iron with
denum AISI 316 steels. The potential- and pH-conditions chromium, nickel, molybdenum, noticeably increases
inside these o.c.c.s, which are about the same whatever the resistance of the metal to pitting corrosion, which
they are formed at low potential (crevices) or at high might result of the presence of air: air pushes the elec-
potential (pits) stabilize at values which are shown trode potential upwards, towards the *oxygen line’ (b); this
schematically by black circles in Figure 70. The ‘protec- improvement of the resistance to pitting is particularly
tion potentials against the propagation of localized corro- great if the metal is electropolished.
sion’ which are shown at Figures Gdand 6e and at the four Figure I7 shows a similar diagram for titanium.
Figures IOa and 70d are, as appears from these four last As said before, crevice corrosion may affect metals
figures, slightly higher (more positive) than the zero- and alloys for which the lower part of the vertical area
current potentials inside the o.c.c.s: these ‘protection drawn around pH 7.4 reaches a corrosion area. It appears
potentials’ are in fact the electrode potentials (measured at Figures 70 that both iron or carbon steel (Figure I&)
on the external passive surfaces) below which the elec- and chromium steel AISI 410 (figure 7Ub) are very sus-
trode potentials inside the o.c.c.s is lowered below its ceptible to crevice corrosion, Chromiun+nickel steel AISI
zero-current value, so that the metal inside these cavities 304 (Figure 70~) behaves better, but is still dangerous.

E E E E

I 1L 8

sg~
Br - <
r -- -.
4 ,
3 -_

P_
A
----SW
_____

P
---

A
P
1_-----

------ ____--

__--_

y.
t
i 0
I 2
I I
4 6
I I
8
I
IO
I
12 14
vH=S pH'7 PHI 13 PH
Figure 9 Behaviourof iron in aqueous solutions containing chloride (10 ’ molar, L e. 0.35 g Cl ///: /a) polarrsatron curves; /bJ corrosion-, immunity-,
prtting-, imperfect passivity- and perfect passwity diagrams.

Biomateriafs 7984, Viol 5 May 729

Metallic corrosion: M. Pourbaix

) 21 Y 6I 01 10 12 I
1 1
E
H

.+f

-0

.-I

a b
t , . I 1 , I 1 I , I I 1
0 2 Y 6 b 10 12 1 02 Y 6 8 10 12 1
PH

2 4 6 8 to 12 14

EH

?l 21

-0 -0

.-t ,_l

C d
I r 1 r 1 I I I i

0 2 4 6 0 10 12 I4 2 4 6 f2 14

P P
Figure 10 Experimental areas ofgeneraf corrosion, immunity, pitt/ng, imperfect andperfectpassivity of iron and steefs in the presence ofsohftions
fO- 1 molar in chloride {3.5 g/f Cf. j at 25°C: (aJ iron and carbon steels; (bj chromium sreel AlSi 4 10 fdraftj; (cj chromium-nickel steel AISl304:
/d) chromium-nickeCmolybdenum steel AI.71 3 16 (draft).

Chromium-nickel-molybdenum steel AISI 316 (Figure
f&Y) is still at the limit between danger and no-danger,
and it is likely that its behaviour depends on its content in
carbon (which should be very low) and on its surface con-
dition (which should best be electropolished). As the
crevice behaviour of such steels essentially depends on
the existence of a protective film, greatest care should be
taken for keeping this film in perfect condition. Any
damaging action to this film, notably by heavy rubbing
when screwing, should be avoided; any local destruction
of the protective film might lead to the formation of a very
acid (pH up to zero) and very corrosive occluded corrosion

130 Biomaterials 1984, Vol5 May

 Metallic corrosion: M. Fourbaix

cell. It is likely that special pretreatments may very much Table 3 A~ifi~ia~ ph~siologi~alsolutions wed for testing the corrosion
behaviour of implant materials
reduce this danger of fretting corrosion.
According to Figure 1 I, titanium, forwhich the verti-
(a) HANKS’s solution (according to Hoar and Mears I@, p. 490)
cal area drawn around pH 7.4 does not reach the corro-
sion area, would not suffer crevice corrosion. @/I @/I

Experience has shown that, for surgical implants as NaCI 8.00 MgCI, .6H,O 0.10
CaCI, 0.14 Na,HPO, ZH,O 0.06
well as in dentistry, crevice corrosion is the most
KCI 0.40 NaH,PO, 0.10
dangerous cause of degradation. Electrochemical tests NaHCO, 0.35 MgSO, 7H,O 0.06
making use of potentiostats, such as those which have glucose 1 .oo
been used for drawing Figure 6 and Figures8 to IO may be This solution has pH 7.4 and contains 5.0 g Cl per Iltre.
particularly useful for predicting the danger of crevice cor-
(b) CIGADA solution 7, p. 149
rosion. Although much work remains to be done in this
8.74 9 NaCl per litre
respect, notably for setting up fully reliable corrosion
0.35 g NaHCOs per litre
diagrams which would improve, and develop for other 0.06 g Na2HP04 per litre
metals and alloys, the provisional schemas given in 0.06 g NaH,PO, per litre
Figures IO and I I, important research has already been
This solution has pH 7 and contains 5.3 grCl per litre. Nitrogen is
performed by many scientists on the electrochemical bubbled contmuously to remove the oxygen.
behaviour of metals and alloys in artificial physiological
(c) A~i~c;a/sa/i~a (modified Fussayama’s solution, according to Meyer
solutions, as well as in vivo. Tab/es 1 and 2 give the et al. 70, p. 299)
chemical analyses of some metals and alloys which have
0.400 gr NaCl per litre
been used in such experiments. Table 3 gives the com-
0.400 gr KCI per litre
position of artificial physiological solutions. 0.690 gr NaH*PO, H,O per litre
Another test, less accurate, but very simple and 0.005 gr Na,S 9H,O per litre
striking, for checking the susceptibility of metals and 1.000 gr urea per litre
0.795 gr CaCI, H,O per litre
alloys to crevice-corrosion, consists, as shown in 1955 by
LaQue et af. “, p39, in immersing in the considered solution This solution contains 4.3 gr Cl per litre.
a plate of the considered material around which has been
stretched a rubber band (Figure 12): by avoiding the
access of oxygen, the rubber band promotes, on metals mended the AISI 302, to which the AISI 316L has been
and alloys for which the dangerous corrosion area at low later found to be far superior, due to its better corrosion
potentials extends to the pH of the solution (e.g. 6.5 to resistance. In 1951, Jergensen and Leventhal started using
9.0), corrosion which leads to local acidification, and thus titanium, and, recently, the use of the ELI titanium-
to local dissolution of the metal in the so formed crevice. aluminiurr+vanadium alloy has been reported.
The stretched rubber band thus cuts the metal slowly. By In 1949-1950 CITCE and CEBELCOR* were created
applying this method on three alloy steels dipped in a 1 simultaneously for promoting basic and applied research
molar NaCl solution (35.5 g Cl/I), De Greve’*, p. “O has in electrochemistry and in some field of technical interest,
observed after 32 days, notches of the following depths: including corrosion20. 2’. 22, and this resulted in an impor-
tant development of electrochemical testing methods in
both scientific and industrial circles. These methods led to
AISI 430 AISI 304 L AISI 316 L
a real mutation in electrochemical science and technology
and the work was published4a. T.P. Hoar, who was one of
Depth of the
the founders and presidents of CITCE, and a scientific
upper notch (mm) 6.5 2.0 0.04
advisor of CEBELCOR, was an outstanding pioneer in the
Depth of the applications of electrochemical testing methods for the
lower notch (mm) 3.2 1.5 0.02 study of metallic implant materials. This led, in 1966, to
the publication of his excellent paper with D.C. Mearslg, in
which they concluded that ‘stainless steels (even of the
higher chromiumnickel quality) and nickel alloys are
PRESENT KNOWLEDGE ON THE CORROSION
unlikely to resist all breakdown by pitting when exposed
BEHAVIOUR OF METALLIC IMPLANT MATERIALS
to the body fluids (or other media containing chloride)
Before closing this report, a short survey will be given con- indefinitely; that the cobalt-based alloys may well withs-
cerning the presence knowledge on the corrosion tand such exposure for very long times; and that titanium
behaviour of metallic implants and dental alloys, as result- and (especially) some of its alloys should withstand such
ing from work conducted both in vitro (in artificial an exposure for an indefinite period. Mears further work
physiological solutions) and in vivo (on animals). Readers was published23. Solaret al. 24 have recently confirmed the
are directed to references 1 and 19. excellent behaviour of titanium implants, and of some
titanium alloys, but they have expressed some concern
Surgical implants about the possible formation of wear debris of oxide parti-
cles which, however, have not been found to be toxic. Cer-
According to a historical review by Laing’, the first fixation
tarn pretreatments before surgery should be able to
of fractured bones was done in 1775 with iron wires, and
remove this risk of formation of debris.
infection was then the main problem. Lever? and Lambotte
could later avoid infection by replacing iron by platinum, *CITCE is the acronym for’comite International de Thermodynamique
gold or silver. In 1923, Smith-Peterson introduced the et de Cindtique Electrochimiq~es‘ (International Committee for Elec-
trochemlcal Thermodynamics and Kmetics), which became m 1970 the
cobalt-chromiu~molybdenum alloy Vitallium, which is
‘International Society of Electrochemistry ISE. CEBELCOR IS the
still successfully used today. Stainless steel started to be acronym for’Centre Beige &Etude de la Corroston’ (Belgian Center for
used around 1942, when Murray and Fink et al. recom- Corrosion Study).

Biomateriafs ?984* Vo! 5 May 131

Metallic corrosion: M. Pourbaix

0 2 4 6 a 10 12 14 manganese improves the resistance of nickel-base alloys.

1 I,/V
‘E
A chromium content above 20% causes corrosion to dec-
rease because of the precipitation of a chromium-rich
phase. The nickel-vanadium system proved to be unsatis-
factory; however, the addition of chromium improved the
corrosion resistance of the resultant ternary Ni-V-Cr sys-
,1 tem. The addition of cobalt and gallium improved the cor-
rosion resistance of nickel-base alloys. The authors
caution, however that since the biocompatibility of ele-

I_--
\ ments such as nickel, vanadium, gallium, etc. . . , is not
fully known, these new alloy systems should be judged
not only by their technical and corrosion properties, but
also by the results of well-controlled biocompatibility
43 tests. Referring to a publication of Valegaz6, Meyer
states”, p.2g6that ‘since nickel is the major component of
the base-metal alloys used for fixed prosthodontics, the
allergenic potential of this element should be stressed;
nickel is one of the most common causes of allergic der-
. matitis and is responsible for more allergic reactions than
-1 all the other metals combined’.
References 27 to 42 indicate chronologically some
recent publications on the corrosion behaviour of dental
. alloys issued (or to be issued) after the 1978 ASTM Kan-
sas City Symposium, and related to work making use of
?I electrochemical methods.
0 2 4 t5 8 70 12 14 Attention is brought to the following results of
these publications:
PH
Figure 11 Areas of general corrosion and passivatlon of titanium at
Galvanic coupling of dentalalloys: Meyers’* has observed
25°C (drat?).
the following values of zero-current electrodes potentials
Since the appearance of the pioneer paperlg elec- in the artificial saliva indicated in Table 3 of the present
trochemical methods have been constantly used for report (page 131):
studying the corrosion behaviour of implant materials,
both in vitro and in vivo. Recent examples of such studies
mVsce i.e. mVshe
in vivo relating to stainless steels, cobalt-chromium-
molybdenum alloys, titanium and titanium alloys may be
Platinum + 130 + 380
found in publications of lman et al6 on corrosion fatigue,
Golds A + 100 + 350
of Cigada et al.’ on localized corrosion, of Solar et aLz4 on
Golds I3 + 90 + 340
titanium release. Electrochemical studies both in vitro and Golds C + 75 + 325
in vivo have been published by Syrett et al.8 and by Golds D + 60 + 310
Sola$5. Golds E + 40 + 290
Stainless steels F - 75 + 157
Dental alloys Stainless steels G - 100 + 150
Results of electrochemical tests performed for studying Ni base alloy H - 150 + 100
the corrosion resistance of dental alloys (see Tab/e 2, Ni base alloy I - 180 + 70
page 124) in artificial saliva (Table 3, page 131) have been Amalgam K - 185 + 65
published’. These tests were conducted by Sarkar et al.’ Amalgam L - 200 + 50
on silver-tin-copper amalgams and on silver-base and Amalgam M - 380 - 130
gold-base casting alloys; they were conducted by Meyer
et al.” on nickel-base casting alloys.
Amalgams: According to Mahler et al.37. creep and corro-
For silver-tipcopper unlike conventional
amalgamsg: sion of traditional amalgams are directly related to their
dental amagals, where corrosion is associated mainly with amount in the Sn-Hg y2 phase.
the presence of the tin-mercury 72 phase, the corrosion
of y2-free dental amalgams results from the presence of
silver-copper eutectic, or copper-tin, or both.

For silver-base and go&base casting alloysg: the corro-

sion stems from the presence of silver-rich micro-
segregations, with a possible minor contribution from a
copper-rich phase.

For nickel-base casting alloys”: Tests have been con- Chromium Steeel Chrom~,uryNtckel Steel Chomlum-llrlcel-llolqbdCnumStcrl
ducted on commercial nickel-chromium alloys, and on Aisi 430 A151 30’1 AiSi 316
newly developed nickel-chromium and nickel-vanadiurn- Figure 12 The rubber-band test for crevice corrosion (after F. Laque et
chromium alloys, The addition of molybdenum and al. and J.P. De Greve).

132 Biomaterials 1984, Vol 5 Mav

 ~etajlic corrosion: M. Pourbaix

According to Meyer et al.27, blended amalgams 4 Pourbaix, M. et al., Atlas of electrochemical equilibria in
(with addition of silver-copper entectic in the form of mic- aqueous solutions (Translated from the French by J.A. Fran-
klin). Foreword by W.G. Burgers. Publ. NACE and CEBELCOR
rospheres) are superior to the conventional amalgams.
(1966, reprinted 1974)
5 Laing. P.G., Clinical experience with prosthetic materials: his-
torical perspectives, current problems, and future directions
Castings: Alloys with high precious metals content (Au, Pt lot. ctt. (1). 199-21 1
Pd) are characterized by immunity or anodic film protec- 6 Iman, M.A., Fraker, A.C. and Gilmore, CM., Corrosion fatigue of
tion over a range of anodic potentials, indicating superior 316 L stainless steel, Co-Cr-Mo ahoy, and ELl Ti-6 A&4\/ Lot.
corrosion resistance (Vadyanathan et a/.3’. Addition of cit. (1). 128-143
Cigada, A.. Mazza, B., Mondora, P., Pedeferrt, G and Sinigaglta.
palladium very much improves the corrosion resistance of
D., Localized corrosion susceptibility of work-hardened stam-
Ag-Cu alloys (Greener et al.38]. less steels in a physiologrcal saline solution LOG. clt (1),
144-l 60
8 Syrett, B.C. and Davies, E.E., Crevice corrosion of implant
Toxicity: Wright et al. 35 found a direct correlation between alloys. A comparison of in-vitro and m-vivo studies Lot. ctt. (1).
corrosion properties and cytotoxic response. Nickel in the 229-244
biologic environment is an element of concern as an 9 Sarkar, N.K., Fuys, R.A. Jr. and Stanford, J.W., Application of
electrochemj~ai techniques to characterize the cormsron of
ellergeeen and a carcinogen. Espevik has found up to
dental alloys Lot. cit. (l), 227-294
44 ppm Ni in artificial saliva in which dental alloys have 10 Meyer, J.M., Wirthner, J.M., Barraud, C.P.. Susz, C.P. and
been stored for two months (Newmann et a/.33). Nally, J.N., Corrosion studies on nickel-based casting alloys
lot. cit. (1 ), 295-315
11 Evans, U.R., The corrosion and oxidarion of metals: scientific
In vitro testing methods: Proteins (which exist in vivo and pnncrpfes and practical applications Arnold, 1960
do generally not exist in vitro inhibit the corrosion of MO, 12 Wagner, C. and Traud, W.. Ueber die Deutung van Korrostons-
vorgangen durch Ueberlagerung van elektrochemtschen
do not affect the corrosion of Al and Ti, slightly increase
Terlvorgangen und iiber die Potenttal-bildung an Mischelek-
the corrosion of Crand Ni, and very much increase the cor- troden Z. Elektrochemie 1938, 44. 391-402
rosion of Co and Cuz9. 13 Pourbatx, M., Lectures on e/ectrochem;ca~ corrosron (Tran-
slated from the French by J.A.S. Green, ed. R.W. Staehle).
Foreword by J. Kruger. Plenum Press and CEBELCOR. 1973
14 Pourbatx, M.. Lecons en corrosron electrochrmrque (2nd Edn.)
CEBELCOR, 1975
15 Evans, U.R., .J. Inst. Metals 1923, 30, 263-267
As a conclusion, it seems that more basic work remains to 16 Brown, B.F., Concept of the occluded corrosion ceil Corrosion
be done for studying thoroughly the conditions of crevice 1970, 26. 249
corrosion and fretting corrosion of metallic surgical I? Laque, F.L., May, T.P. and Uhlig, H.H Corrosron m acfion lnter-
implant materials, for completely clearing-up the best national Nickel Cy., 1955
18 De Greve. J.P., Etude a temperature ambiante de la corrosion
conditions of utilization of existing alloys, for setting-up
caverneuse en solution aqueuse chforuree de pH voisin de la
still better alloys, and finally for achieving a perfect neutral& de lrois aciers de types AtSl430, AISI 3041 et AISI
technology of bone surgery perfect alloys, perfect surface 316L Travatl de fin d’itudes Universite Libre de Eruxelles et
conditions and perfect use of these materials without any Cebelcor, 1972
19 Hoar, T.P. and Mears, D.C., Corrosion resistant alloys in
risk of short- or long-range crevice corrosion, fretting cor-
chloride solutions: materials for surgical tmplants, Proc. Roy.
rosion, and toxicity. Similar work remains useful for Sot. Series A. 1966, 294, 486-510
dental alloys. 20 Pourbatx, M., Le ClTCE et le CEBELCOR Le rnouvement scien-
Electrochemical methods of testing and research tifrque en Belgique VI, 476-481. Publ. Federation Belge des
Societes scientifrques (1961). Publications CEBELCOR F, 201
are a valuable tool for such a task, both in vitro and in vim
(1961)
However, some of the results of such methods already 21 Pourbatx. M., The birth of ClTCE Rapports Techniques
published in the scientific and technical literature should CEBELCOR, 116, RT. 185 (1971)
be accepted only with great caution, often as a result of an 22 Pourbaix. M., ie Cenfra Beige d’Etude de la Corrosion,
insufficient awareness of the exact significance of Memotres Sot. Roy. Belge Ingenieurs et lndustriels, No. 3, 5-
10 (1952). Cebelcor publication F. 32 (1952) C.R. 3e Reunion
electrode-potentials. Greater attention should be brought
du CITCE (Berne 1931), 464-471 (1952). Publ. Tamburini
notably to the thermodynamrc interpretation of polariza- (Milano)
tion curves13 “, 4347. 23 Mears, D.C., J. Biomed. Mater. Res. 1975, 9, 133
24 Solar, R.J., Pollack, S.R. and Korostoff, E., ~;tan;um release
from implants: a proposed mechanism Lot. cit. (l), 161-l 72.
(1979)
ACKNOWLEDGEMENTS 25 Solar, R.J., Corrosron resistance of trtamum surgrcal implant
alloys A review. Lot. cit. (1). 259-273 (1979)
My thanks are due to MM. R. Bourgois and G. Poriau4’, as
26 Valega, T.M., Alternatives to gold affoys in dentistry DHEW
well as to MM. P. Blaimont, M. Guinand, M. Pourtois, H. Publ. No. (NIH) 77-1227, US Dept. of Health, Educatton and
Van Laer and J.B. Van Trappen, who put at my disposal Welfare. National Institute of Health, Bethesda, Md, 83-84
informations about the behaviour of biomedical materials, (1977)
27 Meyer, J.M. and Wiscott, A., Corrosion behavrour of high-
copper amalgams Preprint 16th annual meeting International
Assocratton for Dental Research, Continentat European Divi-
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134 Biomaterials 1984, Vol5 May