Biomaterials 21 (2000) 385}392

E!ect of mechanical surface pretreatment on metal ion release

M. Browne*, P.J. Gregson
School of Engineering Sciences, Materials Group, University of Southampton, Southampton SO17 1BJ, UK
Received 16 April 1999; accepted 22 August 1999

Abstract

The degree of metal ion dissolution from Ti}6Al}4V alloy hip replacement stems subjected to various mechanical and chemical
surface pretreatments was analysed in vitro. High-dissolution rates were observed for nitric acid passivated samples that had been
mechanically surface treated to increase the implant surface area. Signi"cantly lower ion release levels were observed for mechanically
treated samples which had been aged in de-ionised water. The application of an hydroxyapatite coating decreased the metal ion
release from the nitric acid passivated samples (compared to the uncoated sample) and increased the metal ion dissolution from the
aged samples. The dissolution behaviour of the samples is explained in terms of the di!usion processes occurring at the stem/solution
interface and the morphological and chemical characteristics of the surface treated stems. ( 2000 Elsevier Science Ltd. All rights
reserved.

Keywords: Titanium alloy; Dissolution; Bovine serum; Surface treatment; Hydroxyapatite coating

1. Introduction roughening on metal ion release has been investigated in

The long-term interfacial bond between an implant
and bone may be improved by creating a rough, or
porous surface coating on the implant to increase the
surface area available for bone/implant apposition.
Simple methods of surface roughening include grit
blasting and shot peening. More complex methods in-
volve creating a surface consisting of pores of a certain
size (between 100 and 300 lm) [1]; providing the implant
material has good biocompatibility with bone then the
bone may grow into these pores, thus providing extreme-
ly rigid "xation of the implant [2,3]. Other approaches
involve the use of #ame sprayed titanium powder which
creates a porous surface with pores of 25}100 lm, or the
use of a titanium wire mesh surface bonded to the im-
plant to produce pores of around 100 lm [4]. A natural
consequence of these surface modi"cation techniques is
an increase in metal ion release, which is itself a surface
dominated process. A further potential complication of
these mechanical techniques is an increase in wear debris
from micromovement [5] which will also result in in-
creased ion release rates [6]. The e!ect of surface
* Corresponding author. Fax: #44-(0)-1703-593016.
the present study.
Short-term "xation may be facilitated by bioactive
coatings. Hydroxyapatite (HA) coatings, in particular,
have been used extensively in implant surgery to assist in
bone/implant &osseointegration' [7}12]. This is usually
applied via plasma spraying, which in turn requires pre-
treatment (roughening) of the substrate to aid mechanical
keying. The e!ect of an hydroxyapatite coating and the
associated underlying substrate deformation on metal
ion dissolution behaviour has also formed part of this
investigation.
Ti}6Al}4V alloy has proven to be an inert implant
material with excellent mechanical properties. The excel-
lent corrosion resistance is due to the stable passive "lm
which spontaneously forms on the alloy and which pro-
vides a barrier between the bioenvironment and alloy
substrate. The nature of this "lm thus controls metal ion
release and its associated e!ects both local to the implant
and systemically. Metal ion release from implants may
arise due to dissolution, fretting or wear, and has been
a source of concern due to the potentially harmful local
and systemic carcinogenic e!ects [13,14]. Metal ion re-
lease may be of even greater concern due to the growing
awareness of the crucial role played in many biological
systems by a variety of elements in trace amounts, and
the impact that any disturbance in this delicate balance

0142-9612/00/$ - see front matter ( 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 6 1 2 ( 9 9 ) 0 0 2 0 0 - 8
386 M. Browne, P.J. Gregson / Biomaterials 21 (2000) 385}392
could produce. In the case of titanium and aluminium,
there is mounting evidence that these metal ions can
a!ect cell function in vivo [15], as well as cell prolifer-
ation and synthesis of extracellular matrix in vitro
[16}18]. Furthermore, it has been shown that titanium,
aluminium and vanadium ions can inhibit apatite forma-
tion in vitro [19,20] and this could have important im-
plications for mineralisation at bone}metal implant
interfaces in vivo. The increase in the body burden of
aluminium by ingestion of aluminium containing ant-
acids, dietary citric acids or citrates has been implicated
in certain cases of acute aluminium toxicity [21,22].
Aluminium deposition has been associated with a num-
ber of neurological disorders [23,24]. It is evident there-
fore, that a reduction in metal ion release is preferred
given the deleterious e!ect they can have on the sensitive
di!erentiation processes which are necessary for normal
bone formation.
It has been shown that in vitro metal ion release from
nitric acid passivated titanium alloy implants (a typical
commercial treatment) is reduced considerably when
simple thermal treatments such as ageing in de-ionised
water or heating in air are applied prior to immersion in
EDTA/saline or bovine serum [25}27]. This reduction in
metal ion release is attributed to a conversion in the
surface oxide to a stable homogeneous rutile (TiO )
2
structure. The purpose of this investigation is to analyse
the metal ion release behaviour of surface treated tita-
nium alloy hip stems subjected to various commercial
"nishes. Given the disproportionately high level
of aluminium ion release from this alloy [26,27]
and the transportable nature of this element in the body,
this study concentrates on aluminium ion release.
The kinetics of the metal ion dissolution reaction are
assessed and interpreted both in terms of the mechanical
surface pretreatment employed, and the surface coating
applied.
2. Materials and methods
Distal sections of forged Ti}6Al}4V titanium alloy
femoral stems from the Ti-Mod Freeman hip replace-
ment made to BS7252 Part 3 were sectioned and polished
to a 1 lm "nish. A second set of stems was subjected to
a high-purity alumina grit blast to produce a roughened
surface. This standard practice provides an increased
surface area for bone/implant apposition. The stems were
degreased ultrasonically in Triton X-100t for 15 min and
given three ultrasonic washes in double distilled water for
10 min. They were then treated to provide di!erent oxide
surface conditions:
(i) immersed in 30% nitric acid for 16 h (N),
(ii) aged in boiling de-ionised water for 10 h (A).
The standard procedure for hydroxyapatite (HA) coat-
ing of an implant involves severe grit blasting using
high-purity alumina at higher pressures in order to
roughen the surface. This increases HA coverage by pro-
ducing a greater surface area for coating adherence.
Stems, two for each treatment, were severely grit blasted
and either passivated (N) or aged (A). They were then HA
coated to a thickness of approximately 100 lm (Plasma
Biotal Ltd., Derbyshire) and given an ultrasonic wash in
double distilled water. In addition, two stems for each
treatment were left uncoated as a reference. It should be
noted that the two types of blasting procedures were
completed at di!erent facilities, with the severe grit
blasting carried out by the coating vendor.
Surface roughness pro"les of the polished, grit blasted
and severe grit blasted surfaces were obtained using
a Talysurf 10 pro"lometer. The standard roughness para-
meter, Ra, for each treatment was noted.
Sterile foetal calf serum with low trace element content
was obtained from First Link (UK) Ltd, West Midlands,
and dispensed in equal volume (17 ml) into sterile plastic
tubes "tted with a locating hole. All stems were "tted
securely into the tubes and incubated at 37$0.23C for
700 h. One millimeter samples were removed, in clean
room conditions periodically (after approximately every
20 h up to 100 h immersion and after approximately
every 100 h thereafter) and analysed in triplicate for alu-
minium content by Atomic Absorption Spectroscopy
(AAS) in a Perkin}Elmer transverse heated graphite
atomiser furnace. The serum was replenished with un-
contaminated stock serum so as to maintain a 17 ml
volume. Standard solutions of known aluminium con-
centration were analysed and calibration curves were
developed, from which values for ion release could be
ascertained.
Each type of treatment was given the following nomen-
clature:
PP*polished and passivated
PA*polished and aged
BP*grit blasted "nish and passivated
BA*grit blasted "nish and aged
SP*severe grit blasted pretreatment and passivated
SA*severe grit blasted pretreatment and aged
SPH*severe grit blasted pretreatment, passivated and
hydroxyapatite coated
SAH*severe grit blasted pretreatment, aged and hy-
droxyapatite coated
3. Results
3.1. Ewect of surface area
The e!ect of an increase in surface area on metal ion
release was investigated using polished specimens
 M. Browne, P.J. Gregson / Biomaterials 21 (2000) 385}392 387

Table 1
E!ect of surface condition on aluminium ion release rate and total ion
release

Surface treatment Aluminium ion release Total ion release

rate (]10~8 lg/cm2/sec) (lg/cm2)

t"50 h t"700 h t"700 h

Age (A), polished 0.93 0.05 0.022

HNO (N), polished 4.69 0.74 0.06
3
Age (A), blasted 10.42 0.88 0.013
HNO (N), blasted 52.85 15.90 0.88
3

Fig. 2. Aluminium ion release with time from SP, SPH, SA and SAH
specimens.

the polished sample (PA) resulted in a considerably lower

ion release rate (0.05 lg/cm2/s after 700 h).

3.2. Hydroxyapatite coated specimens

The severe grit blasted (R "12.0 lm) and passivated

Fig. 1. Aluminium ion release with time from grit blasted specimens.
(R "0.1 lm) and grit blasted specimens (R "4.0 lm).
! !
There was very high dissolution from the grit blasted
specimens (Table 1). For both surface conditions, the
ageing treatment was particularly e!ective in reducing
metal ion release compared with the nitric acid passiva-
tion treatment (Fig. 1).
The change in ion release rate with time (determined by
taking the tangent of the ion release versus time curve) for
samples (A) and (N) is summarised in Table 1. The ageing
treatment on the grit blasted sample (BA) was e!ective
enough to produce a release rate which approaches that
of the polished nitric acid passivated sample (PP) after
700 h (0.88 cf. 0.74 lg/cm2/s). The ageing treatment on
!
(SP) samples showed a very high release rate which
reduced slightly with time (Fig. 2); when subsequently
coated with HA, the degree of dissolution was reduced
from 0.56 to 0.45 lg/cm2 after 740 h, suggesting the coat-
ing had a bene"cial e!ect. The severe grit blasted and
aged (SA) samples again showed reduced levels of ion
release over their passivated counterparts and there was
a clear reduction in ion release with time (Fig. 2). How-
ever, in the case of the HA coated (SAH) samples, the
degree of ion release increased compared with the un-
coated (SA) sample (0.29 cf. 0.16 lg/cm2 after 740 h).
3.3. Kinetic behaviour
The dissolution process will occur across a number of
layers, notably, the metal oxide layer, the metal
388 M. Browne, P.J. Gregson / Biomaterials 21 (2000) 385}392
oxide/liquid interface, a &boundary layer' at the metal
oxide/liquid interface (made up of surface complexes,
serum proteins, hydrated oxides), and the bulk liquid.
A schematic of this &layer' system has been proposed by
Healy and Ducheyne [28}30], and a model which de-
scribes the kinetics of the dissolution process has been
developed in terms of a di!usion or transport controlled
process (cJt1@2) [31,32]. Implicit in this model are the
following assumptions:
1. The concentration of the metal ions at the metal
oxide/boundary layer interface is constant.
2. The concentration of metal ions in the liquid is negli-
gible compared to that at the metal oxide/boundary
layer interface.
3. Metal di!usion through a boundary layer at the ox-
ide/liquid interface is the rate-controlling step.
Graphs describing the kinetic behaviour of the metal ion
dissolution (c vs. t1@2) were plotted for each of the condi-
tions analysed (Figs. 3 and 4). The gradient of such
a graph is designated the &rate constant' and gives an
indication of the ion release rate. The graphs for the PP,
BP and BA samples were "tted with a straight trend line
for both the passivated and aged oxides, suggesting
a transport controlled dissolution reaction is occurring in
Fig. 3. Ion release kinetics for grit blasted specimens.
both cases (Fig. 3). Previous work has shown that the PA
sample exhibits two-stage dissolution kinetics, suggesting
an additional mechanism is occurring after approxi-
mately 25 h [32]. Measurement of the gradient of these
graphs shows that ageing results in a rate constant 70%
lower than the passivated treatment for the polished
samples, and 80% lower for the grit blasted samples.
Ageing has been shown to promote a rutile structure
[25}27,31], which is the most stable form of TiO [33].
2
Fig. 4 shows the concentration of aluminium ions
released into serum as a function of t1@2 from the coated
and uncoated HA stems. A (single-stage) di!usion con-
trolled reaction is occurring with and without the coating
for the passivated (SPH and SP) samples (Fig. 4), and
a lower di!usion rate constant is evident with the coated
samples (Table 2). The corresponding curves for the age-
ing treatment (SAH and SA) were "tted with straight-line
"ts for comparison. These curves demonstrate that the
aged samples exhibit a signi"cantly lower rate constant
than the passivated samples (Table 2). It can be seen that
the aged samples undergo a reduction in metal ion re-
lease rate after approximately 100 h (Fig. 4), indicating
that a secondary mechanism is occurring in addition to
the transport-controlled reaction, probably involving
adsorption. Titanium implant surfaces are known to
Fig. 4. Ion release kinetics for SP, SPH, SA and SAH specimens.
 M. Browne, P.J. Gregson / Biomaterials 21 (2000) 385}392
Table 2
Kinetic behaviour for aluminium ion release into bovine serum from
hydroxyapatite coated/uncoated specimens
Surface treatment Rate constant
(lg/cm2/s1@2)
Nitric acid passivated, HAP coated 2.43]10~4
Nitric acid passivated, no HAP coating 2.52]10~4
Aged, HAP coated 1.8]10~4
Aged, no HAP coating 7.17]10~5
spontaneously nucleate apatite layers when in contact
with simulated body #uids. In a bovine serum environ-
ment, protein adsorption is likely to dominate. Although
these reactions may be competing with each other, form-
ing a hybrid protein/calcium phosphate "lm, evidence
suggests that the inhibition of apatite formation by pro-
teins is only partial [34].
For the majority of the passivated samples, the "tted
trend line intersected the >-axis at a value greater than
zero (0.1}0.2 lg/cm2). This observation suggests that
there are signi"cant ion release processes occurring im-
mediately upon immersion for all but the HA coated
passivated samples. This may be expected since at t&0,
the boundary layer will not have fully developed and
initial ion exchange processes are occurring at the solu-
tion/implant interface. In contrast, the low initial ion
release from the aged samples resulted in intersection of
the trend line at or near >"0, suggesting that in all
conditions, ageing the sample inhibited the dissolution
process immediately upon immersion.
4. Discussion
There are a number of surface controlled factors that
will a!ect the dissolution behaviour of an implant mate-
rial. These include the nature of the oxide, the surface
condition and the surface coating. The role of the oxide
has been discussed previously [25}27,31], and it has been
shown that ageing treatments result in an extremely
dissolution resistant surface oxide compared with stan-
dard nitric acid passivation treatments. Furthermore,
a number of investigators have shown that dissolution of
the oxide layer occurs during nitric acid passivation
treatment resulting in a thinner, less stable oxide
[26,35}37]. This may be a contributory factor towards
the substantial increase in dissolution observed for the
passivated samples.
The e!ect of surface condition was investigated using
polished and grit blasted specimens, which had surface
roughness (R ) values of 0.1 and 4.0 lm, respectively. The
!
bene"cial e!ect of ageing was not lost when applied to
mechanically pre-treated surfaces with increased surface
area (Fig. 1). Similar results could be expected if the
389
ageing treatment was applied to other mechanically pre-
treated surfaces (porous, shot peened, etc.).
The grit blasted surface produced a seven-fold increase
in ion release over the polished surface for the aged
samples (0.146 cf. 0.022 lg/cm2 after 700 h) and a 15-fold
increase in ion release for the passivated samples (0.87 cf.
0.06 lg/cm2). It is clear that the surface roughness in-
creases with the severity of mechanical surface pre-treat-
ment. As a result, a greater surface area is available for
metal ion release via oxide dissolution or micro-scale
corrosion reactions, particularly if the oxide is less stable
in the case of the passivated oxide. Burstein and Souto
have demonstrated that transient microscopic break-
down of the passive "lm on Ti}6Al}4V is induced by the
presence of chloride ions in Ringer's solution [38,39] at
potentials well below the pitting potential. A rougher
surface would be expected to facilitate such reactions as
the chloride ion concentration (also present in bovine
serum) may increase within the troughs of the surface
roughness pro"le.
In addition to the surface area and oxide stability
arguments mentioned above, the increased aluminium
ion release from mechanically pre-treated surfaces may
be attributed to a number of mechanisms:
1. Aluminium is known to exist in the surface layers of
the oxide that forms on Ti}6Al}4V [40]. The polarisa-
tion caused by the aluminium will di!er from that of
the native titanium ions in the oxide, with the more
electropositive ion more likely to react, for example,
with adsorbed water. Furthermore, it has been dem-
onstrated using XPS that the ageing treatment reduc-
es the concentration of aluminium in the oxide surface
layers considerably [32].
2. The mechanical working of the implant surface and
the associated residual stresses may be transferred into
the oxide during surface treatment, resulting in a more
unstable and hence less dissolution resistant surface.
3. The blasting procedure uses corundum (Al O ) as the
2 3
blasting media. Consequently, alumina particles may
become embedded in the surface and involved in the
dissolution process.
4. A reduction in adsorption processes may occur. Ex-
cessive metal ion release is known to inhibit cell func-
tion and apatite formation [19,20]. This will alter the
development of the boundary layer.
In the case of the HA samples (SPH and SP), the pas-
sivated samples exhibit a minor decrease in ion release
rate with time (Fig. 2). However, there is a 25% reduction
in ion release noted with the coated sample. Similarly,
Ducheyne and Healy [7] have demonstrated a 50%
decrease in aluminium ion dissolution from nitric acid
passivated porous titanium alloy implants in Hanks'
balanced solution after HA coating. This suggests that
the coating does provide some form of physical barrier to
390 M. Browne, P.J. Gregson / Biomaterials 21 (2000) 385}392
dissolution [8]. The aged samples in both conditions
(SAH and SA) exhibit a clear reduction in metal ion
release with time (Fig. 2), at a lower level to that of the
passivated samples (approximately 80% for the uncoated
samples and 40% for the coated sample). In contrast to
the passivated samples, there is a signi"cant increase in
ion release when an HA coating is applied to the aged
surface. The HA coating procedure appears to produce
a surface that is less dissolution resistant in this case.
Ducheyne and Healy [7] have suggested that the dissipa-
tion of thermal and kinetic energy of the ceramic particle
at the time of impact could produce compositional and
structural changes at the metal surface, especially for
titanium alloys. It is possible that the impingement of
hot, high-velocity HA particles onto the implant surface
will disrupt the uniform aged oxide. As the passivated
oxide undergoes the same coating procedure, a similar
disruption of the surface oxide occurs and similar levels
of ion release may be expected. The graphs of ion release
with time indicate lower levels of ion release for the aged
and coated oxide (SAH) over the passivated and coated
oxide (SPH), suggesting that although similar composi-
tional and structural oxide changes may occur as a result
of the coating procedure, the aged oxide remains in
a more dissolution resistant state (Fig. 2).
Abdel Fattah et al. [41] have studied the dissolution
behaviour of both chemically precipitated and biological
veterinary HA immersed in serum. The spaces between
the HA particles formed a series of pores and calcium
levels increased in the serum after 10 h, indicating some
form of leaching was occurring. Similarly, Brossa et al.
[42] have studied the e!ect of alumina and titania
plasma sprayed coatings on stainless steel (316L). They
noted porosity due to a di!erence in thermal expansion
coe$cients between the ceramic and steel and attributed
an unexpectedly high ion release in serum to local cor-
rosion at the bottom of pores at the ceramic}steel inter-
face. Local dissolution of the base material occurred due
to the formation of an oxygen concentration cell. A sim-
ilar structure has been observed for plasma sprayed HA
coatings. Plasma spraying is a line of sight process in-
volving high temperatures. As the plasma impacts the
sample surface, it cools and contracts at an extremely
high rate. A uniform thick coating is the exception rather
than the rule, and a porous-like structure often results.
The development of a pore-like structure will provide
more interstitial spaces for higher serum attack, and
would account for the increased levels of ion release over
the polished samples.
Weng et al. [43] have studied the formation and char-
acteristics of the apatite layer on plasma-sprayed HA.
They suggested that a micro-environment with a su$-
ciently high degree of supersaturation of calcium and
phosphate ions is crucial for apatite to nucleate and grow
in simulated body #uid, while the crystalline HA struc-
ture is not critical in the nucleation process. Bovine
serum is rich in calcium and phosphorus, and the devel-
opment of a pore-like structure within the (calcium and
phosphate rich) coating will result in increased super-
saturation. This would be expected to facilitate the
formation of an apatite layer. In the case of the nitric acid
passivated samples, where there was excessive ion release,
inhibition of apatite formation may be occurring [19].
Abdel Fattah et al. observed precipitation of phosphate
phases into HA along with protein deposition after 48 h
[41]. In addition, Ducheyne and Healy have suggested
that phosphate becomes incorporated into titanium ox-
ide "lms, thus causing a change in dissolution kinetics
after 200 h immersion in EDTA/simulated interstitial
#uid [29]. For the aged samples, the kinetics graphs
indicate a slight deviation from straight-line behaviour
after approximately 140 h, indicating that some form of
adsorption process is occurring. This has been observed
previously using atomic force microscopy [32].
The HA coatings considered in this study were of the
order of 100 lm thickness. It has been suggested that
increasing the thickness of the coating will reduce metal
ion release [44], and this has been demonstrated to an
extent by the passivated samples. Given that the physical
and chemical properties (crystallinity, porosity, Ca/P ra-
tio) of hydroxyapatite coatings will vary with the manu-
facturer, a direct comparison to other results cannot
easily be made [45]. However, it is evident that under
similar mechanical surface pretreatment conditions, the
promotion of a rutile surface oxide structure via ageing
reduces dissolution in all cases.
5. Conclusions
The standard surface mechanical pre-treatment of grit
blasting results in an increase in aluminium ion release of
up to 90% compared with polished titanium alloy hip
stems.
Ageing results in an 80% reduction in ion release over
the nitric acid passivated treatment for samples that have
undergone severe mechanical roughening.
There is a 40% reduction in metal ion dissolution from
hydroxyapatite coated samples which are aged prior to
plasma spraying rather than nitric acid passivated.
The application of a plasma sprayed hydroxyapatite
coating reduces metal ion release from nitric acid pas-
sivated surfaces. However, the coating treatment does
not appear to be bene"cial for aged surfaces. This is
probably due to a modi"cation of the aged oxide by the
impingement of the hot, high-velocity, HA particles.
Acknowledgements
The authors would like to thank the Arthritis Research
Campaign, Chester"eld, for their "nancial assistance.
 M. Browne, P.J. Gregson / Biomaterials 21 (2000) 385}392
The assistance of Miss Susan Co!ey and Dr. H.T. Delves
of the Trace Metal Unit at Southampton General Hospi-
tal, Dr. S. Morrey of Plasma Biotal, and Mr. Mike Tuke
of Finsbury (Development), Leatherhead, Surrey, is
gratefully acknowledged.
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