The bondingof Bioglass@

to
a cobaltxhromiumsurgical
implantalloy
W.R.Lacefield
University of Alabama at Birmingham, School of Dentistry, Birmingham, Alabama 35294, USA

LL Hench
Bioglass@ Research Center, Box J4 13 JHMHC. University of Florida, Gainesville, Florida 32610, USA
[Received 11 April 1985; revised 19 September 1985)

A biocompatible composite implant system was developed by coating BioglasP onto cobalt-chromium
alloy substrates. Strong bonding between glass and metal was obtained by immersion of preoxidized
implants into molten Bioglass under controlled conditions. The thin, adherent Bioglass@ coating provides
the capability of bonding directly to bone, while the underlying metal substrate gives the composite
implants sufficient strength to be used in load bearing applications.

Keywords: Metal alloys, implant, Bioglass, bonding, interface, coating, Vitallium

Previous studies have shown that glasses whose composi- spraying of Bioglass coatings was the high viscosity of the
tions fall within a specific range, termed Bioglasses, glass at the coating temperature. Lower viscosity Bioglass
chemically bond to bone when conditions are favourablels. formulas (Table 7) containing fluorine and boron were
Thus, long-term fixation of a Bioglass* implant can be developed which enabled the production of smooth,
achieved without the need for a porous surface or the use uniform glass coatings on the steel substrates. However,
of a cement such as PMMA. As the reaction layer which porosity at the interface was still a problem and in vitro
develops on exposure to water or tissue fluid is confined to tests showed the coating to have low fatigue strength as
the surface of the Bioglass implant, the intrinsic strength of well as excessive corrosion at the glass-metal interface.
the bulk material is retained. As Bioglass (like most Also, a number of flame-spray coated hip implants
glasses) is relatively weak in tension, the most effective experienced in vivo coating failure after being placed in
use of this unique material in load bearing implant monkeys.
applications is as a coating on a stronger material such as Sputter-coating of Bioglass layers on metallic plastic
dense aluminaW, or alloys such as stainless stee18“’ or and ceramic substrates has been accomplished14. How-
cobalt-chromium (e.g. Vitalliumt)“. For a Bioglass-coated ever, this technique requires a large ion beam source
hip prosthesiss or similar orthopaedic device, the proper which is not readily available. Also, many hours of
functioning of the implant depends not only on a strong sputtering in a partial vacuum are necessary to obtain a
bond between the glass and bone, but also on the integrity glass coating thickness in the range of a few pm.
of the bond between the glass coating and the metal The coating of Bioglass layers on dense alumina
substrate”. substrates has been reasonably successfulW and Bioglass-
Various methods of coating Bioglass compositions coated alumina devices are being developed for use as
onto orthopaedic surgical alloys have been investigated13. dental implants. An important factor in the process for
A flame-spray coating technique was developed in an making Bioglass coated alumina is the large difference in
attempt to get a uniform coating of 45S5 Bioglass (see the thermal expansion coefficients of alumina (about
Tab/e 1 and Reference 2) on a stainless steel substrate 8 X 1O-“/‘C) and 45S5 Bioglass (13-l 5 X 1O-6/“C). This
without the necessity of heating the alloy to the glass mismatch causes high stresses at the interface during
softening temperature13. This method was not completely cooling from the coating temperature, and the lower
successful because of the porosity which developed at the expansion of the substrate puts the glass layer in tension,
glas+metal interface as the hot glass particles struck and thus enhancing its tendency to crack. The alumina/
fused to the metal surface. Another problem with flame Bioglass expansion mismatch results in formation of
micro-islands of Bioglass bonded to the alumina. In order
*Bioglass” is a registered trademark of the University of Florida. to avoid attack at the interface between the coating and the
tVitallium” is a registered trademark of the Howmedica Inc. alumina substrate and thereby minimize possible failure of

01986 Butterworth (i Co (Publishers) Ltd. 0142-9612/86/020104-05$03.00

104 Biomaterials 1986, Vol 7 March

 Bioglass/Vitallium bonding: W. R. Lacefield and L. L. Hence

Table 1 Bioglass” and VItaIlium@ compositions (in %)

-
VitaIlium@ 65 Co 28 Cr 5.5 MO 0.75 SI 0.70 Mn 0.25 C

5284.6 Bioglas@ 52 SiO, 21 Na,O 21 CaO 6 “~0,

45S5 Bioglass@ 45 SiO, 24.5 Na,O 24.5 CaO 6 “~0,
F - BioglassO 45 SiO, 24.5 Na,O 12.25 CaO 12.25 CaF, 6 P,O,
B - BioglasP 40 sio, 24.5 Na,O 24.5 CaO 5 820, 6 P,O,
___.

the coated device, a procedure was developed for double

coating the alumina substrate”. Using this double coating
technique, the first layer of Bioglass takes up the expansion
mismatch so that the second layer has little or no strain
imposed on it during cooling, and an expansion-graded
interface is established.
There are several major advantages to using metals
such as 316L surgical stainless steel or cobalt-chromium
alloys rather than alumina for Bioglass-coated implants. Flat
Metals have long been used in load-bearing applications in
the bod#, have good fatigue strength in a physiological
environment, and are not as subject to brittle or static
failure as are ceramics. Also, the thermal expansion of
these metals (13-l 6 x 1 0P6/“C) is nearly identical to that
of several Bioglass formulas.
The purpose of this study was to investigate the
bonding of 52S4.6 Bioglass to Vitallium, a commonly used
cobalt-chromium surgical implant alloy. One approach
used to coat the Vitallium substrates involved dipping the 6 mm
metal test specimens into a solution containing glass frit Gl,ssscoat
and a suitable vehicle, then firing the coated rods in an
electric furnace. The high temperature firing cycle caused
the glass particles to fuse and flow, forming a uniform glass
coating. This technique is the most common means of
commercially coating or enamelling glass or porcelain
onto steel. Another coating technique investigated in this
study included the rapid immersion15 of the Vitallium Steel test fixture
substrate into a crucible containing molten Bioglass,
followed by withdrawing it from the crucible so that a fairly Figure 1 Push through shear test for determinmg glass-metal bond
uniform glass coating remained after the excess glass had strength.

drained back into the melt.

This paper is primarily concerned with the type of
bond formed, the effect of various processing variables, the The Vitallium test rods vvere subjected to various
surface preparations prior to coating by either the frit
resulting bond strength, and the effect of the coating
enamelling or immersion techniques. Selected specimens
procedure on the mechanical properties of the Bioglass
coated Vitallium substrates for both the frit enamelling and were either grit blasted with a mixture of A1203 and glass
the immersion coating methods. beads, ground with 240 grit silicon carbide paper, or
electropolished in perchloric acid. All specimens were
ultrasonically cleaned in acetone prior to coating.
MATERIALS AND METHODS
Forfrit enamelling purposes, 52S4.6 Bioglass (Tab/e
The compositions of the Bioglass coatings and the 7) pieces were ground (dry) in an alumina ball mill until a
Vitallium rods used in this study are given in Tab/e 1. particle size was reached which would pass through a 400
Vacuum-cast Vitallium rods (6 mm diam. by 150 mm in mesh screen (38 pm or less). A vehicle of 70% toluene and
length) were obtained from Howmedica, Inc. Three test 30% acetone was added to the ground frit so that the
specimens of 6 mm diam. and 45 mm in length were cut transfer and coating of the frit particles onto the metal
from each of the castings. substrate was facilitated. Vitallium rods were dipped into
A shear type of test was developed so that glass-to- the frit solution approx. 6 times, each coating being
metal bond strength could be evaluated quantitatively. In allowed to dry for several min before the next layer was
this test, the coating is stripped off as the metal rod is applied. The coated specimens were heated to a tempera-
pushed through a hollow cylinder (see Figure 7). The glass ture of 1100°C for a minimum of 20 min to allow the
coating typically fractured off in two or three large pieces Bioglass layers to fuse and flow to produce a smooth
immediately as the first interfacial cracks were observed. coating on the Vitallium. The coated specimens were
An lnstron mechanical testing machine was used to annealed at 500°C for 4 h and furnace cooled to room
provide the load at a rate of 0.05 in/min, and the bond temperature. The average glass coating thickness on
strength was determined by dividing the load at failure by Vitallium rods enamelled by the above procedure was
the total contact area of the glass on the metal substrate. approx. 300 pm.
The results were statistically analysed, with Duncan’s For the immersion coating technique, selected
multiple range test used to determine significance Vitallium test rods were first preoxidized in air at tempera-
between means. tures ranging from 350-800°C and for times of 5 to

Blomaterials 1986. Vol 7 March 105

Bioglass/Vitallium bonding: W. R. Lace field and L. L. Hence

30 min. Other test specimens were oxidized in a Jelcraft

furnace under a partial vacuum (about 1 torr pressure) for
similar times and temperatures. The frit enamelled
specimens were not preoxidized as sufficient oxidation
occurred during the initial stages of sintering of the glass
particles.
Prior to immersion coating, previously melted and
homogenized 5284.6 Bioglass pieces were placed in a
platinum crucible and covered with a platinum lid to
minimize contamination and volatilization of the glass
components during remelting. The crucible containing the
glass was placed in an electric furnace, held at the selected
coating temp., and the molten glass was allowed to remain
for a minimum of 30 min prior to coating. The Vitallium
substrates to be coated were held with tongs, immersed in
the molten glass for 3 s, and then withdrawn at a constant
rate so that a fairly uniform glass layer of about 1 mm
Figure 3 Microstructure of Vitalhum” after immersion coating showing
remained on the rod (Figure 2). The coated substrates were typical as-cast structure fX 66.6).
then placed directly in an annealing furnace at 500°C. held
for 4 h, and then furnace cooled.
An electron microprobe (EMP) was used to deter-
mine the extent of diffusion of metallic atoms from the
Vitallium substrate into the Bioglass coating, and the
diffusion of ions from the glass into the metal. Auger
electron spectroscopy (AES) was used to characterize the
glas+metal interfacial region within a few pm of the true
interface. Diffusion gradients were established using this
technique and were used to obtain profiles of elements
across the interface.

RESULTS
The bond test results showed that the immersion coated
Vitallium specimens had significantly higher bond strengths
than the frit enamelled specimens (64.1 versus 48.2 kg/
cm’, respectively). In addition, the mechanical properties Figure 4 Microstructure of Vitalhum” after frit enamelling showing
of the Co-Cr-Mo alloys were adversly affected during the massive carbide precipitation fX 66.6).
frit enamelling heating cycle.
A typical microstructure for a castVitallium specimen large decrease in the ductility of cast Vitallium as
after immersion coating is shown in Figure 3. This determined during mechanical testing.
microstructure is identical to that observed in the same The bond strength test results for selected processing
specimen prior to immersion coating. The microstructure variables in the immersion coating technique are shown in
of a similar specimen after firing at a normal frit enamelling Tab/e 2. Duncan’s multiple range test was used to test
time-temperature cycle (25 min at 1100°C) is shown in significance between means within each group. Means
Figure 4. The most apparent difference is the large amount which are bracketed together indicate that no significant
of carbide precipitation at the grain boundaries which difference was seen. For the range of values tested no
occurs during coating by the frit enamelling process. This differences for the variables of temp. of immersion and
condition has been shown in previous studies to cause a annealing cycle were observed. Significant differences
between bond strength means were observed for changes
in surface roughness, time of immersion, oxidation
pressure, and time and temperature of oxidation.
The shear strength versus time of oxidation is shown
in graphical form in Figure 5 for some of the oxidation
temperatures used in this test. In general, for a given
temperature in the range 500-650°C, the shear strength
increases with increasing time of oxidation to a certain
point, then decreases. For a temp. of 800°C. shear strength
values decrease as oxidation time is increased over 5 min.
A 350°C oxidation temp. gives low bond strengths
regardless of oxidation time.
These results show that an optimum time of
oxidation occurs for each temperature, indicating that a
certain thickness of an oxide layer gives maximum bond
strength. An oxidation temp. in the range 500-65O”C is the
Figure 2 Vitalhum” test specimen immersion coated with 52S4.6 most suitable for Vitallium, with oxidation times being 8 to
Bioglass”. 15 min depending on the temperature. As an example, the

106 Biomaterials 1986, Vol 7 March

 Eioglass/Vitallium bonding: W. R. Lacefield and L. L. Hence

Table 2 *Effect of selected variables on glass-metal bond and failure may occur either within the oxide layer itself or
strength of immersion coated BioglassO/Vitalliumm between the metal and oxide. On the other hand, an oxide
layer which is too thin can be completely dissolved by the
A Surface preparation
1 Grit blasted - 64.1 (2.7) glass, causing loss of saturation of metal oxide at the
2 SIC polished - 62.0 (6.0) glass-metal interface.
3 Electropolished - 55.4 (6.7) Oxygen pressure also had an effect on bond strength
B Glass temperature in a manner similar to the time and temperature of
1 1320°C - 64.6 (4.5) oxidation. Low
oxygen pressure during firing reduced the
2 1335°C - 63.6 (2.6) thickness of the oxide layer at a given time and
3 1350°C - 62.6 (4.7)
temperature. For example, improved bonding could be
4 1330°C - 62.2 (4.3)
obtained by firing at 800°C for 15 min in low oxygen
C Immersion time pressure while the same firing cycle in air produced an
1 3 s - 64.6 (5.0)
2 15 s - 58.1 (4.1)
excessively thick oxide layer.
3 30 s - 51 .o (4.5) The results of this investigation indicate that the
immersion coating process is the method of choice for
D Oxidation pressure
1 650°C; air - 60.6 (4.1) coating Vitallium with Bioglass because: (1) the short time
2 800°C. vacuum - 58.0 (2.9) at coating temp. (e.g. 3 s) does not signiticantly decrease
3 500°C. air - 56.6 (5.3) the mechanical properties of the Vitallium substrate (as
4 650°C. vacuum - 55.2 (3.0) ! does the frit enamelling method), and (2) a smooth, thick
65 8OO”C, coating of glass can be obtained without the excessive
500°C. vacuum - 39.9
air - 43.2 (4.3) (4.9) I
porosity and corrosion which has been encountered using
E Annealing cycle
1 4 h, 500°C - 63.7 (6.1)
the flame-spray technique.
2 6 h, 600°C - 63.3 (3.2) One of the disadvantages of the immersion technique
3 2 h. 450°C - 62.0 (7.1) is difficulty in coating complex shapes. as the molten
4 2 h. 600°C - 62.0 (7.1) glass is too viscous at the coating temperature to penetrate
5 6 h, 450°C - 60.6 (6.5)
into internal cavities during the short immersion time. The
*Mean bond strengths and standard devtations in kg/cm? values coating of these complex types of objects could be more
bracketed together are not significantly different @ = 0.05). easily accomplished by dipping a substrate into a Bioglass
frit solution and then firing the frit layer to form a smooth
Fz- 80 glass coating.
One potential application of Bioglass-coated Vitallium
in orthopaedic surgery is to make devices for total hip
replacement. The traditional and current form of fixation
uses cement at the interface between device and bone.
In some cases loosening of the implant due to failure at the
interface occurs and revision surgery is required. By com-
parison the Bioglass-coated shaft of the nmplant would be
placed inside the femur where it would bond to the bone,
01 I I I I leaving the uncoated head to articulate with the socket.
0 5 10 15 20 The strength and integrity of the Bioglass-metal bond is
Time of initial oxidation (min) vital since failure at the bond would have the same conse-
quences as the cement failures which occur with the pre-
Figure 5 Glass-metal bond strength as a function of time and
temperature of oxidation. sent method of fixation.
The glass-metal bond strength required of a
use of a time-temperature cycle in this range gives about Bioglass-Vitallium hip prosthesis to insure the integrity of
40% better shear strength test results than an oxidation the device is not yet known. The high modulus of the
cycle of 800°C for 10 min. Vitallium substrate would keep the Bioglass coating (which
As reported in the author’s thesis”, AES and EMP is under a slight compression) from fracturing under normal
results show that there was a diffusion of atoms from the bending loads. It is not known what portion of an applied
alloy into the Bioglass during the immersion bonding load would act to cause shearing of the glass coating from
process. Particular diffusion gradients of Co and Cr were the metal, but in normal loading it would be only a small
found to be consistent with good glass-metal bond fraction of the total load. Based on the calculated minimum
strength, and were indicative of the degree of chemical shear strength of Bioglass-Vitallium specimens coated by
bonding between Bioglass and Vitallium for each coating the optimized immersion process, a 5 in Bioglass-coated
cycle. section of a l/2 in diam. implant shaft could withstand
loads of more than 3560 kg without failure of the coating,
assumir:g the same fracture mode as the test specimens. A
DISCUSSION twisting motion of the implant in the femur would be more
likely to concentrate stress at the interface of the coating
The results of this study show that the most important
and substrate, and thus torsion may well be the most
processing variables in the establishment of good glass-
severe type of loading encountered by a coated implant.
metal adherence are the temperature and time of oxidation
of the metal substrate prior to immersion in molten glass.
These factors are responsible for the thickness of the
SUMMARY AND CONCLUSIONS
oxide layerformed during oxidation of the metal at a given
oxygen pressure. Oxide layer thickness is of critical impor- The immersion technique is a satisfactory means of
tance, as an excessively thick oxide layer is usually weak coating Bioglass onto a Vitallium substrate. Adherent glass

Biomatenals 1986. Vol 7 March 107

BioglassNitallium bonding: W. R. Lace field and L. L. Hence

coatings of about 1 mm in thickness are produced under implants, (Ed. D.F. Williams), Vol. 2, CRC Press, Boca Raton, FL,
1982, p 129
controlled conditions. The most important factor in
Wilson, J., Pigott, G.H., Schoen, F.J. and Hench, L.L., Toxicology
attaining maximum Bioglass-Vitallium bond strength is and biocompatibility of bioglass. J. Biomed. Mater. Res. 1981,
the formation of a tightly bonded oxide layer of the proper 15, 805
thickness on the substrate prior to immersion into the Hench, L.L. and Greenspan. D.C., Bioglass” coated AI,Os
molten glass. The glass-metal bond strength is sufficient ceramics, US Patent No. 4 103 002
Greenspan, D.C. and Hench. LL. Chemical and mechanical
to allow Bioglass-coated Vitallium implants to be used in
behavior of Bioglass@ coated alumina, J. Biomed. Mater. Res.
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as endosseous dental implants which anchor single 8 Griss, P., Greenspan, D.C., Heimke, G., Krempien, 8.. Buchiner,
crowns or fixed bridges. R., Hench, L.L. and Jentschura, G., Evaluation of a Bioglass”
coated AI,Os total hip prosthesis in sheep, J. Biomed. Mater.
The frit enamelling coating technique is inferior to
Res. 1976, lO(4). 51 l-51 8
the immersion technique for coating Bioglass onto 9 Piotrowski, G., Hench, L.L. Allen, W.C. and Miller, G.J.,
Vitallium. Problems encountered with the use of the frit Mechanical studies of the bona-Bioglass” interfacial bond,
enamelling technique include low bond strength, exces- J. Biomed. Mater. Res. 11975, 9(6), 47-61
sive diffusion of metal ions into (and sometimes through) IO Hench, L.L., Pantano. C.G.Jr, Buscemi, P.J. and Greenspan, D.C.,
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the glass coating, and loss of certain mechanical
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1981
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device, in Orthopedic Mechanics: Procedures and Devices, (Eds
D.H. Ghista and R. Road), Academic Press, London, 1978,
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108 Biomaterials 1986, Vol 7 March