J. BIOMED. MATER. RES. VOL. 10, PP.

445-453 (1976)

Flame-Sprayed Alumina on Stainless Steel

for Possible Prosthetic Application

C. M. BALDWIN and J. D. MACKENZIE, School of Engineering

and Applied Science, Materials Science Department, University of
California, Los Angeles, California 90024

Summary
Various methods of roughening type 316 stainless steel substrate surfaces for
flame-spraying alumina (A1,O were investigated and tested for the best alumina-
to-metal bond strength. Best strength values were obtained by means of rough-
ening via anodic polarization pitting of the stainless steel. Subsequent in vitro
testing indicated a severe loss in bond strength following exposure to aerated
Ringer's solution. It is suggested that the utilization of flame-sprayed devices
has potential in orthopedic prostheses, but precautions must be observed.

INTRODUCTION
The concept of a physiologically inert ceramic coating such as
alumina (AlZO3)attached to a metal shaft has long been considered
a viable prosthetic design configurat,ion from the standpoint of com-
bining both the corrosion-resistance of a ceramic with the overall
mechanical strength of a metal into one device.' A processing tech-
nique which could produce such a configuration is the flame-spraying
process. This fabrication process involves the passing of a ceramic
powder through a high-temperature oxyacetylene flame (2500°F
maximum) whereupon the molten ceramic particles are then sprayed
onto a prepared' metal substrate. The resultant metal-ceramic con-
figuration consists of a thin (typically about 30 mil thick), slightly
porous ceramic coating bonded to a metal core.2 By controlling the
flame-spraying application parameters, the porosity of the coating
may be regulated whereby a porous ceramic coating capable of ac-
cepting permanent bone or tissue ingrowth can be fabricated.
445
@ 1976 by John Wiley & Sons, Inc.
446 BALD WIN AND MACKENZIE

Clinical studies which have been undertaken to evaluate plasma-

sprayed* alumina bonded to various substrate meta1s3s4have gen-
erally been not too encouraging. Richbourg3 plasma-sprayed 99.9%
pure alumina onto the shaft of a stainless steel hip prosthesis and
implanted the device into dogs for periods up to 2 years. The
prostheses were biocompatible but some coatings were observed to
have flaked off. Because of the density of the alumina coating (the
average pore size being less than 1 p ) , no tissue ingrowth into the
device was observed. In another study, Driskel14 attempted to im-
plant plasma-sprayed alumina devices into the mandibles of mon-
keys, but technical and operative complications prevented any mean-
ingful results.

EXPERIMENTAL
Metco type 101 flame-spray powder (approximately 2.5% TiOz
and 97.5% Alz03) was selected as the flame-spray coating material
and was applied to type 316 stainless steel via a Metco oxyacetylene
flame-spray gun, model 2P. The dimensions of the type 316 stain-
less steel substrate was in accordance with ASTM standards5 for
testing flame-sprayed ceramic-to-metal bond strength; the metal sub-
strate was a 1 in. diameter cylinder by 2 in. in length. The 1 in.
diameter metal surface was lathe-polished and acetone-cleaned prior
to any substrate roughening preparation for flame-spraying.
Several substrate roughening techniques were employed, including
1) conventional alumina grit sandblasting of the metal surface, 2)
mechanical roughening using an engraver’s tool bit on a Bridgeport
model 541614 milling machine, and 3) anodic polarization roughening
where the surface is roughened by electrochemical pitting. In the
latter technique, the metal surface was exposed to a 5 N HC1 solu-
tion and then anodically polarized a t a constant current density of
87 mA/cm2 for various lengths of time. Following exposure, the
samples were rinsed in distilled water and dried.
The strength of the resultant flame-sprayed alumina-to-metal bond
was measured according to ASTM standards5 by using an Instron
model TTCLM 1.6 testing machine. In this test, a viscous, non-
penetrating bonding agent (Devcon “2-ton” epoxy) is coated on the
* This process is similar to flame-spraying but produces a much denser ceramic
coating. See reference 2 for further details.
 FLAME-SPRAYED ALUMINA ON STAINLESS STEEL 447

flame-sprayed ceramic face and a loading fixture is then placed on

the epoxy. After hardening, this assembly is loaded in pure tension
perpendicular to the face of the ceramic coating. The crosshead
speed was held constant at 0.02 in./min. The bond strength u was
calculated such that
Maximum Load
lJ=
Substrate Surface Area
A minimum of six samples prepared under identical conditions were
tested for each data point.
In vitro tests were conducted in an apparatus similar to one de-
scribed by Wheeler and James.6 The artificial body fluid was aerated
Ringer’s solutions (850 mg NaC1, 33 mg CaC12, 30 mg KC1 per 100
ml distilled water) heated to approximately 110°F. The Ringer’s
solution pH was held constant at 7.3 as monitored by a Reckman
model 9600 pH meter. The apparatus was designed to simultan-
ously expose up to 12 specimens. Following exposure, the ceramic-
to-metal bond strengths for all samples were tested according to the
aforementioned technique.

RESULTS AND DISCUSSION

Bonding Characteristics
It is generally acknowledged that the flame- (or plasma-) sprayed
alumina-to-metal bond is entirely mechanical and no interfacial
chemical reaction ~ c c u r s . ’ ~The
~ gross surface roughness of the
substrate therefore dictates the ultimate bond strength of the com-
posite such that, all other processing parameters being equal, the
rougher the substrate surface, the stronger the bond.
Of the various substrate surface roughening techniques attempted,
the maximum ceramic-to-metal bond strengths were obtained from
alumina flame-sprayed onto anodic polarization-prepared metal sur-
faces. The bond strength of this particular configuration was sig-
nificantly higher than the other specimens and of comparable flame-
sprayed alumina-titania mixtures sprayed onto stainless steel from
the literature (see Table I). As seen in Figure 1, the anodically
polarized stainless steel surface is highly pitted, thus enabling the
flame-sprayed alumina particles to penetrate into the metal and ad-
here firmly to the substrate.
448 BALDWIN AND MACKENZIE

TABLE I
Maximum Bond Strength for Flame-Sprayed Alumina on Stainless Steel

Surface roughening Bond strength

Reference method u (max), psi Failure location

Our studies Anodic polarization 1066 Ceramic-metal interface

Our studies Machine roughening 504 Ceramic-metal interface
Our studies Alumina grit sandblast 190 Ceramic-metal interface
7 Alumina grit sandblast 500 Ceramic-metal interface
9 Steel grit blast 408 Ceramic-metal interface

The average surface pit diameter D, as measured by scanning

electron microscopy was observed to grow with time in the anodically
polarized HC1 solution as (see Fig. 2). The corresponding
alumina-to-stainless steel bond strength was observed to vary as
to.’* (see Fig. 2), indicating a direct correlation between substrate
surface roughness (as characterized by the average surface pit diam-

Fig. 1. Scanning electron microscope (225 X ) showing pitted surface of type

316 stainless steel following 4 hr in anodically polarized 5 N HCl with a current
density of 87 mA/cm2. The average surface pit diameter is 57 w.
 FLAME-SPRAYED ALUMINA ON STAINLESS STEEL 449

2000 200

T
1000 100

= 900
800 80 4
=- 700 70
0
5-
I-
0 600
3a
60 z
n"
5 500
5 o K
n w
z I-
w

w
400
" 3n
d
v)
k
3I- 300 30
W
W
s s
200 20

100 10
1 2 3 4 5
LOG TIME (HOURS)

Fig. 2. Type 316 stainless steel surface pit diameter (bottom) and the resultant
flame-sprayed alumina-to-metal tensile bond strength (top) as a function of the
stainless steel substrate anodic polarization time in 5 N HC1 with anodic current
density of 87 mA/cm2. A mechanical ceramic-to-metal bond is implied from
these curves.
4.50 BALDWIN AND NACKESZIE

eter) and eventual bond strength. The resultant bond strength can
therefore be predictably controlled based on the anodic polarization
time in acidic solution. A significant drop in tensile bond strength
was observed for samples exposed t o the polarized solution for
periods longer than 5 hr. This was due to the formation of electro-
chemical metastable phases, such as Cr(OIT)3 and H 2 C r 0 4 ,which
tend to destroy the surface pit morphology.’”
The fiame-sprayed alumina surface porosity was analyzed by scan-
ning electron microscopy and was seen to have only 20 pores/cni2
within the pore size range of 15 and SO p. According to published
resultsll for the minimum interconnecting pore size range necessary
for mineralized bone, osteoid, and fibrous tissue ingrowth into porous
materials, this pore size distribution would appear inadequate for
mineralized bone ingrowth, although muscle tissue growth into the
pores may be assumed. This pore distribution is significantly better
than Richbourg’s plasma-sprayed alumina shafts,3 where no tissue
fixation of any type was observed or expected based on his porosity
studies.
In vitro Studies
A series of six flame-sprayed samples, prepared by spraying alu-
mina onto anodically polarized, pitted 316 stainless steel t o attain
maximum bond strength, were exposed t o the aerated Ringer’s solu-
tion for periods of 1, 2, and 3 weeks. Following exposure, the tensile
bond strength was measured; the results are plotted in Figure 3 . A
significant drop in bond strength is observed with as much as a 70%
loss in strength after just 3 weeks. I n addition, “rust spots”
(analyzed by x-ray diffraction to be a F e 2 0 3 - H 2 0were
) observed to
have formed on the alumina surface of practically all specimens.
The saline Ringer’s solution was able to penetrate through the
porous flame-sprayed alumina layer and attack the stainless steel
surface below. As seen from the literature,12 anodically polarized
pit growth in stainless steels exposed t o chlorine environments re-
sults in a n electrochemically “active” surface. Thus, continued pit
growth will occur upon re-exposure to a chlorine environment (in
this case, the Ringer’s solution). The pits may be passivated either
by heat treatment or by applying a protection potentia1,I3 but some
deterioration would always occur ultimately resulting in loss of bond
strength. The rate of strength loss was seen t o vary with time in
Ringer’s solution as which corresponds t o published radial pit
 FLAME-SPRAYED ALUMINA ON STAINLESS STEEL 45 1

1400

1200

L
h

1000
v
0

:
1-
I-
800
a
kl
0
2
2 600
w
2
z
v)

I- 400

200

0 1 2 3
TIME (WEEKS)

Fig. 3. Flame-sprayed alumina-to-316 stainless steel bond strength following

exposure to simulated body environment. Bars represent standard deviation
from mean.

growth rates of 18Cr-1ONi-Ti steel in 0.1 N NaC1.14 With this in

mind, the severe loss in bond strength would therefore appear to
occur a t the ceramic-metal interface such t h a t as the corrosion pit
continues t o grow when exposed t o the Ringer’s solution, the metal
effectively “pulls away” from the ceramic coating, thus eliminating
the interlocking mechanical bond. No conclusions may be drawn
for losses in the’bulk strength of the alumina coating following ex-
posure to the Ringer’s solution.
4d2 BALDWIN AND MACKENZIE

CONCLUSIONS
In evaluating the potential of flame-sprayed devices, several con-
clusions may be made based on this research. By orthopedic pros-
thesis standards, the strength of the flame-sprayed ceramic-to-metal
bond is very low, and the device could never be expected to last very
long under clinical load-bearing situations. This probably explains
Richbourg’s3 poor clinical results inasmuch as plasma-sprayed bond
strengths are not much stronger than flame-sprayed bond strengths.
Concern should additionally be given to losses in strength due to
the breakdown of the ceramic-nietal bond, although the dramatic
losses in strength as in this study shouldn’t be expected given the
proper precautions for metal substrate passification. Permanent at-
tachment of the prosthesis by tissue ingrowth into the porous alu-
mina coating may occur, but osteoid and mineralized bone growth
into the prosthesis is unlikely. Based on these conclusions, it would
appear that flame-sprayed alumina prosthesis may have some po-
tential under nonload-bearing situations where muscle tissue fixation
into a porous ceramic material is desired.
Follow-up clinical research15 into anodically polarized Vitallium
with a flame-sprayed alumina coating has been encouraging. The
Vitallium substrate after pitting remains “passive,” and subsequent
implantation of flame-sprayed alumina on Vitallium into the muscle
tissue of rabbits has shown very good attachment with no tissue
reaction.
The authors are grateful to the National Institute of Health for their financial
support of this research under research grant No. AM 16120-01.

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 FLAME-SPRAYED ALUMINA ON STAINLESS STEEL 453

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Received August 24, 1975

Revised October 1, 1975