Biomaleriak C 1995

16 (1995)

239-244

Elsevier Science Limited Printed in Great Britain. All rights reserved

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Development of a titanium alloy suitable for an optimized coating with hydroxyapatite

J. Breme, Y. Zhou and L. Groh
Lehrstuhl Metallische Werkstoffe, Universittit des Saarlandes, D-66041 Saarbrticken, Germany

By means material chosen TiMn6 could these

of the metallurgical was adapted a maximum compromise behaviour fulfil with

method

of alloying,

the thermal

expansion material.

coefficient

of commercially composite element With the alloy and the strength

pure titanium

to that of hydroxyapatite adhesion which concerning was found. when strength is an important trace

(HA) in order element coefficient, coatings

to produce

a tailored The alloying organism.

of HA to the metallic

was manganese, a good

in the human with an extremely according

the expansion With this alloy the sol-gel

the mechanical

properties high adhesion

biocompatible layers

be produced,

especially

process

was used for HA precipitation. to theoretical

In addition, considerations.

the requirements

of favourable

thin coatings

Biomaterials Keywords:

(1995), 16 (3) 239-244 Titanium alloy, hydroxyapatite, sol-gel process

Received 5 September

1994; accepted 18 September

1994

In the group of metallic biomaterials, titanium and its alloys are gaining increasing acceptance because of their corrosion-resistant behaviour, their biocompatibility and, contrary to ceramic materials, their ability to endure the high tension stresses present, for example, in hip prostheses, bone joints, dental implants, plates, in titanium materials, an screws etc.l. In addition, adhesion with a high shear strength of the bone to the implants can be observed. This adhesion has a mainly mechanical character because the bone grows in close contact with the implant and penetrates cavities and grooves on the implant surface due to the inert behaviour of the titanium materials provided by the constant presence of an oxide layer, which has an isolating effect due to its high dielectric constant (E = 78) corresponding to that of water. Because of this fact and in order to provide a high shear strength between the bone and the implant during the healing period, any perceptible relative implant/bone motion must be avoided3. Therefore, during this period, which takes about 100 d, implants such as hip prostheses should be loaded to a slight degree only4. The healing period can be decreased to about 20 d by the use of hydroxyapatite (HA), because the bone is able to bridge the gap to the implant by the formation of a chemical bond to the HA. Since HA has insufficient mechanical properties, it is only of advantage if it

Correspondence

to Professor J. Breme.
239

is used as a coating for a composite material based on a titanium alloy. Because of this fact the problem of the implant anchorage is shifted to the metal-ceramic interface. The successful application of HA coatings to titanium is very difficult because the thermal expansion coefficient c( of titanium amounts to only 60% of that of HA. The high shear strength required between the coating and the substrate can be achieved only by chemical bonding, which can be produced by diffusion during annealing of the composite. Because of the misfit of the expansion coefficients during cooling from the annealing temperature, tension stresses will occur which produce a predamaging (cracking) of the ceramic, causing a decrease in the adhesion strength. Therefore, the aim of this investigation was the development of a corrosion-resistant biocompatible titanium alloy with sufficient mechanical properties (similar to standard alloys) and a thermal expansion coefficient adapted to that of HA in order to overcome the predamaging of the ceramic after diffusion bonding. On the other hand, according to theoretical considerations, the HA coating layer should be as thin as possible because with implants such as hip prostheses, which are loaded by bending, the maximum bending strength (tension) is found on the lateral side in the surface fibre which consists of the HA ceramic. Because of this fact, especially thick HA layers risk being damaged. Therefore, another aim of this investigation was the production of thin HA layers.
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et al.

MATERIALS AND METHODS

Since, on the one hand, manganese, as compared with titanium, has an extremely high thermal expansion coefficient (a = 22 x 1O-6 K- and tl = 8.4 x 10m6 K-, respectively, between 20 and 1OOC) and, on the other hand, it is, like iron, an important trace element in the human organism5, it has been chosen as an alloying element in order to adapt the expansion coefficient of titanium to that of HA. Alloys with different contents of manganese (2-8 wt%) were produced by melting from commercially pure (cp) titanium grade 1 and manganese of 99.99% purity in an electric arc furnace in an argon atmosphere (pressure about 600 mbar). Before hot deformation, cigar-shaped samples with a weight of about 200 g were homogenized for 4 h at 1000C in a vacuum. A hot deformation of about 80% was performed with grooved rolls at 750C in the (a + /I) phase field. Part of the material was pulverized by the HDH process (hydrogenation-dehydrogenation) in order to carry out biocompatibility tests by culturing L132 cell-lines with different concentrations of the TiMn alloy powder and by determining the survival rate of the cells. The bulk material was used for the investigation of the microstructure, the mechanical properties and the corrosion behaviour and for the performance of the coating tests. The thermal expansion coefficient was determined with a dilatometer in the temperature range of 20-950C and compared with that of cp-titanium and HA. The corrosion resistance was measured in a 0.9% saline solution which was buffered to a pH value of 7.4 by investigating the influence of the potential, which was changed in steps of 1 mV s-, on the current density. In addition, the repassivation behaviour was studied. The surface of the samples was scratched with alumina in a 0.9% saline solution (pH 7.4). The repassivation time is the time required for the metal to build up a new protecting oxide layer in the region where the passive layer has been damaged6. The repassivation measurements were performed at the constantly applied potentials of 0 and +500 mV in order to investigate a possible change in the repassivation behaviour with the potential. In order to produce the thin coating layers of HA on the titanium materials, two methods were studied. The first method was a direct sintering of HA on the surface of the titanium samples with and without a bonding agent. The bonding agent consisted of a suspension containing 10% phosphoric acid (1 ml), butyl alcohol (9 ml) and HA. The dip-coated suspension was dried at room temperature and at 60C (15 min) and burnt in at 600C (15 min). Finally, the HA layer was produced by annealing commercially pure HA together with the bonding agent at 1200C. The second coating method consisted of a sol-gel procedure, as shown schematically in Figure 1. The starting materials were a solution of CaO and an organic compound, triethylphosphate PO(OC,H,), and trimethylphosphate PO(OCH& respectively. The samples were dip coated with a mixture of the starting materials. The dip coating was follpwed by drying for 1 h at 130C leading to the production of a gel. Finally, by annealing at 600-800C (5-15 min) the
Biomaterials 1995, Vol. 16 No. 3

CaO (dissolved)

RO-$-OR dR mixtire R: CH; , CzHi + HI0 sol dip coating and drying at 130C gel film annealing at 600C - 800C HA film

Figure 1 Schematic representation of the hydroxyapatite (HA) by the sol-gel process.

production

of

coating was developed. With both methods cylindrical samples were coated in order that traction adhesive strength tests could be performed. The resulting HA was characterized by X-ray studies.

RESULTS
the microstructures of the various TiMn alloys after hot deformation. In all cases the former coarse j-grains can be observed. For the alloys TiMn2, TiMn4 and TiMn6, which have been deformed in the (c( + /I) phase region, the coarse z-precipitation started from the grain boundaries of the P-phase. The characteristic oriented cc-plate structure can be seen for the alloy TiMn6 in a higher amplification in Figure3. According to the binary system TiMn, the deformation of the alloy TiMn8 took place in the P-phase field. Therefore, small cr-precipitations occur in the B-grains during cooling from the deformation temperature

Figure2a-d shows

(Figure Zd).
The mechanical properties of the various alloys are summarized in Figure 4 as a function of the manganese content. The strength properties increased in direct proportion to the manganese content, while the elongation at fracture and the reduction in area were diminished. Since the alloy TiMn8 shows practically no elongation at fracture, it cannot be used because of its brittleness. Figure 5 gives the results of the measurement of the thermal expansion coefficient of the various alloys compared with the coefficients of cp-titanium and HA. With increasing manganese content, the misfit between titanium and HA is diminished. Table I shows the average expansion coefficient in the temperature range of 200-700C. For a content of 6% manganese, the difference between the metallic alloys and the ceramic is less than 20%. Table 2 shows the results of the corrosion behaviour. In the passive region the current density increases slightly with increasing manganese content. On the

Titanium-hydroxyapatite

composite:

J. Breme

et a/.

241

Figure

Microstructures

of alloys

rolled

at 750C.

a, TiMnP; b, TiMn4; c, TiMn6; d, TiMn8.

1200 t, I (60

i.

./

cpTi grade

manganese content

( weight % )

(according to AISI, DIN. ISO)

Figure 3 Microstructure tation of cl-plates).

of TiMn6

rolled

at 750C

(precipi-

Figure 4 mechanical

Influence properties

of the manganese of TiMn alloys.

content

on

the

Table 1 Average thermal expansion coefficient c( (200-700C) of TiMn alloys compared with commercially pure (cp) titanium and hydroxyapatite

Table 2 Repassivation time t, and current density i in 0.9% NaCl solution (pH 7.4) of TiMn alloys compared with commercially pure (cp) titanium

te(ms)
OmV cp-Titanium TiMn4 TiMn6 TiMn8 Hydroxyapatite 10.5 11.4 12.0 13.1 14.1 cp-Titanium TiMn4 TiMn6 TiMn8 24.6 22.4 26.2 24.3 + 500 mV 26.1 22.8 23.3 23.4

i (PA cm-)
400 mV 4.6 4.6 5.1 5.2 800 mV 4.7 4.9 5.5 6

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J. Breme et al.

~~~l~l~~l~l~i
0

200

400

600

800

1000

temperature

( C )

Figure 5 Thermal expansion coefficient of TiMn alloys compared with those of commercially pure titanium and hydroxyapatite. 0, Titanium; 0, TiMn4; n . TiMn6; 0, TiMn8; f, hydroxyapatite.

other hand, the repassivation time t, of the TiMn alloys is similar to that of cp-titanium. The results obtained on powder made from the TiMn alloy and cultured with L132 cells showed no significant difference from those obtained on cp-titanium powder. Even with the highest concentration of 40OpgmlK of the highest manganese content (TiMn8), the critical value RrESO (death of 50% of the cells) was not achieved. With this concentration a survival of 80% of the cells was observed. Since the alloy TiMn6 proved to have sufficient mechanical properties, including sufficient ductility, together with a thermal expansion coefficient similar to that of HA and a corrosion-resistant and biocompatible behaviour, this alloy was selected for coating tests with HA. Figures 6 and 7 show scanning electron microscopy (SEM) photographs of samples of cp-titanium and of

TiMn6, which were coated with HA at 12OOC using a bonding agent and cp-HA. While in the case of the HA layer on cp-titanium (Figure 6) many cracks were observed due to the high misfit in the thermal expansion coefficient of the metal and the ceramic, the layer on the TiMn6 alloy was practically free of cracks (Figure 7). Consequently, there is a significant difference in the shear stress of the two coatings (Table 3). The shear strength of the HA layer on the TiMnG was about twice as great as that of the layer on cp-titanium. Figure 8 shows line scans of the various elements over the diffusion metal-ceramic interface after annealing at 1200C. A diffusion zone of about 10 pm thickness originated, especially in the case of the diffusion of calcium and phosphorus into the metallic material. Due to a smaller atomic radius, the diffusion distance of phosphorus is greater than that of calcium. The layer itself has a thickness of about 50 pm. Extremely thin coatings of HA with a thickness of about 1 pm were produced using the sol-gel method. HA powders developed from CaO and PO(OC,H,), by annealing at 600 and 800C respectively were characterized. By means of X-ray diffraction investigations of the HA powder produced by annealing at 600 and 800C respectively, it was possible to observe the diffraction pattern of pure HA according to ASTMJCPDS 9-432 (Figure 9). The only existing difference is in the crystallinity. The HA produced at 600C was seen to be more amorphous than the material produced at 800C. From the (OOZ), (Zll), (112), (300),

Table 3 Shear strength (N mm ) of hydroxyapatite produced by annealing at 12OOC and by annealing bonding agent and cp-hydroxyapatite cp-Titanium One HA layer Two HA layers Bonding agent + HA HA, hydroxyapatlte. 9.7 10.2 9.3 TiMn6 18.8 21.5 22.2

coatings using a

Figure 6 Scanning electron micrographs of a hydroxyapatite coating on commercially pure titanium produced by annealing together with a bonding agent at 1200C.

Figure 7 Scanning electron micrographs of a hydroxyapatite coating on TiMn6 produced by annealing together with a bonding agent at 1200C.

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1995, Vol. 16 No. 3

Titanium-hydroxyapatite

composite:

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243

0 1

20 *

40

60 I

80 1

IOOpm

Ca

V=
Figure 8 Line scans of the hydroxyapatite interface. diffusion zone

500

at the TiMnG

Figure 10 tite coating

Scanning produced

electron micrograph of a hydroxyapaby the sol-gel method at 800C.

DISCUSSION
(222) and (213) reflexes, the lattice parameters of HA (800C) were calculated to be a = 9.423 A and c = 6.884 A. The average grain size of this powder was about 36 nm. Figure 10 shows SEM photographs of the surface of samples which were coated at 800C by using CaO and PO(OCH& as starting materials. The layer is dense and crack-free. An X-ray diffraction diagram of the coating at 800C on the TiMn6 alloy shows, in addition to the HA peaks, peaks of titanium and TiOz (Figure 11). The investigation of the traction adhesive strength of the layers produced at 600 and 800C respectively shows that no real value could be determined because the rupture always occurred in the glue. Since the tensile strength of the applied glue was indicated and also measured to be about 70 N mm-, the value of the adhesion strength of HA applied by the sol-gel process to the TiMn6 alloy must be even higher than iONmm~.

The metallurgical method of alloying titanium with an element, in this case manganese, which is able to shift the thermal expansion coefficient of titanium towards the value of the ceramic HA, was successful for the production of a metal-ceramic composite with a desired high shear strength of the interface. Manganese was chosen as the alloying element because it is an important trace element in the human organism and because no toxic or allergic reactions with the human body have as yet become known. The manganese content of the alloys must be limited to 6 wt%. By the use of higher manganese contents, the eutectoid decomposition of the P-phase to the cc-phase and to the intermetallic compound TiMn is accelerated and intensified. With an increasing amount of this compound, the ductility of the material is diminished. Because of this fact the alloy TiMn8 shows an extreme embrittlement. Theoretical considerations lead to the requirement of a thin ceramic layer on the surface of the metallic material. Under service conditions the implants are

r?i
o HA

Ti

Ti

.G 8 % ._

TiO, b i

20

30
2 8

40

50

60

25

30

35

4
40 45

[ degrees ]

28

[ degrees ]
material TiMn6at 800C. HA,

Figure 9 X-ray diffraction of hydroxyapatite powder produced by the sol-gel method at 600C (a) and 800C (b), respectively.

Figure 11 X-ray diffraction of a composite hydroxyapatite by the sol-gel method hydroxyapatite.

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film I, _.-_.-.-.~-.-.-._.-.-.-.-.~.~.~.~. ._.F&&J+!? Substrate

Figure during 12 Stress contribution bonding (schematic). with a composite material

diffusion of calcium and phosphorus from the ceramic into the metallic material. The diffusion in metals is accelerated by defects such as voids, dislocations and grain boundaries. Therefore, the metallic substrate can be optimized by producing a fine grain size and a certain dislocation density in order to enhance the diffusion at low temperatures, whereby a good chemical bonding will be achieved.

REFERENCES
loaded mainly by bending stresses. As shown schematically in Figure ZZ, the maximum tension stress occurs during bending at the surface itself. Therefore, with a ceramic-metal composite the ceramic layer has to sustain the maximum tension stress and thick layers are extremely subject to failure. Thin HA layers can be favourably produced by the sol-gel method using dip coating. This method has several advantages. Besides an easy performance, the method is very economical. However, the main advantage is to be found in the solgel HA powder. Due to its nanocrystalline scale its activity, especially its sintering activity, is extremely high. Therefore, the production of a dense layer and, for the formation of chemical bonding by diffusion, very low annealing temperatures of about BOO-800C are sufficient. Due to these low annealing temperatures the microstructure of the substrate material and therefore the properties of this material cannot be unfavourably influenced. Due to this advantage the microstructure of the metallic material can be optimized in order to offer the best conditions for the chemical bonding, which is mainly effected by the Breme J. Titanium and titanium alloys -The biomaterials of preference. M&n Etudes Scient Rev-M&d1 1989; 86: 625-637. Schmitz HJ, Gross U, Kinne R, Fuhrmann G, Strunz V. Der Einfluj3 unterschiedlicher Oberftichenstrukturierung alloplastischer Implantate auf das histologische und Zugfestigkeitsverhalten des Interface, 8. DVM-vortragsreihe des Arbeitskreises Implantate, 1987: 163-172. Dillier RM, Lee JM, Mamatopoulos C. Observations on the effect of movement on bone implants into poroussurface implants. Clin Orthop Rel Res 1986;ZOB: 108115.

Eulenberger J, Kelle F, Schroeder A, Steinemann SG. Haftung zwischen Knochen und Titan, 4 DVM-Vortragsreihe des Arbeitskreises Implantate, 1983: 131-140. Geldmacher-v.Mallinckrodt M, Machata G, Niirnberg HW, Schlipketer HW, Stumm W. In: Merian E, ed. Metalle in der Umwelt. Weinheim: Verlag Chemie, 1984. RBtzer-Scheibe HJ, Buhl H. Repassivation of titanium and titanium alloys. In: Liitjering G, Zwicker U, BunkW, eds. Proc 5th Int Conf on Ti. DGM, 1984: 2641-2649.

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