Pergamon

Corrosion Science, Vol. 37, No. 9, pp. 1333-1340, 1995 Copyright 0 1995 Elsevier Science Ltd Printed in Great Britain. All rights reserved ool(r93sx/95 %9.50+0.00

0010-938X(95)00033-X

A COMPARISON OF SINTERED
K.H.W.
Department

BETWEEN THE CORROSION AND UNSINTERED POROUS

R. THAMPURAN, X. CHEN* and

BEHAVIOUR TITANIUM
S.H. TEOH

SEAH,

of Mechanical

Engineering, National University of Singapore, Singapore 0511, Singapore

10 Kent Ridge Crescent,

Abstract-Corrosion tests were performed on sintered and unsintered titanium porous compacts of various porosities, as well as on solid titanium which acted as a control material. The tests were conducted in 0.9% aqueous NaCl solution maintained at 37C to simulate the physiological environment encountered by surgical implants in the human body. The results confirm that solid titanium and sintered porous titanium both possess a distinct passivation range. Unsintered porous titanium does not seem to passivate at all and suffers greater corrosion than solid titanium. Unsintered specimens compacted at higher pressures experienced more corrosion than those compacted at lower pressures, although sintered specimens behaved in the exact opposite fashion. An explanation is given in the paper for these phenomena.

INTRODUCTION For centuries now, metallic devices have been used to repair and replace parts of the human body. It became apparent, from post-surgical infections, that the success of implant surgeries greatly depended on the properties of the implant material. Bannon and Mild listed the characteristics that make a good implant material. These are: (i) no tissue reaction to the implant, (ii) no corrosion of the implant, (iii) design and functionality of the implant, (iv) mechanical properties of the implant, and (v) surgical implications. In addition to stainless steels and Cr-Co alloys, titanium has been found to satisfy the above criteria.* By the mid-1960s, titanium successfully replaced stainless steel and Cr-Co alloys in nearly all such implants, with no reported failures3 Hall and Hackerman were the first to observe pitting corrosion of commercially pure (CP) at 10 V after some samples were anodically polarised in 0.5 M NaCl solution. Later, Tomashov et al. concluded that different conditions of oxidation produced different oxide forms for titanium. Hoar and Mears6 made a comprehensive study of corrosion of surgical implant materials in Hanks physiological solution and various NaCl solutions at 37C, and found that titanium and its alloys formed a stable passivating film on the surface and possessed very high breakdown potentials. Solar et a1.7 confirmed these findings and showed that the corrosion results for titanium in human blood, Hanks solution and chloride solutions were similar. This led to the conclusion that inorganic solutions are satisfactory substitutes for blood, and probably other extracellular fluid, for studying the corrosion behaviour of titanium.

* Metals and Advanced Materials Centre, Singapore Institute of Standards Science Park Drive, Singapore 051 I, Singapore. Manuscript received 14 June 1994; in amended form 19 September 1994. 1333

and Industrial

Research,

1334

K.H.W.

Seah et al

As early as 1951, Leventhals reported that his studies on rabbits and rats showed that titanium is an inert metal and appears to be ideal for fixation of fractures ~~ a conclusion confirmed by other research workers. Methods of fixation include as well as in-situ methyl methacrylate impaction, mechanical internal fixation, polymerisation. Failures of these fixation techniques stimulated interest in the field of biological growth into inert porous materials. Improved distribution of stress, a biological repair system, a biological defense against infection, and a more permanent implant resulting in greater patient comfort are some advantages of adopting such a fixation technique, through which there is bone in-growth into the pores of porous titanium. Parametric studies of the effect of pore size on bone in-growth were performed by Nelson et al. and Ducheyne et ~1.~ The biomedical properties of porous implant materials are important as lower elastic modulus materials with moduli closer to that of bone are able to transfer forces to surrounding bone more readily, thereby reducing stress-shielding effects and enhancing bone in-growth.14 Lucas et a1.15 studied the corrosion behaviour of passivated and steam-sterilised porous titanium in 0.9% aerated NaCl solution at 37C. They found that the porous wire mesh portion of the specimen (having an inherently larger surface area as compared to the solid substrate) experienced a higher current density at each level of potential. Buchanan et ~1.~ conducted anodic polarization tests for porous CP titanium surface layers on solid Ti-6A14V substrates in 10% calf serum and 90% isotonic saline at 37C and found that the anodic current densities for the porous titanium were significantly larger than those for the solid substrate. They concluded that the larger current density for the porous portion was due to the larger true surface area of the porous portion. Seah and Chen17 tested the corrosion characteristics of solid 316 stainless steel, solid titanium and porous titanium of different porosities in 0.9% NaCl solution at 37C. Unfortunately, they made a detailed study of the effect of porosity for only porous titanium specimens which were compacted and left unsintered. Unsintered specimens are invariably brittle and are not suitable for surgical implants. It is conjectured that sintered and unsintered specimens will exhibit different corrosion behaviour. The aim of this present research is to compare the corrosion characteristics of sintered and unsintered porous titanium compacts, produced by the technique of powder metallurgy, of varying degrees of porosity in 0.9% NaCl solution at 37C. A solid titanium specimen was used as a control for the tests. These parameters were chosen to simulate the environment which a typical titanium surgical implant would encounter in the human body.

EXPERIMENTAL

METHOD

The main equipment used for this series of experiments was an automatic polarisation unit comprising the following components: arbitrary function generator (Hokuto Denko HB-105), GPIB potentiostat: galvanostat (Hokuto Denko HB-SOIG); NEC Ih-bit CPU (PC-901 RX); NEC monitor (PC-KD854n); NEC printer (PCPRIOIGS); and a Techne water bath (Tempette TE-RA). Polarisation was controlled by the potentiostat and the input signal was provided by the function generator. The potentiostat included a high impedance (> 10 a), low rise time (below 0.3 ps at no-load condition) electrometer for measuring the potential between the anode and the reference electrode, as well as an electronic milli-ammeter with a maximum output of i_ I A. The instrument was able to test up to a potential of + IOV.

A comparison

between the corrosion

behaviour

of sintered and unsintered

porous

titanium

1335

I II

Reference electrode

Heater

Beaker (test cell)

Constant temperature bath c-

U > ---_

Working electrode (specimen) Counter electrode

Fig. 1.

A schematic

diagram

of the polarisation

test system

An electrometer of high impedance was used for electrochemical potentiometry to avoid polarising the reference electrode. In order to generate anodic polarisation curves by the data acquisition of the computer system, current and potential measurements had to be converted to the digital form by a two-channel analog-digital (AD) converter. AD converters are typically fairly high in impedance and, most importantly, they are connected to the system of electrodes only for the duration of AD conversion (approx. 1 ps), thus eliminating the problem of reference electrode polarisation. The potentiostat had a three-electrode system, namely, a reference electrode, an auxiliary (counter) electrode and a working electrode which was the specimen of interest. A saturated calomel electrode (SCE) served as a reference electrode. A platinised titanium wire was made the counter electrode to complete the circuit. The wire was properly insulated, leaving only an exposed area of 1 cm. A schematic diagram of the arrangement is shown in Fig. 1. Test specimens Commercial 99% pure grade 4 titanium powder was compacted to make the test specimens. Scanning electron microscope (SEM) studies revealed the mean particle size to be 150 pm. The various particle shapes of the powder are observed to be ligamental, aggregate, rounded, flake and irregular, which conform to the qualitative description of the shapes prescribed by German. Each porous titanium compact was made by compacting about 10 g of powder in a punch-die set of diameter 19.2 mm using a hydraulic-driven compaction machine. To obtain compacts of four different porosities for sintering, the powders were respectively compacted to four different pressure levels (5, 10, 14 and 18 t). To obtain compacts of three different porosities for making the unsintered specimens, the powders were, respectively, compacted to three different pressure levels (5, 12 and 18 t). Compaction was done gradually (in steps of2,5,8, 10, 12, 14, 16 and 18 t) to allow the pressurised powder particles to adjust and settle. Each compact produced was at least 10 mm thick.

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Sintering

K.H.W.

Seah a al.

A vacuum oven capable of attaining a vacuum of up to 10~~ mbar was used for sintering so that the compacts would not oxidise in the process. The compacts to be sintered were put into small ceramic tubes 10 cm long whose ends were covered using stainless steel foil, in order to prevent contamination of the vacuum oven by titanium powder. These tubes were then inserted into the vacuum oven and the heating cycle for the sintering process (as shown in Fig. 2) was carried out. Figure 3 is a graph showing the relationship between porosity (measured in terms of ~01%) and compaction pressure for sintered and unsintered titanium specimens.
Mounling ofcorrosion specimen

Each of the specimens was milled to a cubical shape of side 1 cm and to an accuracy of + I % as specified by ASTM.2 A wire was connected to one side of the specimen by means of a steel screw as shown in Fig. 4. The exposed surface of the specimen was limited to 1 cm2 by cold mounting it using a thermosetting resin which acted as an insulator for the other five sides. The hole for the screw was drilled and tapped. This severe wear and deformation produced a pore-free tapped hole. Therefore, no electrolyte would have been able to come in contact with the screw. The exposed surface was polished with close adherence to ASTM G5-82. There were two stages m the polishing process, namely mechanical grinding and electropolishing. Mechanical grinding was done to

, lhr

Zhrs

-----c------Time

2hrs

2hrs

Heating
Fig. 2.

cycle

for sintering

process
process

Heating

cycle for sintering

x Umintered + Sintered

P 1, VI e =

30-

20-

10 Compaction
Fig. 3. Graphs of porosity

12

11

16

18

Pressure

t tonnes)
pressure.

vs compaction

A comparison

between

the corrosion

behaviour Screw /

of sintered

and unsintered

porous

titanium

1337

Wire Polymer resin I

Wire lug

\ Specimen Fig. 4. A schematic diagram of the mounted test sample

remove any resin that may have overflowed on to the test surface. This was done in four stages using SIC paper of 320, 600, 800 and 1000 grit in that order. The samples were then degreased by swabbing with acetone, followed by rinsing in distilled water. Subsequent electropolishing was necessary to re-open pores closed by the mechanical grinding. Also, electropolishing was used to remove wear debris and relieve surface stresses introduced by grinding. The electropolishing was done using the Electromet polishing machine III (Model no: 70-1730) and a voltage setting of 60 V for I min. The electrolyte used for electropolishing was a mixture of 940 ml of acetic (100% glacial) acid and 60 ml of 60% perchloric acid.** Care was taken to add the perchloric acid to the acetic acid and not the other way round. Also, the used electrolyte was not poured away, but stored in a waste bottle for proper disposal. After electropolishing, the test surface was again meticulously washed with acetone and distilled water before drying. Test procedure The experimental set-up is shown schematically in Fig. I. The electrolyte used was 0.9% aqueous NaCl solution as specified by ASTM. Prior to immersion of the electrodes, the beaker of electrolyte was heated to a constant temperature of 37C to simulate the physiological environment in a constant temperature water bath. The test surface of the sample (working electrode) was positioned as close as possible to the reference electrode (SCE) and care was taken to ensure that the sample was at a depth of more than 2 cm from the liquid/air interface. This was necessary to ensure that oxygen supply was identical for all samples.* Following immersion of the electrodes, the corrosion potential of the test surface was continuously monitored for I h. Anodic polarisation measurements started only after the I h period. A scan speed of 25 mV/min was decided on after referring to several reports of past trials6. Data collection was done at I s intervals and was halted only when the anodic polarisation range of 2500 mV was exceeded. The duration of each test was about 160 min. Every corrosion test was repeated several times to ensure repeatability.

EXPERIMENTAL

RESULTS

AND

DISCUSSION

Unsinteredporous titanium Figure 5 shows the plots of the potential-current curves for unsintered porous titanium. The curve for solid titanium is included in the figure for comparison. All the results were found to be repeatable. The large passivation region seen in the solid titanium is expected,4.7 and so is the fact that porous titanium is more susceptible to corrosion than solid titanium.Sm17 Porous titanium does not seem to exhibit any passivation region at all. What is really surprising, however, is that with increase in compaction pressure (which corresponds to a lowering of porosity), current density increases. Previous research workers 15- have shown that a porous specimen will have a higher corrosion current density than a solid one since its true surface area is larger

1338

K.H.W.

Seah et al.

0 0.01 -500 1

I , , _,I 0.1

.;

Log Current Anodic Fig. 5. polarisation

Anodic polarisation

Density (IJ.A/cm2) for unsintered porous

porous

curves

titamium

curves for unsintered

titanium.

than the nominal surface area. By the same reasoning, a more porous specimen should also suffer more corrosion than a less porous one. The corrosion results obtained for unsintered porous titanium are therefore contrary to this commonly held view.
Sinteredporous titanium

Figure 6 shows the plots of the potential-current curves for sintered porous titanium. The curve for solid titanium is included in the figure for comparison. All the results were found to be repeatable. Once again, the large passivation region seen in

Compadin Ressure _ 18tonnes

Log Current Anodic Fig. 6. polarisotion

Anodic

Oensity ( M/cm2 I curves for sintered porous titamium

titanium.

polarisation

curves for sintered porous

A comparison

between the corrosion

behaviour

of sintered

and unsintered

porous

titanium

1339

the solid titanium is expected,4,7 and so is the fact that porous titanium is more susceptible to corrosion than solid titanium.5-7 However, there is only a small passivation region in the former case. In this figure, it can be observed that with increase in compaction pressure (which corresponds to a lower porosity), current density decreases. This effect is contrary to what is seen in Fig. 5. Explanation for the discrepancy In order to explain why a difference is observed between the corrosion behaviour of sintered and unsintered porous titanium, it is necessary to study the pore morphology of porous structures. In the case of green (unsintered) compacts, the pores/crevices are sharper, smaller and closer together when the compaction pressure is high. In order to function as corrosion sites, the crevices must be wide enough to allow liquid entry and, at the same time, sufficiently narrow to maintain stagnancy of the electrolyte. Highly dense green compacts appear to have a pore morphology that promotes crevice corrosion. In highly porous green compacts, however, pore morphology is predominantly one with wide, interconnected channels that allow the free flow of liquid and, thus, fewer sites are available for promoting crevice corrosion. These differences in pore morphology seem to account for the greater corrosion resistance observed in the highly porous green compacts. In sintered compacts, however, particle-to-particle diffusion and grain boundary movement (caused by the sintering process) change the pore morphology. In highly porous compacts (produced under low compaction pressure), the wide open channels are narrow and isolated, thereby providing a large number of sites capable of trapping liquid that eventually promote crevice corrosion. In the low porosity compacts (produced under high compaction pressure), the high densification promotes pore closure during sintering, and the resultant number and size of crevices are smaller, causing these compacts to be more resistant to crevice corrosion attack. Polarisation curves for the 5 t specimens In both Figs 5 and 6, it can be seen that the polarisation curves for the 5 t specimens are quite far away and different from the curves for the samples compacted to higher tonnages. This can be explained by considering the relationship between the porosity of a specimen and its compaction pressure, as shown in Fig. 3. In this figure, it can be observed that as compaction pressure increases, porosity decreases at a decreasing rate. The drop in porosity is less and less severe as compaction pressure increases. This means that the 5 t specimen has a porosity that is significantly higher than those compacted to higher pressures. Therefore, it can be deduced that the 5 t specimens should have a pore morphology that is significantly different from that of the other specimens, the latter ones having greater similarity in corrosion behaviour with one another since their porosities are closer to one another.

CONCLUSIONS The experiments conducted confirm that solid titanium and sintered porous titanium both possess a distinct passivation range. However, unsintered titanium does not seem to passivate at all and suffers greater corrosion than solid titanium. Moreover, unsintered specimens which were compacted at higher pressures experienced more corrosion than those compacted at lower pressures, although

1340

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Seah et al.

sintered specimens behaved in the exact opposite fashion. Pore morphology compacts is a possible explanation for this observed discrepancy.
Acknowledgements- -The authors in the collection of data. would like to express their appreciation to Anuj Agrawal

of the

for his assistance

REFERENCES
I. 2. 3. 4. 5. 6. 7. 8. 9. IO. Il. 12. 13. 14. 15. 16. 17. IX. 19. 20. 21. 22. 23. B.P. Bannon and E.E. Mild, ASTM STP 796, 7 (1983). R.T. Bothe, L.E. Beaten and H.A. Davenport. Surg. Gynec-01. Ohstet. 71, 598 (1940). G.H. Hille, J. Mater. 1. 373 (1966). C. Hall and N. Hackerman, J. Phys. Chem. 57, 262 (1953). N.D. Tomashov, R.M. Altovsky and M.Y. Kushnerev, Doklady Akademii Nauk 141, 913 (1961). T.P. Hoar and D.C. Mears, Proc. Roy. Sot. A 294, 486 (1966). R.J. Solar, S.R. Pollack and E. Korostoff, ASTM STP 684, I61 (1979). G.S. Leventhal, J. Bone and Joint Surgery 33A, 475 (1951). P.G. Laing, A.B. Ferguson and E.S. Hodge, J. Biomed. Mater. Res. 1. 135 (1967). F.W. Rhinelander, M. Rouweyha and J.C. Milner, J. homed. Muter. Res. 5, 81 (1971). F. Escales, J. Galante, W. Rostoker and P. Coogan, J. Biomed. Mater. Res. 10, 175 (1976). D.D. Nelson, H.E. Rubash and D.C. Mears, ASTM STP 796, 255 (1983). P.Ducheyne, P. Martens, P. De Meester and J.C. Mulier, ASTM STP 796, 265 (1983). M. Spector, M.J. Michno, W.H. Smarook and G.T. Kwiatkowski, J. Biomed. Mater. Res. 12, 665 (1978). L.C. Lucas, J.E. Lemons, J. Lee and P. Dale, ASTM STP 953, 124 (1987). R.A. Buchanan, E.D. Kigney Jr and CD. Griffin, ASTM STP 953, 105 (1987). K.H.W. Seah and X. Chen, Corros. Sci. 34, 1841 (1993). D.C.Tipton, ASTM STP 866, 24 (1985). R.R. German, Powder Metallurgy Science. Metal Powder Industries Federation, Princeton, NJ (1984). Annual Book qf ASTM Standards, p. 102 (1991). Annual Book of ASTM Standards, p. 73 (1991). R.R. Ogden, Titanium in Rare Met&s Handbook. Prentice-Hall, NJ (1965). Annual Book qf ASTM Standards, p.29 (1991).