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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 37°C 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 Hank’s physiological solution and various NaCl solutions at 37”C, 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, Hank’s 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,

1

Buchanan et ~1.9% NaCl solution at 37°C. Seah and Chen17 tested the corrosion characteristics of solid 316 stainless steel. NEC monitor (PC-KD854n). and a more permanent implant resulting in greater patient comfort are some advantages of adopting such a fixation technique. and a Techne water bath (Tempette TE-RA). low rise time (below 0. 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. 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).’ ” Methods of fixation include as well as in-situ methyl methacrylate impaction. solid titanium and porous titanium of different porosities in 0.‘~ 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.3 ps at no-load condition) electrometer for measuring the potential between the anode and the reference electrode. 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. thereby reducing stress-shielding effects and enhancing bone in-growth. It is conjectured that sintered and unsintered specimens will exhibit different corrosion behaviour. polymerisation. mechanical internal fixation. Failures of these fixation techniques stimulated interest in the field of biological growth into inert porous materials. They concluded that the larger current density for the porous portion was due to the larger true surface area of the porous portion. GPIB potentiostat: galvanostat (Hokuto Denko HB-SOIG).1334 K. The aim of this present research is to compare the corrosion characteristics of sintered and unsintered porous titanium compacts. A solid titanium specimen was used as a control for the tests. NEC printer (PCPRIOIGS). 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. Improved distribution of stress. they made a detailed study of the effect of porosity for only porous titanium specimens which were compacted and left unsintered. . produced by the technique of powder metallurgy. Seah et al As early as 1951. NEC Ih-bit CPU (PC-901 RX).15 studied the corrosion behaviour of passivated and steam-sterilised porous titanium in 0. of varying degrees of porosity in 0. a biological defense against infection.9% aerated NaCl solution at 37°C. a biological repair system.W.H. The instrument was able to test up to a potential of + IOV.” and Ducheyne et ~1. as well as an electronic milli-ammeter with a maximum output of i_ I A.14 Lucas et a1. Polarisation was controlled by the potentiostat and the input signal was provided by the function generator. The potentiostat included a high impedance (> 10” a).9% NaCl solution at 37°C. Unfortunately. Unsintered specimens are invariably brittle and are not suitable for surgical implants.‘~ conducted anodic polarization tests for porous CP titanium surface layers on solid Ti-6A14V substrates in 10% calf serum and 90% isotonic saline at 37°C and found that the anodic current densities for the porous titanium were significantly larger than those for the solid substrate.

A platinised titanium wire was made the counter electrode to complete the circuit. 1. namely. they are connected to the system of electrodes only for the duration of AD conversion (approx.” The potentiostat had a three-electrode system. Test specimens Commercial 99% pure grade 4 titanium powder was compacted to make the test specimens. a reference electrode. 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. the powders were.8. 1 ps). current and potential measurements had to be converted to the digital form by a two-channel analog-digital (AD) converter. most importantly. 16 and 18 t) to allow the pressurised powder particles to adjust and settle. 14 and 18 t). thus eliminating the problem of reference electrode polarisation. flake and irregular. an auxiliary (counter) electrode and a working electrode which was the specimen of interest.A comparison between the corrosion behaviour of sintered and unsintered porous titanium 1335 I II Reference electrode Heater I I Beaker (test cell) Constant temperature bath c- U > ---_ Working electrode (specimen) Counter electrode Fig. respectively. leaving only an exposed area of 1 cm’. 1.2 mm using a hydraulic-driven compaction machine. . In order to generate anodic polarisation curves by the data acquisition of the computer system. A schematic diagram of the arrangement is shown in Fig. AD converters are typically fairly high in impedance and. 12 and 18 t).5. 10. which conform to the qualitative description of the shapes prescribed by German. rounded. To obtain compacts of three different porosities for making the unsintered specimens. aggregate. the powders were respectively compacted to four different pressure levels (5. 14. Each compact produced was at least 10 mm thick. 12. A saturated calomel electrode (SCE) served as a reference electrode. 10.” Each porous titanium compact was made by compacting about 10 g of powder in a punch-die set of diameter 19. A schematic diagram of the polarisation test system An electrometer of high impedance was used for electrochemical potentiometry to avoid polarising the reference electrode. To obtain compacts of four different porosities for sintering. The wire was properly insulated. compacted to three different pressure levels (5. Compaction was done gradually (in steps of2.

The hole for the screw was drilled and tapped. Graphs of porosity 12 11 16 18 Pressure t tonnes) pressure. Zhrs -----c------Time 2hrs 2hrs I Heating Fig. 3. VI e = 30- 20- 10 Compaction Fig. namely mechanical grinding and electropolishing. in order to prevent contamination of the vacuum oven by titanium powder. no electrolyte would have been able to come in contact with the screw. lhr . Therefore. cycle for sintering process process Heating cycle for sintering x Umintered + Sintered P 1. 2) was carried out.2” A wire was connected to one side of the specimen by means of a steel screw as shown in Fig. 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.H.1336 Sintering K.W.” There were two stages m the polishing process. The compacts to be sintered were put into small ceramic tubes 10 cm long whose ends were covered using stainless steel foil. These tubes were then inserted into the vacuum oven and the heating cycle for the sintering process (as shown in Fig. The exposed surface was polished with close adherence to ASTM G5-82. 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. vs compaction . Mechanical grinding was done to . Figure 3 is a graph showing the relationship between porosity (measured in terms of ~01%) and compaction pressure for sintered and unsintered titanium specimens. Seah a al. 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. 2. This severe wear and deformation produced a pore-free tapped hole. 4.

the test surface was again meticulously washed with acetone and distilled water before drying. 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 . Anodic polarisation measurements started only after the I h period. but stored in a waste bottle for proper disposal. however. The electrolyte used for electropolishing was a mixture of 940 ml of acetic (100% glacial) acid and 60 ml of 60% perchloric acid.7 and so is the fact that porous titanium is more susceptible to corrosion than solid titanium. A scan speed of 25 mV/min was decided on after referring to several reports of past trials6. is that with increase in compaction pressure (which corresponds to a lowering of porosity). The electrolyte used was 0. 4. 600. the beaker of electrolyte was heated to a constant temperature of 37°C to simulate the physiological environment in a constant temperature water bath. The samples were then degreased by swabbing with acetone. The electropolishing was done using the Electromet polishing machine III (Model no: 70-1730) and a voltage setting of 60 V for I min. Subsequent electropolishing was necessary to re-open pores closed by the mechanical grinding. 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. The large passivation region seen in the solid titanium is expected. The duration of each test was about 160 min. Every corrosion test was repeated several times to ensure repeatability.4. This was done in four stages using SIC paper of 320. the corrosion potential of the test surface was continuously monitored for I h. Test procedure The experimental set-up is shown schematically in Fig.” Prior to immersion of the electrodes.A comparison between the corrosion behaviour Screw / of sintered and unsintered porous titanium 1337 Wire Polymer resin I d Wire lug \ Specimen Fig. The curve for solid titanium is included in the figure for comparison. This was necessary to ensure that oxygen supply was identical for all samples.” ” Data collection was done at I s intervals and was halted only when the anodic polarisation range of 2500 mV was exceeded. All the results were found to be repeatable. followed by rinsing in distilled water. After electropolishing.‘Sm17 Porous titanium does not seem to exhibit any passivation region at all.*’ Following immersion of the electrodes.** Care was taken to add the perchloric acid to the acetic acid and not the other way round. A schematic diagram of the mounted test sample remove any resin that may have overflowed on to the test surface. electropolishing was used to remove wear debris and relieve surface stresses introduced by grinding. I. EXPERIMENTAL RESULTS AND DISCUSSION Unsinteredporous titanium Figure 5 shows the plots of the potential-current curves for unsintered porous titanium. the used electrolyte was not poured away. Also. current density increases.9% aqueous NaCl solution as specified by ASTM. 800 and 1000 grit in that order. Also. What is really surprising.

.A/cm2) for unsintered porous porous curves titamium curves for unsintered titanium. The corrosion results obtained for unsintered porous titanium are therefore contrary to this commonly held view. Once again.1 .1338 K.I 0. Sinteredporous titanium Figure 6 shows the plots of the potential-current curves for sintered porous titanium. 5. Seah et al.W. a more porous specimen should also suffer more corrosion than a less porous one. polarisation Anodic polarisation Density (IJ. _. the large passivation region seen in Compadin Ressure _ 18tonnes Log Current Anodic Fig. The curve for solid titanium is included in the figure for comparison.H.01 -500 1 I . Log Current Anodic Fig. 0 0. All the results were found to be repeatable.. polarisotion Anodic Oensity ( M/cm2 I curves for sintered porous titamium titanium. 6. By the same reasoning. polarisation curves for sintered porous . than the nominal surface area.

In sintered compacts. the latter ones having greater similarity in corrosion behaviour with one another since their porosities are closer to one another. In the case of green (unsintered) compacts. 5. causing these compacts to be more resistant to crevice corrosion attack. it can be observed that as compaction pressure increases. 3. it can be observed that with increase in compaction pressure (which corresponds to a lower porosity). unsintered specimens which were compacted at higher pressures experienced more corrosion than those compacted at lower pressures. interconnected channels that allow the free flow of liquid and. porosity decreases at a decreasing rate.A comparison between the corrosion behaviour of sintered and unsintered porous titanium 1339 the solid titanium is expected. the crevices must be wide enough to allow liquid entry and. This can be explained by considering the relationship between the porosity of a specimen and its compaction pressure. smaller and closer together when the compaction pressure is high. unsintered titanium does not seem to passivate at all and suffers greater corrosion than solid titanium. This effect is contrary to what is seen in Fig. however. In highly porous compacts (produced under low compaction pressure). However. sufficiently narrow to maintain stagnancy of the electrolyte. it can be deduced that the 5 t specimens should have a pore morphology that is significantly different from that of the other specimens. In this figure. thereby providing a large number of sites capable of trapping liquid that eventually promote crevice corrosion. particle-to-particle diffusion and grain boundary movement (caused by the sintering process) change the pore morphology. In order to function as corrosion sites. the wide open channels are narrow and isolated. Therefore. Moreover. These differences in pore morphology seem to account for the greater corrosion resistance observed in the highly porous green compacts.4. In the low porosity compacts (produced under high compaction pressure). as shown in Fig. however. Explanation for the discrepancy In order to explain why a difference is observed between the corrosion behaviour of sintered and unsintered porous titanium. the high densification promotes pore closure during sintering. it is necessary to study the pore morphology of porous structures.‘5-‘7 However. In highly porous green compacts. In this figure. although . CONCLUSIONS The experiments conducted confirm that solid titanium and sintered porous titanium both possess a distinct passivation range. at the same time. there is only a small passivation region in the former case.7 and so is the fact that porous titanium is more susceptible to corrosion than solid titanium. the pores/crevices are sharper. and the resultant number and size of crevices are smaller. pore morphology is predominantly one with wide. 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. thus. Highly dense green compacts appear to have a pore morphology that promotes crevice corrosion. fewer sites are available for promoting crevice corrosion. current density decreases. The drop in porosity is less and less severe as compaction pressure increases. Polarisation curves for the 5 t specimens In both Figs 5 and 6. This means that the 5 t specimen has a porosity that is significantly higher than those compacted to higher pressures.

Escales. Leventhal. 16.D. 15. 265 (1983).T. 19. 21. p. 17. 262 (1953). Mater. Pore morphology compacts is a possible explanation for this observed discrepancy. Res.P. 7.C. Mild. Seah and X.J. Hille. 57.H. G. H. Kushnerev. Rostoker and P.Ducheyne. 598 (1940). would like to express their appreciation to Anuj Agrawal of the for his assistance REFERENCES I. 6. W. 14. Chem. Ferguson and E. J. M. A 294. F. F. 12.C. 124 (1987). W. 665 (1978). 20. . 102 (1991). Coogan. Il. ASTM STP 953.H. J. J. ASTM STP 866. Surg. J. K.C. Chen. Lee and P. Muter. Davenport. Hodge. Annual Book qf ASTM Standards.R.A. Smarook and G. NJ (1984). J. 913 (1961). Res. NJ (1965). 10. Solar.W. Lemons.A. D. Mater. sintered specimens behaved in the exact opposite fashion. C.1340 K.G. R.B. Prentice-Hall. R. 175 (1976). S. Hoar and D. 12. 3. Mears. 373 (1966). J. IX. Rhinelander.D. Bone and Joint Surgery 33A. De Meester and J. 22. 5. 475 (1951). Nelson.H. 24 (1985).-The authors in the collection of data. Proc. Rouweyha and J. Gynec-01. J. 13. Titanium in Rare Met&s Handbook. G. 73 (1991). Tomashov. ASTM STP 796.R. Kigney Jr and CD. J.Y. Laing.E. R.M. Roy. Seah et al.C.C. 5.P. p.C. Phys. Lucas. 1. Spector. I61 (1979). Buchanan. 8. Korostoff. D. homed. 23. R.R. Dale. Milner. Biomed. P. Hall and N. Bannon and E. Acknowledgements. 34.T.S. Kwiatkowski. Mulier. Doklady Akademii Nauk 141. 81 (1971). ASTM STP 953. Martens.S. ASTM STP 684. ASTM STP 796. Ohstet. Bothe. Griffin. R. 71. German.W. 486 (1966). Michno.D. R. Mater. Annual Book qf ASTM Standards.H. 2. p. Powder Metallurgy Science. Altovsky and M. Biomed. J. N. Res. Mears. M. Pollack and E.E. A. J. P. Beaten and H.E.Tipton.W. P. 1.29 (1991). Princeton. Ogden. 105 (1987). Rubash and D. ASTM STP 796. Biomed. E. 4.E. Res. Sci. B. Metal Powder Industries Federation. T. P. IO. M. 255 (1983). 1841 (1993). L. Mater.J. Hackerman. 9. 135 (1967). Corros. Sot. 7 (1983). Annual Book of ASTM Standards. L. Galante.