Alloys of Platinum and Tungsten FURTHER INVESTIGATION OF THE ALLOYING BEHAVIOUR COULD HELP TO IDENTIFY ADDITIONAL APPLICATIONS

By A. G. Knapton Group Research Centre, Johnson Matthey & Co Limited

The availability of a complete and accurate phase diagram is an essential requirement if a full understanding of the properties, and hence the potential applications, of an alloy system is to be gained. Although the general nature of the tungsten-platinum constitutional diagram has been known for many years, it is now apparent that intermediate phases which are not incorporated in the published phase diagrams may exist, and evidence to support this is presented.

It might be expected that the combination of such as nib tips for fountain pens or for gramo- the highest melting point metal with one of the phone needles (4). Tungsten-platinum alloys most oxidation resistant would result in also featured as electrical contact materials (5), materials with particularly useful technological but do not appear to be used currently for this. properties, but few applications have in fact Perhaps due to the limited range of uses of been found for alloys of tungsten with the alloys, the constitution of the tungsten- platinum. One such application is the composi- platinum system has received very little atten- tion containing 4 weight per cent tungsten and tion, compared for example with the closely a small amount of thoria which is used with related molybdenum-platinum alloys. Interest advantage as the sparking plug electrode in in the latter stems largely from the require- internal combustion engines where high ments of the glass industry, where stirrers, reliability and a long life are required (I). This electrodes and mandrels used in glass melting material has good erosion resistance and good are frequently fabricated from platinumdad electron emission properties and finds applica- molybdenum components. In such applications tion in helicopter and light aircraft engines. the life of the platinum sheath is largely The alloys in wire form are used to a limited dictated by the interdiffusion of molybdenum extent as electrical resistance materials. For and platinum, which may be limited to a con- example 8 weight per cent tungsten in platinum siderable degree by interposing a suitable is included as Regalohm 62 in the Johnson barrier layer. It was during the course of studies Matthey Metals Limited range of resistance of the use of tungsten as a possible barrier that wires, and similar compositions may be information was obtained on the formation of employed in high temperature strain gauges (2). intermediate phases in the tungsten-platinum At the other end of the alloy system, small addi- system. This paper describes the evidence tions of platinum to the tungsten targets of X- accumulated for the existence of these phases ray tubes are claimed to result in exceptionally during this investigation, and reviews other long lives (3). The additions inhibit roughening published information on the alloying of the targets even after prolonged operation. behaviour of the metals. In the past, tungsten-platinum alloys have The general nature of the tungsten-platinum also been applied in wear resistant situations, liquidus and solidus relationships were first

Platinum Metals Rev., 1980,24, (21, 64-69 64 determined many years ago (6) and are shown Sinha in a study of ordered AB, phases detected in the upper part of Figure I. At the higher an intermetallic compound, WPt, with the temperatures, the phase diagram is of the orthorhombic Mort, structure in an alloy simple peritectic type with the peritectic at annealed at 900OC (I 2). about 2460OC. The solid solubility of tungsten Other more recent studies by Luo (9) and by in platinum is high, with a maximum of about Khan and Raub (10) have concentrated on the 60 atomic per cent tungsten*, while the limit of anomalous behaviour of the face-centred cubic the solubility of platinum in tungsten was platinum solid solutions, and largely ignore the placed at about 4 per cent. The form of the possible intervention of intermediate phases. diagram and the absence of intermediate phases Lattice spacings reported by these two authors from the melt has been abundantly confirmed are shown plotted in Figure 2. Luo found that by subsequent investigations (7 to IO), but more the values passed through a minimum at I 8 per accurate determinations of solubility and cent tungsten followed by the increase that temperature data are obviously required. would be expected from Goldschmidt atomic Although it had been suggested from diameter considerations. Data from Khan and hardness or other anomalies that additional Raub on the other hand show a relatively flat phases were present at lower temperatures in minimum, with considerably lower values the platinum-tungsten system (6), the first especially at the higher tungsten contents. The direct evidence for these appears to be from the discrepancy in these results undoubtedly arises diffusion measurements of Rapperport, Merses from the difference in sample preparation. and Smith (I I). The data available are repro- Rapidly quenched alloys were used by Luo, duced in Table I and showed the presence of whereas Khan and Raub gave a relatively short two new phases (y) near 35 per cent tungsten annealing treatment of 4 hours at IOOO~C.Con- and (E) at 45 to 50 per cent, but no hrther sequently, it is probable that the latter alloys details of these phases have been published. are not truly representative of the platinum

Platinum Metals Rev., 1980, 24, (2) 65 structure changes in the alloys. As far as the constitution of the alloys is concerned, the information given by these investigators is a further demonstration of the extensive solubility of tungsten in platinum.

Diffusion Study During a limited study of the interdiffusion of platinum and tungsten at the Johnson Matthey Research Laboratories, a number of observations were made pertinent to the alloy- ing behaviour of the metal. A diffusion couple comprising a high purity tungsten rod encased in a tightly fitting platinum tube was annealed for 256 hours at 14ooOC. A cross-section of this couple was examined by electron probe micro analysis, and the tungsten trace taken with WLa radiation is shown in Figure 3. Three distinct zones can be recognised in this trace, corresponding to (i) the limit of solid solubility, 25 per cent of tungsten in platinum at 14oo0C, (ii) a comparatively wide band (I 5 microns) of solid solution and that some precipitation of a intermediate phase (y)at 33 to 37 per cent tung- second phase has occurred in the 25 to 50 per sten, (iii) a narrower band (5 microns) of a cent tungsten range. The results of Luo must, phase (E) occurring over the composition range therefore, be considered as more accurate in 45 to 52 per cent tungsten. this instance. Superconducting transition These results will be seen to be substantially temperatures and magnetic susceptibility in agreement with those of Rapperport and measurements have been used by these authors co-workers and the nomenclature y and E used to confirm that the anomalous minimum in the by these authors has been adopted here. lattice parameters has its origin in electronic The findings of this diffusion study have

Table I Diffusion Data on Tungsten-Platinum from Rapperport, Merses & Smith ( 1 1>

Composition Atomic per cent A Q platinum Phase cm2/s Kcal/mol Temperature, "c I

T 3.1 x 1CF2 139 13061 743 4.7 x 10-3 83.6 553 3.3 x 10-3 82.1 65 4.4x IW 92.0 1473-1 743

x 1.8 1e2 78.0 1300-1743 1.2 x 1e2 75.4 } 1.3 x 74.2 13061700

Platinum Metals Rev., 1980, 24, (2) 66 been included in the phase diagram shown in From the diffraction data it is apparent that Figure I, which illustrates that these phases are the y phase detected near 35 per cent in the formed at some temperature below the solidus diffusion couple is a tetragonally deformed from the platinum-base solid solution. Such a version of the face-centred cubic platinum study has not of course resulted in any detailed structure. This phase appears in a number of information on the precise mode of formation samples shown in Table 11, and typically has of these structures from the solid solution, but lattice parameters a = 3.896.4, c = 3.933A, by analogy with the molybdenum-platinum c/a = 1.010.In this respect it is very similar to system, the phase relationships in this region of the P(Pt,Mo) phase described by Rooksby and the diagram may prove to be complex (13, 14). Lewis (I5) in the molybdenum-platinum system. A similar analogy can be drawn Alloy Investigations between the hexagonal close-packed phase Additional confirmatory evidence for the (a = 2.80A, c = 4.5oA, da = 1.61) and the presence of these phases coupled with crystal corresponding 6 Pt,Mo, phase. structure data were obtained from a study of The lattice spacings of the platinum solid three selected alloy compositions namely solution show a substantial increase with addi- platinum with 35, 50 and 70 per cent tungsten tions of tungsten from a = 3.923A for the pure respectively. Alloys were prepared by metal to a = 3.947A for the 50 per cent tung- thoroughly mixing appropriate quantities of sten alloy. The values obtained have been high purity platinum and tungsten powders, plotted in Figure 2 and tend to confirm the and pressing the mixture into compacts. The results of Luo rather than the lower figures compacts were further treated by sintering at given by Khan and Raub. 14oo0C, or by arc melting, to effect alloying. A number of anomalies are present among Melted samples were also given prolonged the data presented in Table I1 and in view of anneals at 1400OC to allow precipitation of the these it cannot be claimed that complete intermediate phases in these alloys. The equilibrium has been achieved during the heat resultant compositions were examined by X-ray treatments at I 400°C. diffraction and electron probe micro analysis Electron probe micro analysis was carried and the results are given in Tables I1 and 111. out on samples in the arc melted condition and

Platinum Metals Rev., 1980, 24, (2) 61 Table I I X-rav Diffraction Data on Tunesten-Platinum Alloys

Alloy Lattice Constants treatment :om position t 140OOC Phases present a (k C(A) cia

'latinurn Sintered Tetragonal (Y) 3.896 3.943 1.012 15 per cent 50 hours Cubic b.c. 3.1 65 - - ungsten Sintered Tetragonal (y) 3.895 3.943 1.012 268 hours Cubic b.c. 3.1 66 - -

Melted 50 hours Cubic f.c. 3.922 - -~

Melted 218 hour Tetragonal (y) 3.896 3.933 1.010

'latinurn Sintered Tetragonal (7) 3.91 5 3.946 1.008 50 per cent 50 hours Hexagonal (c) 2.796 4.493 1.607 ungsten Cubic b.c. 3.1 66 - -

Sintered Tetragonal (y) 3.903 3.940 1.009 268 hours Cubic b.c. 3.1 65 - -

Melted Cubic f.c. 3.947 - - 50 hours

Melted Tetragonal (Y) 3.91 1 3.940 1.007 218 hours ~- ____

'latinurn Sintered Tetragonal (Y) 3.934 3.935 N 70 per cent 50 hours Hexagonal (E) 2.793 4.507 1.614 ungsten Cubic b.c. 3.1 66 - -

Sintered Cubic f.c. 3.934 - - 268 hours Hexagonal (E) 2.80 4.50 1.61 Cubic b.c. 3.168 - -

Melted Cubic f.c. 3.945 - - 50 hours Hexagonal (E) 2.79 4.50 1.61 Cu bic-b.c. -3.1 70 - - Table Ill Electron Probe Micro Analysis Results on Melted and Annealed Tungsten-Platinum Alloys I I Arc melted Melted+annealed at 1400°Cfor 50 hrs ~ ~~ ~~ ~ ~- Composition Platinum per cent Tungsten per cent Platinum per cent Tungsten per cent

~ ~- 35 per cent 71.7 28 3 (min) 67 1 33O(min) tungsten 1 63.2 1 36.8 (rnax) 1 63.6 1 36.4 (maxl I 50 per cent 1 53.2 46.8 (min) 62.0 1 38.0* tungsten 48.6 I 5 1.4 (max) 46.5 53.5 i 41.7 58.3t 70 per cent 40.0 60.0 tungsten 1 8.3 1 91.7 64 1 ".3 i1 91.7

tuggests that Y formation was occurring on 1400°C annealing tX-ray diffracrian shows the c phase, PI and W base solid ~oIuli0nsIn this aliov

Platinum Metals Rev., 1980, 24, (2) 68 after annealing at 1400°C for 50 hours with the reported by earlier workers in the molybdenum- results shown in Table 111. The melted samples platinum system. confirmed the peritectic form of the diagram, There is a high probability that further the 35 and 50 per cent tungsten alloys consist- developments of advanced power sources, ing of cored solid solutions with the maximum such as thermonuclear fusion, mag- and minimum composition variations as shown. netohydrodynamic systems or thermoelectric The 70 per cent tungsten alloy was duplex, the generators, will make increasing demands for primary tungsten solid solution phase contain- materials capable of withstanding extremes of ing 8.3 per cent platinum in a matrix composi- temperature. In such applications the tion of 40 per cent. importance of refractory metal alloys or clad After the 50 hour anneal, partial structures cannot be overemphasised, and a full homogenisation of the cored structure had understanding of these relies heavily on proper occurred in the 35 per cent tungsten alloy. constitutional diagram information. In this Some precipitation of the y phase was suggested context it is perhaps curious that certain of the by the probe results on the 50 per cent alloy, more exotic platinum group metal systems, for but the proportion of this phase present was example osmium-tungsten or iridium-tungsten, insufficient to be detectable by X-ray diffrac- have been the subject of reasonably complete tion. Three distinct areas could be distinguished studies, whereas tungsten-platinum has been in the 70 per cent tungsten alloy after anneal- largely neglected. Further phase diagram ing. The tungsten-base primary phase was studies are obviously well overdue on what accompanied by a fine eutectoid-like structure must surely be something of a Cinderella analysing at 64 per cent tungsten in a single among platinum alloy systems. phase matrix of 58.3 per cent. This is obviously a non-equilibrium structure and cannot be References interpreted with certainty from the data avail- I Eritkh Patent 578,956; 1946 able. During this study no evidence was 2 A. P. Adakhovsky, N. S. Agushevich and E. Yu. obtained for the existence of the orthorhombic Nekhendzi, Tr. Inst. Fiz. Met. Ural. Nauchn. WPt, phase described by Sinha (12). As the heat Tsentra Akad. Nauk SSSR, 1971,28,184 treatment temperature used by this author was 3 British Patent 1,243,279; 1971 4 C. J. Smithells, “Tungsten”, Chapman and Hall, 900°C compared with 1400OC in the present London, 1936, p. 225 investigation, this may be indicative of further 5. G. Windred, “Electrical Contacts”, Macmillan solid state reactions occurring at low and Co. Ltd.,.London, 1940, p. 350 . temperatures in the system. 6 M. Hansen and K. Anderko, “The Constitution of Binary Alloys”, McGraw Hill Book Co, New York, 1958, p. I 146 Conclusions 7 P. Greenfield and P. A. Beck, Trans. AIME, I 956,106,265 It has now been firmly established that at 8 A. G. Knapton,J. Inst. Met., 1958-59, a%, 87 least two intermediate phases are present in the 9 H. L. Luo,J. Less-Common Met., 1968,15,(3), 299 tungsten-platinum system which have not been I0 H. R. Khan and C. J. Raub, Metall, (Berlin), incorporated in the published phase diagrams. 1972,26, (I2), I222 I1 E. J. Rapperport, V. Merses and M. F. Smith, Evidence obtained from diffusion studies, arc U.S. Rep. ML-TDR-64-61, March 1964 melted or sintered samples are compatible with (Quoted in C. J. Smithells, “Metals Reference Book”, Butterworths, London, 1976) the formation of a tetragonal phase (y) near 35 I2 A. K. Sinha, Trans. Metall. SOC.AIME, 1969, pet cent tungsten and a hexagonal phase (E) 2459 (8,237 near 50 per cent tungsten, both phases being ‘3 G. L. Selman, Platinum Metals Rev., 1967, XI, stable at 140oDC.Electron probe micro analyses (41, 132 and X-ray diffraction have been used to deter- 14 G. L. Selman, Platinum Metals Rev., 1968, 12, (413 I34 mine composition and lattice spacing data for ‘5 H. P. Rooksby and B. Lewis, 3. hs-Common these phases. Analogous structures have been Met., 1964,6, (6), 451

Platinum Metals Rev., 1980, 24, (2) 69