Be-NAV-04 15:08 +44 e707 arreir pager 1 fhe Se, egEESS PAPER 171 ' Wear, (3973) 337-98 bo! © Elsevier Sequola $.A., Lausanne ~ Printed in The Netherlands EFFECT OF PHOSPHORUS ON THE FRICTION AND WEAR ca CHARACTERISTICS OF GREY CAST IRON A : 3 T.S. EYRE ond P, WILLIAMS a Brunel University, Uxbridge, Middlesex (Gt. Britain) yn (Received February 2, 1973) SUMMARY Using a pin on ring machine the effects of phosphorus content on the friction and wear characteristics of grey cast icon were studied, Critical speed transitions are related to the physical properties of iron~phosphorus alloys and in conjunction with metallographic studies, theories regarding the wear mechanisms are discussed. INTRODUCTION Extensive use of grey cast iron in wear situations has enabled the desirable properties for wear resistance to be fairly well defined'?. A randomly distributed “A” type flake graphite of medium flake size in the range 4-5, in a pearlitic matrix, with a phosphorus content of approximately 0.8% is generally recommended, Al- though the beneficial effects on wear resistance afforded by phosphorus have often been reported, reasons for its effect are ill defined. This paper shows the effect that phosphorus has on the [riction and wear characteristics of a grey cast iron. Critical speed transitions are related to the physical properties of iron~phosphorus alloys and in conjunction with metallographic studies, theories regarding the wear mechanisms are discussed. Phosphorus is invariably present in cast iron occurring as lakes of phos- phide eutectic when it exceeds 0.1% The use of phosphorus with « pearlitic or pearlitic-ferritic matrix increases the strength while decreasing the. impact resistance, Tt is generally agreed that phosphorus increases the wear resistance of a cast iron, the maximum effect of the phosphorus being obtained when sufficient is present to form a continuous phosphide eutectic network. Angus® found that phosphoric irons had good resistance to seizure under conditions of marginal lubrication such as occur with machine tool slideways. [t was suggested that this was due to the lakes of phosphide eutectic standing proud of the surface enabling the bearing surface to retain some lubricant by capillary action between the phosphide eutectic network, "Experience in service had indicated that phosphorus improved the running-in characteristics of grey cast iron and reduced the tendency to scuffing of internal ‘combustion engine rings and liners*, To obtain increased scuffing resistance, the phosphorus content had to be maintained above 0.5%, however it would normallyee-Hav-e4 15:01 ow ° . +44 e707 erraiz pase: 2 338 T.S. EYRE. P. WILLIAMS be kept below 0.8% to avoid shrinkage and cracking problems during casting and in service due to thermal stresses, F Grey cast iron containing phosphorus is widely used for friction braking in railway transportation and 1.2% phosphorus has become standardised in France and the U.K. : Tt has been shown that an increase in phosphorus content decreases the weight loss at the end of the running-in period, although it would appear that little advantage is to be gained by increasing the phosphorus content much beyond 1% The effect of ferrite on the wear characteristics ofa phosphoric cast iron has also been investigated, showing little difference in equilibrium mild wear rates between a fully ferritic and a ferritic~pearlitic matrix structure. However, the presence of free ferrite markedly increases wear during the running-in period, The transitional nature of the wear of grey cast iron has been established by other investigators®® and a transition load versus sliding speed curve for a flake grey iron which has been taken from Wilson's paper is shown in Fig. 1 Fig. 1, Transition load os, sliding speed. MATERIALS AND EXPERIMENTAL PROCEDURE, The present investigation was concerned with a series of pearlitic flake cast irons containing 0.15%, 1% and 3% phosphorus. The composition aitd quantitative estimation of the microstructural constituents are given in Table 1, Wear pins, 0.64 om in diameter were machined from these materials which were cast as 3 cm diameter cylindrical bars,o6-mny-a4 15:02 444 e707 e7zel7 Pree: ° FRICTION AND WEAR OF GREY CAST IRON 339 TABLET ‘ COMPOSITION Element Matertal Grey cast iron Steel . Dise O1%P I%P IP c 3.02 22 24 on si 203 1832.00 o2s Mn 0.52 0390.32 0.89 s 0.092 Olds * 0.108, 0.038 P 0.106 18282 0.016 Mg 0.08 0.005 0.005, O17 Ni % FeyP less than 1% 15% 30% 0.12 Cr 1 Ferrite 0% ”% 0.03 Mo % Pearlite 93% 60%, a ar pin Gancry Pee eae eerie Fig. 2 Pin on ring wear machine, The weur pins were rubbed against rings which were produced trom steel, the composition and hardness of which are also given in Table I, The steel is similar to that used for railway wheels in the U.K, The experimental pin on ring machine is shown in Fig. 2. Experiments were carried out under dry sliding conditions, at a constant applied joad of {0 kg until all running-in was complete and equilibrium conditions were established. A 10 kg load was selected because it can be seen from Fig. 1 that this load would be sufficient to bring about transitions in wear rate and other experi- ments had shown that it produced thermal conditions similar to those obtained during actual braking. The wear rate (expressed as g/om of sliding) under these equilibrium conditions was then plotted against sliding speed and the resulting wear curves are shown in Fig, 3, Frictional resistance was obtained by measuring the displacement of the gantry supporting the wear pin, Values of coefficient of friction were calculated from340 slang Sb om 6) Fig, 3, Wear rate us. sliding speed. TABLE (1 Speed Coefficient of frletion (emis) —_— ose | I%P KP 600 032 058 062 000 025 0320.36 1400 o2t 02 042 1800 02k 02504} 2200 023 0320.46 2600 032 032034 5200 0.08 aos = O07 TABLE ffl X-RAY ANALYSIS PREE! 4 7.S. BYRE, P. WILLIAMS Load Speed fron Constituents identified aFe Fe FeO, Fe0, FeO eC Phophide 10 Trace 10 10 Trave Trace 10 Teace 0 Trace 10 OD 0.15% P Trace Trace 10 4000 1% P” Trace Teno Trace 0 4000 3% P Trace@e-nAv-o4 13:02 ° +48 e7e7 s77ei7 Pace: FRICTION AND WEAR OF GREY CAST IRON, 341 the formula = F/R where u is the coefficient of friction, F the frictional force, and R the normal reaction (load); the results obtained are shown in Table II. X-ray diffraction analysis of the debris was carried out using a Debye~ Sherrer camera with cobalt radiation and an iron filter, the results are shown in Table UL RESULTS. The wear curves obtained exhibit both mild and severe forms of wear, which have been defined by other investigators ** as (a) Mild Wear: is controlled by oxidation at the wear interfuce, resulting in oxidised debris and wear tracks, (b) Severe Wear: occurs due to breakdown of the protective oxide fitm formed during mild wear. Metal to metal contact results in heavily grooved and often pitted tracks, The debris in this region of wear is predominantly metallic. The iron containing 0.15% P exhibited a mild form of wear at low sliding speeds. Transition to a severe mode of wear occurred as the speed was ‘increased and the wear rate increased by about two orders, of magnitude (Fig, 3). During severe wear plastic flow at the surface as apparent and there was no evidence of oxidation on either of the wearing surlaces. Metallic debris appeared to result mainly from fracture along graphite flakes (Fig. 4). As the speed increased a transi- tion occurred to another mild form of wear, and the wear rate decreased by approximately one order of magnitude, Fig. 4, Surface low under sovere wear conditions (0.157% phosphorus: 500 emys; 4% preral etchant: longitudinal section). (x 400) 5as-nay-o4 13:03 +45 e7e7 s77ei7 PAGED 6 ° 342 T.S. EYRE, P. WILLIAMS. Ss Fix, 5. Stereoscan view of wear debris: '% phosphorus alley; (a) low speod—oxide debris: 5) high speed oxide and metal debris. (x 300)Be-nay-e4 13:04 +46 e707 e77017 Pree: FRICTION AND WEAR OF GREY CAST [RON 343 Another transition occurred at even higher sliding speéds and the increased wear appeared to be accompanied by surface melting with the production of spheroidised particles (Fig. 5). Thermocouples embedded close to the wear face, recorded temperatures in excess of {,000°C which is close to the melting points of these alloys. 7 The one percent phosphorus alloy exhibited a mild form of wear at 500 cm/s (Fig. 6) and the wear rate increased at an approximately linear rate as the speed was Fig. 6. Onide formation during mild wear (1% phosphorus: 500 em «: 2", pieral etchant, longitudin vection). (400) increased to 1000 emis but still remained some 1-2 orders of magnitude lower than that for the 0.15%, phosphorus alloys, Wear in this‘region was mild with the production of oxidised surfaces and oxide wear debris, A reversal in wear rate occurred suddenly at 1000 emys. Mild wear was once more established for the 0.15°,, alloy but the wear rate continued to increase for the 1.0%; alloy (Fig, 3). At approx. imately 1500 ems the 1.0%, alloy gradually changed from mild to severe wear, and thereafter the wear rate remained high, Severe plastic flow and surluce roughening is shown in Fig. 7. The addition of 3% phosphorus resulted in an extremely low wear rate at low speeds. The disc wear track was covered with oxide indicating that mild wear was operative. However, visual examination of the worn pin, in this low speed range, showed it to consist of two distinct areas (Fig, 8(4)), (i) White areas, which appeared relatively smooth and at, (ii) Grey regions surrounding the white areas, Alter etching in a 2% nital solution the grey areas were preferentially attacked ‘© reveal black areas (Fig. 8(b)) whilst the white areas exhibit a herringboneo6-may-aa izeas +44 e707 avvaiz Pree: @ 344 7S. EYRE, P. WILLIAMS Fig. 7. Transition to severe wear (1% phosphorus; 200 ems; 4% picral etchant, transverse section}. (200) structure, which after further etching shows more clearly the characteristic structure of a phosphide eutectic (Fig. 8(c)). Taper sections taken transverse to the wear direction indicated that the phosphide eutectic was the load bearing member of the surfuce (Fig, 9). The areas adjacent to the phosphide eutectic having reached a sufficiently high temperature to permit some oxidation. For the 3% phosphorus iron, the wear rate increased with sliding speed, until complete oxidation of the wearing surface occurred, illustrated in (Fig. 10). Thea6-nay-a4 isras +48 97e7 er7e17 Prog: 9 ° FRICTION AND WEAR OF GREY CAST IRON 345 Fig. 8, (a) Direct view of "as worn” surface (3% phosphorus; $00 cm/s) ( x 200); (b) after etching for 2 min in 2% nital; (c) after etching for 10 min in 2% nital and.tilting the specimen to clearly ceveal the herringbone structure of the phosphide eutectic, wear rate was then approximately the same as that of the 0.15% P iron previously discussed. A transition to a higher wear rate, indicative of the more obvious type of severe wear with surface plastic flow and the production of grooved surfaces, did not take place as the speed increased. A transition did however occur at higher siding speeds to a melting form of wear with the production of « globular wens lebris, The coefficient of friction values shown in Table II indicate the following general features,Be-nay-0s 15106 ° +44 e707 e77ei7 Pane: 16 346 ‘ T. 8, EYRE, P. WILLIAMS Fig, 10, Oxide produced by lld wear conditions (3% phosphorus; 2000 emys; 4% pieral etchant transverse section). ( x 400) (1) A transition in wear behaviour is accompanied by a corresponding change in coefficient of friction. (2) Providing that there is no transition in wear behaviour the coefficient of friction gradually decreases with increase in sliding speed. (3) The coefficient of friction decreases with the change from severe to mild wear,a6-nay-a4 ase07 +44 e707 e77e17 Pane: ° FRICTION AND WEAR OF GREY CAST IRON 347 (4) Melting wear occurs with a corresponding low value in coefficient of friction (values of 0.1), for all alloys at speeds above 5200 cm/s. (5) The effect of phosphorus is to increase the coefficient of friction and by changing the transitional characteristics establish a more consistent speed/p rela~ tionship. This is particularly pronounced for the three percent phosphorus iron. DISCUSSION Considering the 0.15% phosphorus alloy, at a load of 10 kg and a sliding speed of 200 crn/s, mild wear conditions were established which was expected based on the examination of Fig. 1 ‘The addition of 1% phosphorus appears to shift the transition curve to higher sliding speeds so that the initial mild wear persists to higher speeds prior to the onset of severe wear, This was probably caused by an increase in the tate of production of oxide brought about by increased frictional heating. The coefficient of friction is higher (Table I) and the thermal conductivity is lower (Table IV) so for a given load and sliding speed the surface temperature will be increased, TABLE IV Temperature Thermal conductvley ec) (eal em™? per {°Cjom™') 7!) 024% P «HP AOSAP 100 023 0.108 0.089 200 0.120 0.105 0.087 300 oe O01 0.084 400 outs 0097 0.081 500 on 0.992 0079 As the sliding speed is increased heat build up at the surface of the 1%, phosphoric iron caused thermal softening of the substrate. The surface was unable to support the oxide and severe wear occurred (Fig. 7) illustrating that deformation of the underlying metal is a critical factor in initiating severe weat. For the 3% phosphorus iron the phosphide eutectic appeared to be the major constituent in intimate contact with the disc at low speeds (Figs. 8 and 9) and the matrix structure would seem to be of secondary importance once equilibrium mild conditions have been established (Fig. 10), Classification of the type of wear occurring at these relatively low speeds for this iron is difficult, as the wear rate under these conditions is extremely low, but the mechanism in operation is not dependent on the production and maintain- ment of an oxide film, A small quantity of oxide was however, produced as oxidation of the areas adjacent to the load carrying phosphide eutectic occurs. X-ray diffraction analyses of the debris produced from this iron phosphorus alloy showed it to consist of FeO, aFe, Fe,C and Fe,P (Table Il). An oxide was also produced on the surface of the steel disc.although this was not analysed, A mild form of wear is, therefore, indicated by visual observations of the dise wear track, X-ray analysis of the wear debris and by the wear rate of the pin, However@6-MAY-04 13:07 @ +44 8707 a7zat7 paaer 12 348 : 1.5, EYRE, P. WILLIAMS a2 Pitan AG A aa See Fig. [1 Oxide formation on 3% phosphorus (4000 ems; 4% pital etchunt; longitudinal seetion). (400) the pin wear face appeared to be extremely smooth and mainly metallic in appearance. Microscopic examination, showed that metal to metal contact predominated and the wear mechanism appeared severe on the Archard classification?. A transition tou severe mode of wear did not take place as the speed was increased. This is probably a consequence of the massive ternary phosphide eutectic increasing the flow strength of the iron hence giving the micro-structure sufficient rigidity for the formation of a compact oxide layer. Stresses are then built up in the oxide film as a result of the volume change that occuts during oxidation and these are relieved by fracture of the oxide to form wear particles. As the speed was increased the proportion of Fe and Fe,C present in the debris decreased and was replaced with a larger propor- tion of FeO and austenite (Table 111). There was some evidence to indicate that the addition of phosphorus increased the tenacity of the oxide formed at the wearing, interface (Fig. 11) by aiding mechanical interlocking of the oxide to the substrate. Tt has been suggested that the formation of phosphates between the oxide and matrix structure increases the tenacity of the oxide formed'®. The addition of the 3% phosphorus has, therefore, suppressed the generation ofa severe form of wear at higher sliding speeds by permitting oxide formation to occur, The intimate contact of the phosphide eutectic at low sliding speeds decreases the wear rate and increases the friction between the sliding couple. It can be seen from Table II] that the coefficient of friction decreases when a transition occurs from a mild to a severe form of wear. However Farrell® in tests conducted on chromium containing steels, showed that the coefficient of friction was greater during the initial transitory severe running-in wear region preceding mild wear, This disparity is probably accounted for by the fact that during the severe wear of cast iron frictional resistance is reduced by the graphite acting as a dry lubricant. The effect of the phosphorus in the 3% alloy is to some extent masked as the speed is increased, At higher sliding speeds the frictional heat developed is sufficientBe-MAv-84 15:08 “ +44 sve? svz0i7 PAGE: 15 FRICTION AND WEAR OF GREY CAST [RON 49 to produce a continuous adherent oxide film;and the wear rate becomes similar to that of the 0.13% phosphoric iron. This is to be expected’as the wear rates are then influenced by fctors controlling the rate of oxidation and its adherence to the substrate, The 3% P iron does not exhibit the severe form of wear indicated in ig. 1, possibly due to the volume of continuous phosphide eutectic present giving it sufficient high temperature Mow strength. The 3% P iron, however, lowers the thermal conductivity sufficiently to promote higher surface temperatures and causes melting wear at a tower sliding speed than that for the 0.15% phosphorus alloy. CONCLUSIONS (J) The presence of 1.0% phosphorus completely iahibits the low speed mild to severe wear transition. (2) Above approximately 1,500 crys the presence of 1.0% phosphorus in- creases the weac cate of grey cast iron {3) Above approximately 1.750 om/s the 1.0% phosphorus alloy has o higher wear rate than both the 0,15 and the 3.0% alloys. Above 3,000 cms the 3.0%, alloy thay a higher wear rate than the 0.13% alloy. However at speeds up to 3000 em/s the 3% phosphorus iron has a lower wear rate than both the 0.15% and the 1.0% phosphorus irons. Above 4,500 cm/s the wear cates of all alloys are approximately the same (4) The coefficient of friction increases us the phosphorus content increases, however at speeds above 4,500 em/s they are approximately the sume with values (0f0.07-0.08, indicating wear by melting. The 3.0% phosphorus alloy has & markedly higher coefficient of friction at sliding specds up to 2,200 cm/s. (5) Phosphorus modifies the wear characteristics of grey, iron under dry sliding conditions, by providing « herd eutectic which stabilises the microstructure AUioads and speeds when mild wear would normally be expected to change to severe wear, This hard eutectic stands peoud of the wear surface during sliding contact, and carries the applied load, ACKNOWLEDGEMENTS This work was carcied out in the Metallurgy Department and the author would like to thank Professor Bodsworth for his support. British Rallwoys Board financially supported one of the authors (Paul Williams) for the three yesr period, during which this york was carried out and the authors would like to thank them. REFERENCES LH, T, Aegus, Wear, | (1987) 40 2A, L. Boogiold, Trans Am Foundrymens Soc, 41 (1933) 573 3 FCT, Angus BCA. Conf, April 1-9, 1970 4 -M.1, Neale, Pow, Ins. Mech’ Engrs, 185 ((970-7() 26-32. F, Wilson and T.S. Bye, Metals Mater, 3 (1969) 86 G, Yoshimate and T. Tsukizos, War, 1 (1857) 472, Ts, Bye, PhD. Thasl, Brunel University, 1971 R 1 ar M. Fartll wad T.S, Eyre, Wear, 15 (1970) 358, F. Acchaed und W. Hugs, Proc, Roy Soc (London), 283A (1957) S15. Ibvight and Wilton, personel communication.