Wear 250 (2001) 449461

The wear behaviour of high-chromium white cast irons as a function of silicon and Mischmetal content
A. Bedolla Jacuinde , W.M. Rainforth
Department of Engineering Materials, The University of Shefeld, Mappin Street, Shefeld S1 3JD, UK

Abstract The sliding wear behaviour of high-chromium white cast iron (16.8% Cr) has been examined as a function of silicon and Mischmetal alloy additions (1, 2, 3 and 5% Si and 0.1 and 0.3% Mischmetal). Such additions are known to modify the structure, but there is considerable controversy as to the exact effect. Silicon was found to rene the dendritic structure and increased the eutectic carbide volume fraction. However, for contents above 3%, transformation of the austenitic matrix to pearlite occurred in preference to martensite. Mischmetal additions reduced the austenite dendrite arm spacing, but did not have a signicant effect on the carbide structure. The wear behaviour was investigated for each alloy in the as-cast (austenitic matrix) and hardened (martensitic) conditions using a block on ring conguration in pure sliding in the load range 42238 N for a distance of 70 km against a hardened M2 steel counterface. For low loads (42 and 91 N), all the alloys showed a similar wear rate (3 104 to 4 104 mm3 /m), associated with the formation of a thin (3 m) oxide lm of Fe2 O3 , the formation of very ne debris and a small depth of deformation below the worn surface (7 m). For higher loads, wear was a strong function of microstructure, and was associated with a thicker lm of the oxides Fe2 O3 and Fe3 O4 and greater depths of deformation. The iron with 2% silicon exhibited the best performance with a wear rate of 7 104 mm3 /m and this was attributed to its ner structure and the formation of a thicker oxide lm. In contrast, the iron with 5% silicon exhibited the worst performance, with a wear rate of 14 104 mm3 /m, attributed to the pearlitic matrix. A linear relationship was observed between the depth of carbide fracture and the wear rate. The relationship between microstructure and wear mechanism is discussed. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Wear; High-chromium; Mischmetal content

1. Introduction High-chromium (Hi-Cr) irons exhibit excellent abrasion resistance, and are therefore, used widely as a hard facing material in, e.g. the mining and mineral processing industry [13]. In this case, a primary requirement is good abrasion and fracture resistance in cyclic loading, high impact loading, and corrosive environments. In addition, they are used in rolling/sliding contacts in applications such as work rolls for the hot rolling of metals [4], where the mechanisms of damage are abrasion of the matrix and rolling contact fatigue [5,6]. The high-chromium and carbon contents (1130 and 1.83.6%, respectively) [1], generate an as-cast structure of hard eutectic carbides of the type M7 C3 (where M represents the metallic species, Fe and Cr mainly) in a matrix of austenite. Once solidied, is not commercially viable to modify the carbide morphology by subsequent heat treatments. In contrast, the as-cast austenitic matrix is often destabilised to form a mixture of martensite/austenite
Corresponding author. E-mail address: m.rainforth@shefeld.ac.uk (W.M. Rainforth).

with small precipitated secondary carbides within the prior austenite dendrites, which provides maximum hardness in the system [2]. During solidication, the M7 C3 carbides grow as rods and blades with their long axes parallel to the heat ow direction in the mould [7]. While these carbides promote the excellent wear performance of Hi-Cr irons, their low fracture toughness results in a brittle material. The carbides are often large (up to 0.5 mm long [4]) and interconnected throughout the structure, and therefore, act as easy crack paths [8]. Thus, much attention has been directed at the control of the shape, size, interconnectivity, volume fraction and distribution of the carbide phase by means of the addition of some modier elements to the molten alloy. Previous attempts to control the structure of alloy white cast irons have been reported by various authors [2,4,917]. Rapid cooling during conventional casting can reduce carbide size, but this is limited to thin sections, (<50 mm) and is therefore, inappropriate to the manufacture of large items. Similarly, Hanlon et al. [4] demonstrated that spray forming, which gave over an order of magnitude reduction in carbide size, substantially improved wear response, but the high cost of the spray forming process is a limiting factor. Alternative strategies have relied

0043-1648/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 0 4 3 - 1 6 4 8 ( 0 1 ) 0 0 6 3 3 - 0

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on the adjustment of alloy chemistry. For example, boron additions to a 13% Cr iron [9] and to a 28% Cr iron [10] have changed the carbide morphology from interconnected, coarse, clustered, rods to a parallel distribution of isolated, ne rods. Rare earth elements have been successfully used to modify the carbide structure of low chromium white irons [1114] where the carbide phase is of the type M3 C, but they apparently have no effect in the morphology of the M7 C3 carbide in Hi-Cr irons [13]. Antimony and potassium caused a change in the quasi-regular lamellar eutectic carbides into rods and bent blades under directional solidication of the quasi-eutectic Fe4.24% C4% Cr [12]. Powell and Randle [15] observed a reduction in the carbide interconnectivity when adding 1.3% silicon to a 18% Cr iron. Laird and Powell [2] report that silicon inhibits the nucleation of the M7 C3 carbides in a 18% Cr iron, while in contrast Shen and Zhou [16] report an increase in the number of carbide phase nuclei due to silicon additions. The carbide phase has also been modied by the addition of carbide forming elements, such as niobium, vanadium, and titanium. The presence of such elements signicantly affects the mechanical properties by inuencing the strength of the matrix structure and the composition and dispersion of the carbide phases [1822]. The wear behaviour of white irons has been reviewed by Tabrett et al. [1]. Many microstructural factors such as the carbide type and hardness, carbide volume fraction, carbide spacing and matrix structure are reported to play an important role in the abrasive wear behaviour of these materials. However, the relationship between microstructure and wear response is complex. For example, increasing volume fraction of carbide has been reported to be both benecial [23] and detrimental [24] to the wear resistance. The complex behaviour is partly a result of the different contact stresses used by different authors. It the contact stresses that determine whether the carbide fractures or not, and this effect has an over-riding effect on wear. There remains no systematic study of the effect of quaternary alloy additions on microstructure and the subsequent effect on wear. On this basis, this work presents a systematic analysis of the effect of silicon and rare earth additions on the structure of a chilled 17% Cr iron. The microstructure has been rigorously characterised and related to the sliding wear behaviour.

Mischmetal were made (the commercial Mischmetal alloy contains mainly cerium and lanthanum). The alloys containing Mischmetal additions are denoted RE to reect its rare earth addition. These alloys were then cast at 1400 C into steel moulds to produce ingots of dimensions of 2.5 cm 1.5 cm 20 cm. A thermocouple (PtPt/Rh) was introduced through the side of the mould and was located centrally half height of the mould cavity. Thermocouple output was logged and indicated a cooling rate of 7 K/s. Fourteen ingots for the seven chemical compositions were cast for this study. Materials were investigated in both the as-cast and heat treated conditions, with the latter process aimed at destabilising the austenitic matrix. Heat treatment consisted of heating the ingots to 1100 C, holding for 45 min, air cool room temperature, then tempering at 250 C for 3 h. Ingots tested in the as-cast condition were given a stress relieve treatment at 250 C for 3 h. The microstructure was characterised using optical and scanning electron microscopy (SEM, JEOL6400) techniques. Microstructure was revealed through an etch in Villelas reagent for about 30 s. The phases present in the alloys were determined by X-ray diffraction (XRD, Philips model PW1710) using Co K radiation in a 2 range of 30130 , recording data each 0.02 at a speed of 0.2 /min. The fraction austenite and martensite were determined using the procedure described by Kim [25]. The sample was rotated during diffraction and data was acquired on three perpendicular faces of each sample, in order to remove any effect from preferred orientation. Microhardness was undertaken in matrix using the Vickers scale with a load 25 g (HV25 g ), while macrohardness was carried out by using a Rockwell C indenter. PC-based image analysis software was used to evaluate carbide sizes (area, perimeter and Feret diameter), and the carbide volume fraction for the as-cast irons. A total of 50 digitalised images at 250 magnication were obtained from each sample, which had been deeply etched (3 h in a solution of 50 ml FeCl3 plus 20 ml HCl in 940 ml ethyl alcohol) maximise contrast between matrix and carbides. The same procedure was used to measure the secondary dendrite arm spacing, but on samples etched with Villelas reagent. The wear behaviour of the Hi-Cr irons was investigated by pin-on-ring sliding using a Cameron Plint wear testing machine under dry sliding conditions. Pins of 1.0 cm

2. Experimental procedure A master alloy of 17% Cr white iron was made in a 10 kg capacity induction vacuum furnace using high purity elements under an argon atmosphere. The melt was poured into a metallic mould and let to cool. The chemical composition of this alloy is shown in Table 1. From this master alloy, 750 g samples of material were re-melted in a 1 kg capacity vacuum furnace under an argon atmosphere and additions of 1, 2, 3 and 5 wt.% of silicon, and 0.1 and 0.3% of
Table 1 Chemical composition of the masteralloy Element Carbon Chromium Nickel Molybdenum Sulphur Phosphorus wt.% 2.56 16.8 1.77 1.93 0.008 0.005

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diameter and 1.5 cm height were worn for 70 km against a 6 cm diameter counterface disc made of hardened M2 steel, at a sliding speed of 0.94 m/s (300 rpm). Both pins and counterface were polished to 0.25 m nish. Five tests were carried out for each alloy in the load range 42238 N, in both as-cast and heat treated conditions. Wear debris, worn surfaces, and worn surface cross-sections were characterised using XRD, SEM and optical microscopy.

3. Results 3.1. Microstructure and hardness Fig. 1 gives typical microstructures of the base Hi-Cr iron (i.e. without quaternary addition) in the as-cast and as-heat treated conditions. The as-cast state comprised M7 C3 in an austenite matrix, while the matrix in the heat treated condition comprised predominantly martensite, but containing secondary carbides and some retained austenite. A full description of the modication of the microstructure by Si and

Mischmetal will be presented elsewhere. Fig. 2 provides optical micrographs illustrating the changes induced by the Si addition. This demonstrates that Si had a signicant effect on the secondary dendrite arm spacing (SDAS). A fully quantied analysis of the microstructural changes are provided in Fig. 3, which gives secondary dendrite arm spacing and Fig. 4, which gives carbide volume fraction (CVF). The reasons for these changes will be published in detail at a later date. Both additions reduced SDAS, but Si had the major effect. The Si addition increased CVF from 0.24 in the base iron to 0.32 for the 5% addition, while the Mischmetal addition had no perceivable effect. The addition of 5% Si

Fig. 1. Microstructures of the base irons: (a) as-cast showing the austenitic matrix (A) and the eutectic carbides (M7 C3 ); (b) heat treated condition, showing the precipitated secondary carbides (SC) in a matrix of martensite (M) plus retained austenite (A).

Fig. 2. Optical micrographs showing the renement of the structure as silicon content is increased in the alloy: (a) base iron; (b) 1% Si; and (c) 3% Si.

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Fig. 3. Secondary dendrite arm spacing as a function of Mischmetal and silicon content for the experimental Hi-Cr iron.

resulted in destabilisation of the M7 C3 phase, replaced by M3 C (i.e. a pearlitic structure), and a removal of the dendritic morphology. Fig. 5 shows the effect of silicon on the phase constitution of the alloy for three silicon contents [26]. Note that for 0.5% silicon, the alloy has a hypoeutectic composition, lying within the austenitic phase eld. The 2% silicon alloy is close to eutectic, while the 4 and 5% silicon alloys have a hypereutectic composition, such that solidication starts with the formation of M7 C3 . The addition of the Mischmetal resulted in no systematic change in austenite content, which was 70% for the as-cast state and 30% in the heat treated condition. Similarly, additions of Si up to 3% led to a small reduction in retained austenite from 75% in the as-cast base alloy to 68% in the alloy with 3% Si, while contents were constant at 30% in the heat treated condition. However, additions of Si above

Fig. 5. Effect of silicon content on the liquidus projection of the CCrFe system: (a) 0.5% Si; (b) 2% Si; and (c) 4% Si (After [26]).

3% destabilised the austenite, with only 15% retained in the as-cast condition for a 5% addition. Table 2 gives the results of area, perimeter and shape factor of the M7 C3 . In the iron without silicon the carbides were present as eutectic colonies in sizes of 6 m and very

Table 2 Carbide size measurements obtained by image analysis Alloy Fig. 4. Variation of the carbide volume fraction for the different silicon and Mischmetal additions to the experimental irons. Base 5% Si Area (m2 ) 14 8 Perimeter (m) 34 13 Shape factor 0.3 0.6

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Fig. 6. Hardness variations for the different Hi-Cr irons as a function of the silicon and Mischmetal contents.

irregular in shape, while in the 5% Si iron the size is reduced to 3 m and more globular in shape. Fig. 6 gives the hardness results for the both as-cast and as-heat treated experimental irons. The major effect on hardness was the addition of Si in the as-cast condition. An increase was observed from 49 HRC for the base iron to 59 HRC for the 5% Si alloy resulting from the increase in carbide volume fraction induced by the Si addition. In contrast, in the heat treated condition, a small increase in hardness occurred for the both additions up to 0.3 wt.% Mischmetal and 3% Si. Greater additions of Si resulted in a substantial reduction in hardness. Microhardness measurements were also made of the matrix, and these followed a similar trend. Microhardness of the matrix increased from 300 HV25 g for the as-cast base iron to 550 HV25 g for the 5% Si iron. This increase is due to the solid solution strengthening caused by the dissolution of silicon in the austenite phase. For the heat treated irons, microhardness increased from 530590 HV25 g until 3% Si (highly martensitic matrix with secondary carbides) and then fell to 427 HV25 g for the 5% Si alloy (reecting a destabilisation of the austenite in favour of softer ferrite). Once again, Mischmetal additions exhibited no signicant effect on the microhardness of matrix. 3.2. Wear response Fig. 7 gives the friction coefcient () for the different loads of two irons (base and 5% Si). Friction coefcient increased from its initial value to a steady state value after 10 km sliding. Friction generally reduced with load, being 1 at 42 N and 0.6 at 238 N for the base iron. The addition of 5% Si increased friction slightly at all loads. All other additions had a minimal effect on friction. Figs. 8 and 9 give the Lancaster wear coefcient as a function of load and show a complex relationship. The Mis-

Fig. 7. Friction coefcient for the different loads of two irons: (a) base iron and (b) 5% silicon iron.

chmetal additions had no systematic effect on wear coefcient, irrespective of load or material condition. For the Si additions, very similar wear values were found in all the irons for loads of 42 and 91 N in both as-cast and heat treated conditions. However, as the load was increased to 140 N and above, systematic differences were observed for both as-cast and heat treated conditions, with the composition/wear resistance relationship being the same for both as-cast and heat treated conditions. The 2% Si iron exhibited the greatest wear resistance at these loads. In contrast, the 5% Si systematically exhibited the worst wear resistance, followed by the 3% alloy. The base iron exhibited the mid point behaviour. The wear mechanism was found to be predominantly oxidative at all loads for all materials, although, at 42 N there was a metallic component. No obvious differences in wear surface morphology were found as a function of composition. Fig. 10 shows the worn surface of the base iron at a load of 42 N. The surface was locally grooved, but in other regions was covered in a uniform, smooth, oxide layer. At 42 N, the oxide lm contained carbide fragments within it. The wear debris, Fig. 10c, was identied as principally Fe2 O3 , but

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Fig. 8. Variation of the Lancaster wear coefcient for the different applied loads during the wear test for the as-cast irons: (a) silicon-added irons and (b) Mischmetal-added irons.

Fig. 9. Variation of the Lancaster wear coefcient for the different applied loads during the wear test of the heat treated irons: (a) silicon-added irons and (b) Mischmetal-added irons.

also contained -Fe and carbide M7 C3 . Occasional abrasive grooves were present (Fig. 11). An increase in load to 91 N (which resulted in a decrease in wear coefcient) resulted in a smoother surface, Fig. 12a, with fewer abrasive grooves. Wear debris was predominantly Fe2 O3 with some traces of the carbide M7 C3 , but unlike at 42 N, no -Fe was present. The morphology of the debris was of delaminated oxide sheets and ne particulate oxide debris. At higher loads, the worn surface structure did not change dramatically, Fig. 13, although no abrasive grooving was found. However, evidence of roughening of the surface, indicative of local adhesion was observed (Fig. 14). Fe3 O4 was also detected in the debris along with the Fe2 O3 (Fig. 12c). In addition, the thickness of the oxide layer increased, as shown by thicker delaminated sheets observed in the wear debris (Fig. 13b). Cross-sections were taken of the worn surface to investigate fracture of the M7 C3 , subsurface deformation and the thickness of the oxide surface layer. Fig. 15 gives a longitudinal cross-section from the 0.1% Mischmetal at 42 N. An intermittent surface oxide layer was present, but difcult to

resolve in some areas. Below this, there was a layer of fractured oxide particles in a heavily deformed matrix. At 91 N (Fig. 16), the oxide surface layer was easily resolved, but otherwise the surface appeared similar to the tests at 42 N. At 189 N the oxide layer was again thicker (Fig. 17) and contained fragments of M7 C3 . The extent of carbide fragmentation was much greater at this load, and extended to a depth of 25 m in this case. This gure shows the initial stages of carbide fracture, followed by complete disruption of the carbide rods closer to the surface. The same features were present at the highest load, 238 N, but the interface between oxide and substrate became more diffuse, Fig. 18. The oxide contained numerous M7 C3 fragments, derived from a heavily deformed substrate layer. At this load, the effect of M7 C3 size and morphology, as a result of Si addition, could clearly be seen. The smallest carbide corresponded to 2% Si and this resulted in a thinner, more stable deformation zone, Fig. 19). Fig. 21. In contrast, the 3% Si sample, which contained larger carbide particles, exhibited greater extents of cracking within the surface deformed layer (Fig. 20 gives a detail of this crack formation.

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Fig. 10. (a) Worn surface of the base iron after the test at 42 N showing some exposed areas. The arrow indicates the sliding direction; (b) another area of the same sample where the oxide lm is continuous. Note the presence of small carbide particles embedded in the oxide lm; (c) debris produced during this test; and (d) XRD traces for the debris from (c).

Fig. 11. Groove on the surface of the 0.3% Mischmetal iron tested at 42 N, showing evidence of abrasive wear.

The material composition did not strongly affect the near-surface microstructural evolution, except the extent of cracking. In order to try to quantify the effect of composition on worn surface microstructure, the total depth of deformation and strain as a function of depth were measured. The maximum depth of the deformed layer below the worn surface was measured in each material by nding the maximum depth at which fracture of eutectic carbides was observed. While this choice was somewhat arbitrary, it was a reproducible measure. Moreover, there was evidence that even a small surface strain would result in fracture of the carbide. The equivalent tensile strain () was calculated by measuring the shear angle ( ) derived from a measurement of the displacement of eutectic carbides in regions where they were initially oriented perpendicularly to the worn surface. The shear strain was calculated, using the well known

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Fig. 12. (a) Worn surface of the as-cast 1% Si iron tested at 91 N load, showing the presence of carbide particles on the surface of the oxide lm, (b) debris produced during this test, and (c) XRD traces for the debris produced from (b), which are composed by Fe2 O3 and M7 C3 .

formula: =1 3 3 tan

(1)

highest load. The depth of deformation as a function of material composition showed the same trend as wear coefcient, with the 5% Si alloy exhibiting the greatest depth of deformation, while the 2% Si alloy exhibited the least.

gives the shear strain as a function of depth below the worn surface, while Fig. 23 Fig. 22 gives the depth of deformation as a function of load for all materials. The largest surface shear strains were observed for the 5% Si material, while the smallest were obtained for the 2% Si material. Interestingly, there was little difference in shear strain between heat treated and as-cast condition, with the strongest effect coming from the applied load. The depth of deformation followed an almost identical trend to the wear coefcient, with little difference being found at low load, but signicant differences found at the

4. Discussion A detailed discussion about the effect of the added elements on the microstructure will be published at a later date. However, it is clear that Mischmetal additions have a minimal effect on the microstructure. It has been widely reported [14] that the solubility of the rare earth elements in austenite or ferrite is very limited and during solidication these elements tend to segregate, even where cooling rates

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Fig. 13. (a) Worn surface of the as-cast base iron tested at 238 N, (b) debris produced during this test, and (c) XRD traces for the debris produced from (b), which are composed by the oxides Fe2 O3 and Fe2 O4 and the carbide M7 C3 .

are rapid, as in this study. This segregation contributes to the reduction of the secondary dendrite arm spacing, Fig. 3, but does not affect the volume fraction carbide or austenite. In contrast to the Mischmetal, Si additions up to 5% rened the size of the carbide, modied connectivity and increased volume fraction. The renement of the structure with Si addition is due to a change in the solidication range. The base Hi-Cr iron is hypoeutectic, but silicon moves the chemical composition of the alloy closer to the eutectic composition and eventually to the hypereutectic region for the iron with >4% silicon, Fig. 5. At the eutectic

composition the solidication range is shorter; the shorter the solidication range the ner the obtained structure of the alloy. In addition, to the effect on solidication range, Si also stabilises the ferrite phase, and this is shown by the reduction in austenite content with increase in Si content. This change was gradual up to 3% Si, but drastic for the 5% Si (where only 15% austenite was retained). The microstructure of the 5% addition was signicantly different to all other materials, and showed classical features of eutectoid transformation producing pearlitic-based products. An additional effect of the addition of Si was to change the proportion of

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Fig. 14. Localised zone of plastically deformed oxide on the worn surface of the 0.3% Mischmetal iron tested at the highest load, 238 N. This local roughening of the surface was detected in most of the irons tested at 238 N.

Fig. 17. Cross-section of the 1% silicon heat treated iron tested at 189 N, showing the deformation of matrix and fracture of carbides below the surface.

Fig. 15. Longitudinal cross-section of the 0.1% Mischmetal iron tested at 42 N showing a thin oxide layer and the deformed matrix below and surface. The arrow indicates the sliding direction.

Fig. 18. SEM image of cross-section of worn surface of the as-cast iron with 0.1% Mischmetal tested at 238 N. Note the thick oxide layer and the presence of carbides in it.

Fig. 16. 1% silicon heat treated iron tested at 91 N. Note the thin oxide lm and deformation below the worn surface is restricted to 6 m.

Fig. 19. Cross-section of the 2% silicon heat treated iron tested at 238 N showing carbide fragmentation.

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Fig. 20. SEM image of worn surface cross-section showing fracture of large carbides in the as-cast 3% silicon iron tested 238 N, the arrow indicates the sliding direction.

Fig. 21. Crack formation at the inferface between matrix and carbides. As-cast base iron tested at 189 N.

secondary carbides. The Si increased primary carbide fraction, thereby reducing the available carbon for subsequent precipitation on tempering. The wear mechanism was predominantly oxidational at all loads, although there was some evidence of abrasive grooving at the lower loads. The thickness of the oxide layer generally increased with load. The composition of the wear debris indicated some metallic wear at low loads, but only oxidational wear at 189 N and above. The composition of the oxide debris changed with load, being entirely Fe2 O3 at low load, but a combination of Fe2 O3 and Fe3 O4 at high load. As load increased, the oxide increasingly contained M7 C3 fragments. While the surface temperatures were not measured, previous work [27] indicates that if the only oxide is Fe2 O3 then the surface temperature is less than 140 C. The presence of Fe3 O4 indicates surface temperature in the range of 140280 C, while the absence of FeO suggests a maximum surface temperature of 280 C. The wear coefcient of all materials exhibited a significant fall between 42 and 91 N. This was associated with

Fig. 22. Equivalent tensile strain below the worn surface for three tested irons: (a) base iron; (b) 2% silicon iron; and (c) 5% silicon iron.

a reduction in the proportion of metallic wear, replaced by milder oxidative wear. The surface became smoother and the oxide coverage became more uniform, of a thickness 23 m that prevented metal/metal contact. This change in mechanism also gave a reduction in friction coefcient. The Mischmetal additions had no effect on wear resistance at any load. As discussed earlier, the only signicant microstructural inuence was the reduction in secondary dendrite arm spacing, but carbide volume fraction was largely unchanged.

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Fig. 24. Plot of wear rate against depth of deformation for the silicon-added irons.

Fig. 23. Variation of the depth of deformation below the worn surface as a function of the load test for the Hi-Cr irons with silicon additions: (a) as-cast and (b) heat treated.

This indicates that secondary arm spacing has little effect on wear behaviour. In contrast to the Mischmetal, Si had a signicant effect on wear behaviour, particularly, at loads of 140 N and above. The wear coefcient for 1 and 2% decreased slightly with load in the range 91238 N, while it increased substantially for 3 and 5%, with the base iron showing intermediate behaviour. Metallographic observations suggested that there was no fundamental change in wear mechanisms, i.e. a thick oxide lm dominated the contact in all cases. However, the change in microstructure did lead to a change in the depth of deformation. In this case, even very small surface strains led to fracture of the oxide. Thus, the depth of deformation axis in Fig. 23 could also be read as the total depth to which carbide fracture occurred. Fig. 24 gives a plot of depth of deformation against wear rate, which shows an approximate linear relationship. Therefore, this provides direct evidence that the wear rate correlates linearly with the extent of carbide fracture.

In agreement with the current ndings, Hanlon et al. [4] have shown that an order of magnitude reduction in carbide size results in a substantially reduced depth of deformation/carbide fracture, which resulted in a signicant improvement in wear resistance. The current work suggests that the carbide size, and the extent to which the carbide is connected, is therefore, the over-riding factor, with the effect of carbide volume fraction secondary. For example, the 3% Si alloy contained a higher carbide volume fraction, improved hardness in both as-cast and heat treated conditions, but exhibited poor wear resistance relative to the 2% alloy. The wear and friction data demonstrate that the microstructure and wear response are sensitive to small changes in Si content. The literature on the effect of Si on the microstructure is contradictory. For example, Laird and Powell reported [2] that silicon inhibits the nucleation of the M7 C3 carbides in a 18% Cr iron, while in contrast Shen and Zhou [16] report an increase in the number of carbide phase nuclei due to silicon additions. The current work suggests that these differences almost certainly arise from differences in exact Si content, and differences in casting procedure, in particular cooling rate, that will inuence segregation effects. Thus, while Si has been shown to have a benecial effect on wear behaviour, it is clear that close control on the composition will be required. It is interesting that there was minimal difference in wear response between as-cast and heat treated conditions. This suggests that the austenite phase is destabilised during the wear process close to the surface. The combination of high surface strain and temperature rise can promote transformation of austenite to martensite (e.g. this effect is well known for Hadelds manganese steels). However, no evidence of this was shown by either X-ray diffraction or by the hardness of matrix in the deformed layer. Further work is underway to identify the detailed surface microstructural changes. However, the current results suggest that it is the fragmentation of the carbide that is rate controlling over and above the properties of the matrix.

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5. Conclusions 1. At 42 N load, all materials exhibited similar wear behaviour, with a mixture of metallic wear, as shown by metallic wear debris and the presence of abrasive grooves, and oxidative wear, through the formation of a thin layer of Fe2 O3 . 2. The wear coefcient decreased for all alloys at a load of 91 N. This was associated with a reduction in metallic wear and a thicker surface oxide lm of Fe2 O3 . 3. In the base-iron, the 2 and 3% Si alloys and the Mischmetal alloyed irons, the wear resistance remained more or less constant for loads of 140238 N. This was associated with the formation of a thick (up to 10 m) oxide layer, comprising a mixture of Fe2 O3 and Fe3 O4 and fragments of M7 C3 . 4. For the irons with high silicon contents (3 and 5%), an increase in load in the range 140238 N resulted in increased wear coefcient. However, the surface microstructural features were similar to those observed in the other materials. 5. The wear resistance correlated directly with the depth of deformation and the depth to which carbide fracture occurred. This depth was minimised by a reduction in carbide size and connectivity, found in the 1 and 2% Si alloys. 6. There was no appreciable difference in wear resistance between as-cast (with a predominantly austenitic matrix) and heat treated (with a predominantly martensitic matrix) conditions. This indicates that the dominant effect on wear resistance is the morphology and size of the carbide.

(CONACyT) for the sponsorship during the carrying out of this project. References
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Acknowledgements One of the authors, A. Bedolla, would like to thank the National Council of Science and Technology of Mexico