AU2004240953B2 - Wear resistant cast iron - Google Patents

Description

WO 2004/104253 PCT/AU2004/000678 WEAR RESISTANT CAST IRON The present invention relates to white cast iron alloys for high erosion and high abrasion applications and 5 to a method of producing castings of white cast iron alloys. The components of most mining and processing equipment that are subject to wear (eg slurry pumps, 10 cyclones and crushers) are produced from wear resistant white cast iron alloys. Castings of these white cast iron alloys have high wear resistance and provide good service life for 15 process equipment that is subject to erosion and abrasion wear. Australian Standard 2027 describes inter alia the following two families of wear resistant white cast iron 20 alloys: (a) high chromium white cast iron alloy, eg 27%Cr; and 25 (b) chromium - molybdenum white cast iron alloy, eg 20Cr-2Mo and 15Cr-3Mo. The microstructures of all these white cast iron alloys consist of two phases, namely: 30 (a) M 7

C

3 carbides (where M = Fe, Cr, Mn, Mo), which have a hardness of 1200 - 1500 HV; and 35 (b) ferrous matrix that consists of one or more of the following structures(i) a saturated solution of austenite which is metastable WO 2004/104253 PCT/AU2004/000678 -2 at room temperature, (ii) solute-depleted austenite containing secondary carbide precipitates and is destabilised at room temperature (iii) destabilised, retained 5 austenite partially transformed to martensite and (iv) destabilised, retained austenite wholly transformed to martensite. The wear resistance of these white cast iron 10 alloys is due to (a) the presence of the extremely hard

M

7

C

3 carbides and (b) the presence of a hard martensitic structure in the ferrous matrix. It is essential to avoid the formation of 15 pearlite in the ferrous matrix in these alloys during cooling after heat treatment in order to ensure adequate wear resistance in service. It is a common practice to subject white cast 20 iron alloys to an intermediate annealing process to deliberately form pearlite in order to soften the alloy for machining purposes. However, the machined white cast iron alloys are then subjected to a final heat treatment process to harden the alloys prior to service. 25 The ferrous matrix of AS2027, Grade 27%Cr (high chromium) white cast iron alloys can be readily hardened by forming martensite in the ferrous matrix during air cooling after heat treatment. One of the functions of the 30 chromium in the alloys is to suppress the formation of pearlite during cooling from elevated temperatures. However, white cast iron alloys containing lower chromium contents, eg 20Cr-2Mo and 15Cr-3Mo, require the 35 addition of molybdenum and/or nickel to suppress the formation of pearlite on cooling after heat treatment, particularly in heavy section castings, ie castings - 3 greater than 10cm thick. However, molybdenum and nickel are each expensive alloying elements and add substantially to the material cost of white cast iron alloys. 5 An object of the present invention is to provide a white cast iron alloy that is a lower cost alternative to the currently available white cast iron alloys described above. 10 The present invention is based on the realisation that it is possible to produce a white cast iron alloy that can produce castings that have at least comparable wear resistance to castings of currently available white cast iron alloys at considerably lower cost by 15 substituting manganese for at least some of the molybdenum, nickel, and chromium in the currently available white cast iron alloys. According to the present invention there is 20 provided a casting of a white cast iron alloy that comprises: (a) the following alloy composition, in wt%: 25 chromium: 20 - 25%; carbon: 1.5 - 6%; manganese: >4 and up to 7%; silicon: up to 1.5%; molybdenum: up to 2%; 30 nickel: up to 4%; microalloying elements selected from the group consisting of titanium, zirconium, niobium, boron, vanadium, and tungsten: up to 2% of each of one or more of the elements; and 35 iron: balance; and (b) a microstucture that comprises 15 - 60 17628551 (GHMatters) 16/09/09 volume% eutectic carbides and primary carbides dispersed in a ferrous matrix that comprises martensite and is at least substantially free of pearlite. 5 The term "at least substantially free of pearlite" indicates that the objective of the present invention is that there be no pearlite in the matrix but at the same time recognises that in any given situation in practice there may be a small amount of pearlite. 10 With the above in mind, the term "substantially free of pearlite" is understood herein to mean that the casting contains no more than 2 volume% pearlite. 15 The casting may comprise a microstructure that comprises 25-60vol% eutectic carbides and primary carbides dispersed in a ferrous matrix that comprises martensite and is at least substantially free of pearlite. 20 The casting may comprise 3.3-6wt% carbon. Preferably the white cast iron alloy comprises 20 - 23 weight% chromium. 25 As indicated above, chromium suppresses pearlite formation and, therefore, as the chromium concentration within the stated range of 20 - 25 weight% in the white cast iron decreases it is necessary to increase the concentrations of manganese (or other additives) to 30 counteract the higher susceptibility to pearlite formation at lower concentrations of chromium. One advantage of using lower concentrations of chromium is that lower chromium concentrations increase the instability of austenite. This results in an increase in the amount of 35 the desirable hard martensite phase in the white cast iron. 17628551 (GHMatters) 16/09/09 - 5 Preferably the white cast iron alloy comprises >4 and up to 6 weight% manganese. The applicant has found that as the concentration 5 of manganese increases, the temperature at which the retained austenite starts to transform to martensite (Ms temperature) on cooling from the precipitation hardening temperature decreases. At manganese concentrations above 6 weight% manganese, the martensite start temperature may 10 be below room temperature and thus the matrix may be predominantly retained austenite. Accordingly, for applications requiring high hardness, it is preferred that the manganese concentration be no more than 6 weight%. i5 More preferably the white cast iron alloy comprises >4 and up to 5.5 weight% manganese. Preferably the white cast iron comprises up to 1.5 weight% silicon. 20 Preferably the white cast iron comprises no nickel and molybdenum. However, it is within the scope of the present 25 invention for the white cast iron to include molybdenum and nickel up to the stated maximums of 2 and 4 weight%, respectively. Preferably the ferrous matrix comprises 30 martensite and retained austenite. Preferably the eutectic carbides, and primary carbides comprise M 7

C

3 carbides, where "M" is a metal and "C" is carbon. 35 According to the present invention there is also provided a method of producing the above-described casting 17628551 (GHMatters) 16/09/09 - 6 of the white cast iron alloy which comprises the steps of: (a) forming a molten melt of the above described white cast iron alloy; 5 (b) pouring the molten melt into a mould to form the casting; (c) allowing the casting to air cool to room 10 temperature. The method produces a casting having a microstucture that comprises 15 - 60 volume% eutectic carbides and primary carbides dispersed in a ferrous 15 matrix that comprises martensite and retained austenite and is at least substantially free of pearlite. The method may produce a casting having a microstructure that comprises 25-60vol% eutectic carbides 20 and primary carbides dispersed in a ferrous matrix that comprises martensite and retained austenite and is at least substantially free of pearlite. Preferably the method further comprises heat 25 treating the room temperature casting by: (a) heating the casting to an elevated temperature where austenite decomposes to form secondary carbide precipitates in a 30 solute-depleted austenite; and thereafter 17628551 (GHMatters) 16/09/09 WO 2004/104253 PCT/AU2004/000678 -7 (b) air cooling the casting to room temperature and transforming the solute-depleted austenite to martensite. 5 Preferably the austenite-destabilising temperature is in the range of 950 - 1000*C. Preferably step (a) includes holding the casting at the austenite-destabilising temperature for at least 4 10 hours to ensure substantial secondary carbide precipitation has occurred. The present invention is described further by reference to the following experimental work which was 15 carried out for the purpose of comparing the performance of castings of white cast iron alloys in accordance with the present invention against the performance of castings of currently available white cast iron alloys. 20 EXPERIMENTAL PROGRAM A number of white cast iron alloys containing systematic variations in chromium, molybdenum and manganese levels from a base alloy composition (Fe-20Cr 25 3.3C - 0.6Si (weight%)) were manufactured in an electric arc melting furnace under an inert atmosphere. The alloys were then processed as described below and the resultant samples were evaluated using the following test procedures: 30 Test Procedure Purpose Dilatometry Phase changes that occur during cooling of white cast iron alloys are often accompanied by changes in the contraction of the alloys as a function of temperature.

WO 2004/104253 PCT/AU2004/000678 -8 Metallography The presence of pearlite and other phases are readily detected by microstructural examination. Hardness testing Different phases in white cast iron alloys exhibit a range of hardness values. Ferrite content The magnetic response of white cast iron alloys is an indication of the presence of various phases. SUMMARY OF TEST RESULTS A first series of pin samples of the base alloy 5 (Fe-20Cr-3.3C - 0.6Si (weight%)) and the variations of the base alloy were heated in a dilatometer to 1150 0 C, held for one hour to ensure equilibrium, and furnace cooled to obtain contraction cooling curves. 10 The above test procedure closely simulates the cooling rate of castings in a sand mould after solidification. Accordingly, the samples have properties and microstructures that are representative of properties and microstructures of as-cast castings. 15 The pin samples were subjected to hardness testing, ferrite content and metallographic examination. A summary of the metallographic, hardness, and 20 ferrite test results for each alloy is set out in Table 1 below. Table 1.- Summary of Test Results 25 Alloy (Wt%) Test No Hardness Ferrite Microstructure (HV 50) (%) WO 2004/104253 PCT/AU2004/000678 -9 Base alloy + 2Mn +2Mo OD674 766 32 No Pearlite Base alloy (no Mn/Mo) OD676 380 49 Pearlite Base alloy + iMn OD677 420 47 Pearlite Base alloy + 2Mn OD673 533 40 Pearlite Base alloy + 3Mn OD681 719 33 Trace of pearlite Base alloy + 4Mn OD675 700 24 No Pearlite The test results for four of the above alloys (OD676, OD674, OD675, and OD681) are discussed further below, particularly in the context of the dilatometry 5 results. Base alloy (OD676) - no Mo/Mn The contraction characteristics of the base alloy 10 (ie alloy with no molybdenum and no manganese) during furnace cooling from 1150 0 C is illustrated in the dilatometer curve of Figure 1. The total percent linear contraction (PLC) is 15 about 2.1% on cooling through the temperature range. There is a sharp discontinuity in the cooling curve at a temperature of about 700 0 C indicating the formation of undesirable pearlite at that temperature. 20 Final Hardness = 380 HV50 due to the presence of the soft ferrite phase in the pearlite. Ferrite Content = 49% due to complete transformation of the high temperature austenite phase to 25 body-centred-cubic ferrite which is ferromagnetic and absence of any retained face-centred-cubic austenite which is paramagnetic. Metallographic examination demonstrated the 30 presence of pearlite throughout the microstructure.

WO 2004/104253 PCT/AU2004/000678 - 10 Base alloy + 2Mn + 2Mo (OD674) The contraction characteristics of the conventional white cast iron 20Cr-2Mo-2Mn alloy during 5 furnace cooling from 1150*C is illustrated in the dilatometer curve of Figure 2. The percent linear contraction (PLC) is about 2.1% on cooling through the temperature range. The 10 observed contraction is continuous down to a temperature of about 300 0 C where the discontinuity in the linear contraction curve indicates the onset of martensite formation (Ms temperature). 15 Final Hardness = 766 HV50 due to the presence of martensite. Ferrite Content = 32% due to the presence of martensite and some retained austenite. 20 Metallographic examination demonstrated the presence of martensite and the absence of undesirable pearlite in the microstructure. 25 Base alloy + 4Mn (OD675) The contraction characteristics of the base alloy containing no molybdenum and 4% manganese in accordance with the present invention during furnace cooling from 30 1150 0 C is illustrated in the dilatometer curve of Figure 3. The total percent linear contraction (PLC) is about 2.3% on cooling through the temperature range. There is a discontinuity in the linear cooling curve at a 35 temperature of about 200*C indicating the onset of formation of martensite (Ms temperature) at that temperature.

WO 2004/104253 PCT/AU2004/000678 - 11 Final Hardness = 700 HV50 due to the presence of partial transformation of the austenite phase to secondary carbides and partial decomposition of the solute-depleted 5 austenite to martensite on cooling to room temperature. Ferrite Content = 24% due to the presence of martensite and some retained austenite in the microstructure. 10 Metallographic examination demonstrated the absence of pearlite in the microstructure. Base alloy + 3Mn (OD681) 15 The contraction characteristics of the base alloy containing no molybdenum and 3% manganese in accordance with the present invention during furnace cooling from 1150 0 C is illustrated in the dilatometer curve of Figure 4. 20 The total percent linear contraction (PLC) is about 2.0% on cooling through the temperature range. There is a discontinuity in the linear cooling curve at a temperature of about 230 0 C indicating the onset of 25 decomposition of the retained austenite to martensite (Ms temperature) as that temperature. Final Hardness = 719 HV5O due to the presence of martensite. 30 Ferrite Content = 33% due to the presence of martensite and some retained austenite in the microstructure. 35 Metallographic examination demonstrated the presence of a trace amount of undesirable pearlite in a ferrous matrix that is otherwise solute-depleted austenite WO 2004/104253 PCT/AU2004/000678 - 12 that is partially transformed to martensite. In summary, the above results for simulated as cast samples indicate that the Base alloy + 4Mn (OD675) 5 and the Base alloy + 4Mn (OD681) in accordance with the present invention had comparable performance to the conventional white cast iron 20Cr-2Mo-2Mn alloy (OD674) and considerably better performance than the Base alloy (OD676), ie with no Mn and no Mo. 10 As indicated above, the above-described experimental program involving the formation of rapidly chilled pin samples and heating the samples to 1150 0 C and thereafter cooling the samples in the dilatometer 15 simulates the cooling of white cast iron alloys in a sand mould after solidification. In practice, such castings are finally hardened by heat treatment, typically by holding at 950-970*C for a 20 period of time and air cooling to room temperature. In order to investigate the impact of heat treatment on the above-tested range of white cast iron alloys, pin samples of each alloy prepared as described 25 above were heat treated at 960 0 C for 4 hours and thereafter allowed to cool to room temperature. A summary of the metallographic, hardness, and ferrite test results for four of the alloys (OD674, OD676, 30 OD681, and OD675) is set out in Table 2 below. Table 2 - Summary of Test Results Alloy (Wt%) Test No Hardness Ferrite Microstructure (HV 50) (%) Base alloy + 2Mn + 2Mo OD674 857 32 No Pearlite WO 2004/104253 PCT/AU2004/000678 - 13 Base alloy OD676 371 52 Pearlite Base alloy + 3Mn OD681 779 35 Trace amount of _______pearlite Base alloy + 4Mn OD675 807 33 No Pearlite It is evident from Table 2 that the heat treated Base alloy + 4Mn (OD675) and Base alloy + 4Mn (OD681) in accordance with the present invention had comparable 5 performance to the conventional heat treated white cast iron 20Cr-2Mo alloy (OD674) and considerably better performance than the Base alloy (OD676), ie with no Mn and no Mo. 10 In a further series of test work a number of white cast iron alloys containing systematic variations in chromium, molybdenum and manganese levels from a base alloy composition (Fe-20Cr-3.3C - 0.6Si (wt%)) were manufactured in an electric arc melting furnace under an 15 inert atmosphere. The alloys were then processed as described below and the resultant samples were evaluated by hardness testing, ferrite content testing, dilatometry testing, and metallographic examination 20 The samples were processed as follows. (a) simulated casting in sand mould - heating to 11500C in a dilatometer furnace under an inert atmosphere at a rate of 3 0 C per 25 minute, holding at temperature for 2 hours to achieve equilibrium, and furnace cooling to ambient temperature; and (b) heat treatment of the simulated castings 30 heating to 960 0 C in a dilatometer furnace under an inert atmosphere at a rate of 30C per minute, holding at temperature for 4 hours, and air cooling to ambient WO 2004/104253 PCT/AU2004/000678 - 14 temperature to simulate the microstructure after heat treatment. A summary of the metallographic, hardness, and ferrite 5 test results for each alloy is set out in Tables 3 and 4 below. Table 3 - Summary of Test Results Simulated Castings Alloy (Wt%) Test No Hardness Ferrite Microstructure (HV 50) (%) Base alloy + 5Mn OD744 666 17 No Pearlite Base alloy + 6Mn OD745 574 8.4 No Pearlite Base alloy + 7Mn OD759 645 9.6 No Pearlite Base alloy + 8Mn OD749 536 2.5 No Pearlite 10 Table 4 - Summary of Test Results -Heat Treated Samples Alloy (Wt%) Test No Hardness Ferrite Microstructure (HV 50) (%) Base alloy + SMn OD744 727 27 No Pearlite Base alloy + 6Mn OD745 629 10 No Pearlite Base alloy + 7Mn OD759 622 13.6 No Pearlite Base alloy + 8Mn OD749 557 3.8 No Pearlite 15 The microstructural and dilatometry evaluations of the above samples indicated that the amount of martensite in the matrix of each sample decreased with increasing manganese concentration to the point that at high manganese concentrations (13%) there was no 20 martensite and the matrix comprised retained austenite. The test data in Table 4 demonstrates that manganese levels above 7 weight% stabilises the softer austenite phase and suppresses the transformation to the 25 harder martensite phase. Consequently, manganese contents WO 2004/104253 PCT/AU2004/000678 - 15 greater than 7 weight% adversely affect the final hardness of these wear resistant alloys. Many modifications may be made to the present 5 invention as described above without departing from the spirit and scope of the present invention.

Claims (14)

1. A casting of a white cast iron alloy that comprises: 5 (a) the following alloy composition, in wt%: chromium: 20 - 25%; carbon: 1.5 - 6%; 10 manganese: >4 and up to 7%; silicon: up to 1.5%; molybdenum: up to 2%; nickel: up to 4%; microalloying elements selected from the group 15 consisting of titanium, zirconium, niobium, boron, vanadium, and tungsten: up to 2% of each of one or more of the elements; and iron: balance; and 20 (b) a microstucture that comprises 15 - 60 vol% eutectic carbides and primary carbides dispersed in a ferrous matrix that comprises martensite and is at least substantially free of pearlite. 25

2. The casting defined in claim 1 wherein the alloy comprises a microstructure that comprises 25-60vol% eutectic carbides and primary carbides dispersed in a ferrous matrix that comprises martensite and is at least substantially free of pearlite. 30

3. The casting defined in claim 1 or claim 2 wherein the alloy composition comprises 20 - 23 wt % chromium.

4. The casting defined in any one of claims 1 to 3 35 wherein the alloy composition comprises 20 - 23 wt% chromium. 17628551 (GHMatters) 16/09109 - 17 5. The casting defined in any one of the preceding claims wherein the alloy composition comprises 4.0 - 5.5 wt% manganese.

5

6. The casting defined in any one of the preceding claims wherein the alloy composition comprises up to 1.5 wt% silicon.

7. The casting defined in any one of the preceding 10 claims wherein the alloy composition comprises no nickel and molybdenum.

8. The casting defined in any one of claims 1 to 6 wherein the alloy composition include molybdenum and is nickel up to the stated maximums of 2 and 4 wt%, respectively.

9. The casting defined in any one of the preceding claims wherein the ferrous matrix comprises martensite and 20 retained austenite.

10. The casting defined in any one of the preceding claims wherein the eutectic carbides comprise M 7 C 3 carbides, where "M" is a metal and "C" is carbon. 25

11. A method of producing the casting of the white cast iron alloy defined in any one of the preceding claims which comprises the steps of: 30 (a) forming a molten melt of the white cast iron alloy; (b) pouring the molten melt into a mould to form the casting; 35 (c) allowing the casting to air cool to room temperature. 17628551 (GHMatters) 16/09/09 - 18

12. The method defined in claim 11 further comprises heat treating the room temperature casting by: 5 (a) heating the casting to an austenising temperature and precipitating secondary carbides from the ferrous matrix; and thereafter 10 (b) air cooling the casting to room temperature and transforming the solute-depleted austenite to martensite.

13. The method defined in claim 12 wherein the heat 15 temperature is in the range of 950 - 1000 0 C.

14. The method defined in claim 12 or claim 13 wherein step (a) includes holding the casting at the heat temperature for at least 4 hours. 20 17628551 (GHMatters) 16/09109