WO2016164360A1 - Fine-grained high carbide cast iron alloys - Google Patents

Fine-grained high carbide cast iron alloys Download PDF

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Publication number
WO2016164360A1
WO2016164360A1 PCT/US2016/026043 US2016026043W WO2016164360A1 WO 2016164360 A1 WO2016164360 A1 WO 2016164360A1 US 2016026043 W US2016026043 W US 2016026043W WO 2016164360 A1 WO2016164360 A1 WO 2016164360A1
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Prior art keywords
alloy
carbide
chromium white
carbides
white iron
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PCT/US2016/026043
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French (fr)
Inventor
Justin Lee Cheney
Cameron EIBL
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Scoperta, Inc.
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Publication of WO2016164360A1 publication Critical patent/WO2016164360A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C37/00Cast-iron alloys
    • C22C37/06Cast-iron alloys containing chromium
    • C22C37/08Cast-iron alloys containing chromium with nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C37/00Cast-iron alloys
    • C22C37/06Cast-iron alloys containing chromium

Definitions

  • ALLOYS the entirety of which is incorporated herein by reference.
  • the disclosure relates generally to cast iron alloys used in wear-prone environments and which are resistant to wear.
  • the alloy family known as chromium white irons or chromium white cast irons can refer to alloys containing Fe, C, and Cr which can form eutectic chromium carbides.
  • alloys having chromium levels in the range from 15-30 wt. % (or about 15 to about 30 wt. %) and having carbon levels in the range of 1-3 wt. % (or about 1 to about 3 wt. %) can form such chromium white irons.
  • formation of primary chromium carbides is typically avoided which can occur as either Cr or C content is increased.
  • the alloy system can be in the hypoeutectic region of the Fe-C phase field (i.e., the C level is below the eutectic point in the alloy system).
  • Exceeding the C eutectic level in these systems can create Cr C 3 carbide precipitates which are long, rod-like, and can be very embrittling to the material.
  • the addition of chromium can shift the eutectic point to more iron-rich compositions. Therefore, as Cr is added for various benefits (such as corrosion resistance), the amount of carbon which can be added before the alloy enters the hypereutectic regime drops. For example, an Fe-5Cr type alloy has a eutectic point over -4% C while an Fe-25Cr alloy has a eutectic point at around 3.3% C.
  • Chromium white irons are generally very useful for applications where resistance to abrasion is advantageous.
  • the relatively high content of chromium carbides in the microstructure are very hard and thus contribute to the abrasion resistance of the material.
  • the volume fraction of carbides in the alloy can dictate the wear resistance of the material, e.g., increased carbide contents can create increased wear resistance.
  • the carbon beyond the eutectic point can be increased to increase the total carbide fraction. However, this is done at the expense of toughness.
  • computational metallurgy can be used to explore alloy compositional ranges where the total carbide content can be increased without introducing coarse carbide structures known to embrittle the material.
  • the thermodynamic limit for hypoeutectic carbide volume fraction can be 35-40% (or about 35 - about 40%).
  • This disclosure describes embodiments of alloys which can meet a set of thermodynamic criteria which can exceed the 40% (or about 40%) carbide content limit, but may not introduce the formation of hypereutectic M-7C3, M23C6 or generally any Fe,Cr-rich type carbides.
  • microstructure which can have a very high level, >40% mole fraction (or > about 40% mole fraction) as defined by thermodynamic models, of fine-grained carbides.
  • this new class of materials can be defined as fine-grained high carbide content cast irons.
  • the utility of such a material can be an increased wear resistance, while maintaining similar levels of toughness to hypoeutectic cast irons.
  • an alloy, or an article of manufacture which can contain in at least a portion of its structure a component comprising Fe, Cr, and C in which the total carbide and/or boride content in the microstructure exceeds 40 volume %, and the grain size of all carbides and borides does not exceed 50 micrometers in their longest dimension.
  • the alloy further can further comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, W: 0-9 wt%.
  • the alloy can further comprise Mn: 0-1 wt %, Mo: 0-1 wt%, Si: 0-1%, Ti: 0-0.5%, V: 0-3 wt.%.
  • the alloy further can further comprise C: 2.2-4.02 wt.%, Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, W: 4.37-9 wt%.
  • the total carbide and/or boride content can exceed 45 volume %. In some embodiments, the total carbide and/or boride content can exceed 50 volume %.
  • the grain size of all carbides and borides does not exceed 25 micrometers in their longest dimension. In some embodiments, the grain size of all carbides and borides does not exceed 5 micrometers in their longest dimension.
  • the article can be produced via the casting process. In some embodiments, the article can be utilized as a wear resistant component. In some embodiments, the article can be used as a sleeve or layer in pipelines designed to carry abrasive slurries.
  • a maximum carbide fraction can be 50% mole fraction or higher. In some embodiments, a maximum carbide fraction can be 60% mole fraction or higher.
  • the composition can comprise, in weight %: Fe, C: 3.2 - 4% (or about 3.2 - about 4), Cr: 6-20% (or about 6 - about 20), and W: 4-10% (or about 4 - about 10).
  • the composition can comprise, in weight %: Fe, C: 2.5 - 3.8% (or about 2.5 - about 3.8), Cr: 10-28% (or about 10 - about 28), Mn: 0-1% (or about 0 to about 1), Mo: 0-1% (or about 0 to about 1), Nb: 0-5% (or about 0 to about 5), Si: 0-1% (or about 0 to about 1), Ti:0-0.5% (or about 0 to about 5), V: 0-3% (or about 0 to about 3) and W: 0-9% (or about 0 to about 9).
  • an article of manufacture which can comprise Fe, Cr, and C in which the total carbide and/or boride content in the microstructure exceeds 40 volume %, and the grain size of all carbides and borides does not exceed 50 micrometers in their longest dimension.
  • an article of manufacture which can contain at least a portion of a component comprising Fe, Cr, and C in which the total carbide and/or boride content in the microstructure exceeds 0.4 mole fraction, and the total volume of segregated carbides is less than 0.05 mole fraction, whereas a segregated carbide is defined as Fe or Cr - rich boride or carbide, Fe+Cr >50 wt.%, which is thermodynamically stable at a temperature above the temperature at which austenite is thermodynamically stable.
  • the alloy can further comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, W: 0-9 wt%.
  • the alloy can further comprise Mn: 0-1 wt %, Mo: 0-1 wt%, Si: 0-1%, Ti: 0-0.5%, V: 0-3 wt.%.
  • the alloy can further comprise C: 2.2-4.02 wt.%, Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, W: 4.37-9 wt%.
  • the total carbide and/or boride content can exceed 0.45 mole fraction. In some embodiments, the total carbide and/or boride content can exceed 0.50 mole fraction.
  • the article can be produced via the casting process. In some embodiments, the article can be utilized as a wear resistant component. In some embodiments, the article can be used as a sleeve or layer in pipelines designed to carry abrasive slurries
  • Also disclosed herein is a method of forming a component which can contain in at least a portion of its structure a component comprising Fe, Cr, and C in which the total carbide and/or boride content in the microstructure exceeds 40 volume %, and the grain size of all carbides and borides does not exceed 50 micrometers in their longest dimension.
  • the alloy can further comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, W: 0-9 wt%.
  • the alloy can further comprise Mn: 0-1 wt %, Mo: 0-1 wt%, Si: 0-1 %, Ti: 0-0.5%, V: 0-3 wt.%.
  • the alloy can further comprise C: 2.2-4.02 wt.%, Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, W: 4.37-9 wt%.
  • the total carbide and/or boride content can exceed 0.45 mole fraction. In some embodiments, the total carbide and/or boride content can exceed 0.50 mole fraction.
  • the article can be produced via the casting process. In some embodiments, the article can be utilized as a wear resistant component. In some embodiments, the article can be used as a sleeve or layer in pipelines designed to carry abrasive slurries.
  • an article of manufacture comprising an alloy comprising Fe, Cr, and C, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %, and wherein a grain size of all carbides and borides is less than or equal to 50 micrometers in their longest dimension.
  • the alloy can be an iron based alloy and can comprise C: 2.2-4.02 wt. % and Cr: 10-34 wt. %.
  • the alloy can comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, and W: 0-9 wt. %.
  • the alloy can further comprise Mn: 0-1 wt. %, Mo: 0-1 wt. %, Si: 0-1 wt. %, Ti: 0-0.5 wt. %, and V: 0-3 wt.%.
  • the alloy can comprise C: 2.2-4.02 wt.%. Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, and W: 4.37-9 wt. %.
  • the total carbide and boride content can exceed 45 volume %. In some embodiments, the total carbide and boride content can exceed 50 volume %.
  • the grain size of all carbides and borides may not exceed 25 micrometers in their longest dimension. In some embodiments, the grain size of all carbides and borides may not exceed 5 micrometers in their longest dimension.
  • the article of manufacture can comprise a sleeve or layer for use in pipelines designed to carry abrasive slurries. Also disclosed herein are embodiments of a wear resistant component comprising embodiments of the disclosed article of manufacture.
  • an article of manufacture comprising an alloy comprising Fe, Cr, and C, wherein a total carbide and boride content in a microstructure of the alloy exceeds 0.4 mole fraction, and wherein a total volume of segregated carbides is less than 0.05 mole fraction, segregated carbides being defined as Fe or Cr - rich boride or carbide meeting the equation: Fe+Cr >50 wt.%, wherein the segregated carbides are thermodynamically stable at a temperature above a temperature at which austenite of the alloy is thermodynamically stable.
  • the alloy can be an iron based alloy and can comprise C: 2.2-4.02 wt. %, and Cr: 10-34 wt. %. In some embodiments, the alloy can comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, and W: 0-9 wt. %. In some embodiments, the alloy can comprise Mn: 0-1 wt. %, Mo: 0-1 wt. %, Si: 0-1 wt. %, Ti: 0-0.5 wt. %, and V: 0-3 wt.%.
  • the alloy can comprise C: 2.2-4.02 wt.%, Cr: 12.7- 34 wt.%, Nb: 3.8-5 wt. %, and W: 4.37-9 wt. %.
  • the total carbide and/or boride content can exceed 0.45 mole fraction. In some embodiments, the total carbide and/or boride content can exceed 0.50 mole fraction.
  • the article of manufacture can comprise a sleeve or layer used in pipelines designed to carry abrasive slurries. Also disclosed herein are embodiments of a wear resistant component which can comprise embodiments of the disclosed article of manufacture.
  • a method of forming a component comprising providing an alloy comprising Fe, Cr, and C, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %. and wherein a grain size of all carbides and borides is less than or equal to 50 micrometers in their longest dimension, and forming a component from the alloy.
  • the alloy can be an iron-based alloy and can comprise C: 2.2-4.02 wt. %, and Cr: 10-34 wt. %.
  • the alloy can comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt.
  • the alloy can comprise C: 2.2-4.02 wt.%, Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, and W: 4.37-9 wt. %.
  • the total carbide and/or boride content can exceed 0.45 mole fraction. In some embodiments, the total carbide and/or boride content can exceed 0.50 mole fraction.
  • the method can comprise forming the component via a casting process. In some embodiments, the method can comprise forming the component into a sleeve or layer.
  • a chromium white iron alloy comprising a composition comprising Fe, Cr, and C, the composition being predominantly Fe, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %, and wherein a melt temperature range of the alloy is below about 300 °C.
  • the melt temperature range can be below about 200 °C. In some embodiments, the melt temperature range can be below about 100 °C.
  • the alloy can be formed into a sleeve or layer for use in pipelines designed to carry abrasive slurries. Also disclosed herein are embodiments of a wear resistant component comprising the chromium white iron alloy disclosed herein.
  • an article of manufacture comprising an alloy having a composition comprising Fe, Cr, and C, the composition being predominantly Fe, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %, and wherein a melt temperature range of the alloy is below about 300 °C.
  • the melt temperature range can be below about 200 °C. In some embodiments, the melt temperature range can be below about 100 °C.
  • the article of manufacture can comprise a sleeve or layer for use in pipelines designed to carry abrasive slurries. Also disclosed herein are embodiments of a wear resistant component comprising the article of manufacture disclosed herein.
  • a method of manufacturing a chromium white iron alloy comprising providing an alloy comprising Fe, Cr, and C, the alloy being predominantly Fe, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %, and wherein a melt temperature range of the alloy is below about 300 °C, and forming a component from the alloy.
  • the melt temperature range can be below about 200 °C. In some embodiments, the melt temperature range can be below about 100 °C. In some embodiments, a grain size of substantially all of the carbides does not exceed 50 micrometers in their longest dimensions. In some embodiments, the total carbide content in the microstructure of the alloy may exceed 60 volume %.
  • the composition can comprise, in weight %: Fe, C: 3.2 - 4% (or about 3.2 - about 4), Cr: 6-20% (or about 6 - about 20), and W: 4-10% (or about 4 - about 10).
  • the composition can comprise, in weight %: Fe, C: 2.5 - 3.8% (or about 2.5 - about 3.8), Cr: 10-28% (or about 10 - about 28), Mn: 0- 1% (or about 0 to about 1), Mo: 0-1% (or about 0 to about 1), Nb: 0-5% (or about 0 to about 5), Si: 0-1 % (or about 0 to about 1), Ti:0-0.5% (or about 0 to about 5), V: 0-3% (or about 0 to about 3) and W: 0-9% (or about 0 to about 9).
  • forming the component can comprise forming the component via a casting process. In some embodiments, forming the component can comprise forming the component into a sleeve or layer.
  • a chromium white iron alloy comprising a composition comprising Fe, Cr, and C, the composition being predominantly Fe, a maximum carbide fraction in the alloy which is thermodynamically stable at temperatures ranging from the room temperature to a temperature where the alloy is 100% liquid of 40% mole fraction, and a segregated carbide fraction, defined as Fe,Cr - rich carbides existing at a temperature above the highest temperature at which an austenite or ferrite iron based matrix phase is thermodynamically stable, of 5% mole fraction or lower.
  • Figure 1 illustrates a solidification diagram of an embodiment of, in wt. %, Fe: bal, Cr: 25%, C:3.6%.
  • Figure 2 illustrates a solidification diagram of an embodiment of, in weight %, Fe: 17%, C:3.6%, Nb 5%, W 5%.
  • Figures 3A-B illustrate an SEM micrograph of embodiments of alloy X22 at 1,000X magnification ( Figure 3A) and 5,000X magnification ( Figure 3B).
  • Figure 4 illustrates an SEM micrograph of embodiments of alloy X24 at 1 ,000X magnification.
  • Figure 5 illustrates a solidification diagram of an embodiment of an alloy having a composition of, in wt.%, Fe: bal, Cr: 8 %, C 4%, and W 10%.
  • an alloy material such as an alloy containing Fe, C and Cr, having high carbide contents, as well as a method of increasing carbide content in an alloy.
  • the alloy is pushed towards increased amounts of primary, or eutectic, chromium carbide fractions, so embodiments of the disclosed alloys may fall within the group known as chromium white irons.
  • the disclosed alloys can be "iron based," indicating that they have a composition that is predominantly iron, e.g., at least 50 wt. % iron.
  • different criteria that can be used for producing a high carbide content alloy.
  • Thermodynamic, microstructural, and compositional criteria could be used to produce such an alloy.
  • only one of the criterial can be used to form the alloy, and in some embodiments multiple criteria can be used to form the alloy.
  • the term alloy can refer to the chemical composition of powder used to form a desired component, the powder itself (such as feedstock), the composition of a metal component formed, for example, by the heating and/or deposition of the powder, and the metal component itself.
  • an alloy can be described fully by thermodynamic models.
  • Two thermodynamic criteria can be used to define fine-grained high carbide content cast irons as are described herein: 1) the maximum mole fraction of the carbide or boride content in the material formed during cooling from a liquid state, and 2) the mole fraction of Fe,Cr-rich type carbides formed prior to the initial formation of the austenitic or ferritic matrix.
  • Fe,Cr-rich type carbides are defined as those where the Fe+Cr weight percent exceeds 50% (or exceeds about 50%).
  • An example solidification diagram is shown in Figure 1 that demonstrates embodiments of the thermodynamic criteria described in this disclosure. As shown in Figure 1, three phases can exist in the temperature range shown, Liquid, FCC_A1 (austenite), and M C 3 . The maximum mole fraction of carbide as shown on this plot can be 45% (or about 45%). The mole fraction of M C 3 type carbide which forms prior to the formation of the austenite can be 9% (or about 9%), and thus can be defined as segregated carbides.
  • Figure 1 shows an example within the Fe-Cr-C system where the total carbide content in the system may not exceed 40% (or about 40%) without introducing undesirable segregated M C 3 type carbides.
  • Figure 2 shows an example of an alloy system which can possess a high total carbide content (50-55% mole fraction or about 50 to about 55% mole fraction) that may not have any Fe,Cr-rich type carbide phase which forms above the liquidus temperature of the austenite. As will be described, the alloy shown as an example in Figure 2 can possess the disclosed thermodynamic criteria.
  • the first thermodynamic criterion (the maximum mole fraction of the carbide or boride content in the material formed during cooling from a liquid state) can be used as an indicator for the wear resistance of the material.
  • the criterion will be abbreviated as carbide-max.
  • carbide-max Generally, increased carbide or boride contents can lead to increased wear resistance and can be desirable.
  • the maximum mole fraction of the carbide or boride content can be calculated by evaluating the phase fractions of thermodynamically stable phases as a function of temperature over a range from room temperature to a temperature where the alloy is thermodynamically 100% liquid.
  • the maximum content of carbides or borides at any one temperature is defined as carbide -max.
  • Carbide-max can be the sum of all types of carbide or boride phases at that temperature.
  • the carbide-max can be at least 41% (or at least about 41 %) mole fraction.
  • carbide-max can be at least 45% (or at least about 45%) mole fraction.
  • carbide- max can be at least 50% (or at least about 50%) mole fraction.
  • the second thermodynamic criterion (the mole fraction of Fe,Cr-rich type carbides formed prior to the initial formation of the austenitic or ferritic matrix) can be used as an indicator for the toughness of the material.
  • the criterion will be abbreviated as segregated carbide fraction.
  • an increased mole fraction of segregated carbides can decrease the toughness of the material and can be undesirable.
  • the segregated carbide fraction is calculated by 1 ) identifying the highest temperature at which an iron matrix phase (austenite or ferrite) exists; and 2) calculating the total mole fraction of M-7C3 type carbides at 5K higher.
  • the segregated carbide content can be below 5% (or below about 5%).
  • the segregated carbide content can be 0% (or about 0%).
  • the alloy it may be advantageous for the alloy to have an increased resistance to corrosion.
  • an additional thermodynamic criterion can be utilized.
  • This third criterion can be the chromium content in the Fe-based matrix phase, whether austenite or ferrite, at 1300K (or about 1300K). This criterion is thereby designated the matrix chromium content. This value has been selected as it can be similar to the value measured in casting experiments for several candidate alloys.
  • the matrix chromium content can be above 5 weight % (or above about 5 weight %).
  • the matrix chromium content can be above 9 weight % (or above about 9 weight %).
  • the matrix chromium content can be above 12 weight % (or above about 12 weight %).
  • Table 1 contains a list of some, but not all, alloys which can meet the thermodynamic criteria.
  • the melting behavior of alloys can be modelled to predict the casting feasibility of the alloy. For example, as the precipitation temperature of primary carbides or borides increases, the casting feasibility of the alloy may decrease. High temperature phase precipitation can reduce the fluidity of the material and thus increases manufacturing difficulty and expense.
  • melt range is calculated as the difference between the formation temperature of the carbide or boride phase with the highest formation temperature and the formation temperature of the matrix phase, whether austenite or ferrite. In cases where the matrix phase forms at a higher temperature than any carbide or boride phase, the melt range is zero.
  • the thermodynamic parameter e.g., melt range
  • melt range can be used to predict a decrease in fluidity. As the melt range parameter increases, the fluidity of the alloy can decrease and the manufacturing difficulty and cost can increase.
  • Table 2 includes chemistries of experimental ingots which were produced and the relevant corresponding thermodynamic parameters, including melt range.
  • Table 3 details embodiments of alloys where a total carbide fraction exceeds 60 mole %, and the primary CrC level is still at 5% or lower, and the melt range is still at 50K or lower.
  • An example embodiment is shown in the solidification diagram of Figure 5 for the Ml 05 alloy. As shown, the alloy has a 75.46% M 23 C 6 mole fraction [501] when measured at 1300K. However, no phase is thermodynamically stable in substantial quantity (>5%) at a temperature above the austenite formation temperature [502], which is about 1500K for this alloy. Thus, this alloy is expected to form a very high fraction, >60wt.%, of hard eutectic carbides, be able to cast easily due to the low melt range, and remain relatively tough due to the lack of segregated carbides.
  • the alloy can be described by the microstructural features it possesses. Similar to the concepts described as the thermodynamic criteria, it can be advantageous to have a high fraction of carbides (40% volume fraction or higher, or about 40% volume fraction or higher) to increase hardness and wear resistance.
  • embodiments of the disclosed alloys can have a hardness between 55-70 HRC (or between about 50 and about 70 HRC).
  • the disclosed alloys can have a hardness between 60-65 HRC (or between about 60 and about 65 HRC).
  • the disclosed alloys can have high abrasion resistance as classified by ASTM 65 testing of at least below 0.2 grams lost (or below about 0.2 grams lost).
  • the disclosed alloys can have high abrasion resistance as classified by ASTM 65 testing of at least below 0.15 grams lost (or below about 0.15 grams lost). In some embodiments, the disclosed alloys can have high abrasion resistance as classified by ASTM 65 testing of at least below 0.2 grams lost (or below about 0.2 grams lost). However, it can be also advantageous for these carbides to be relatively fine-grained in order for the structure to maintain a minimum toughness.
  • the measured volume fraction of the carbides or borides in the alloy can exceed 40 volume % (or exceed about 40 volume %). In some embodiments, the measured volume fraction of the carbides can exceed 45 volume % (or exceed about 45 volume %). In some embodiments, the measured volume fraction in the alloy can exceed 50 volume % (or exceed about 50 volume %). In some embodiments, the measured volume fraction in the alloy can exceed 50 volume % (or exceed about 60 volume %).
  • the grain size of any carbides and borides present in the microstructure may not exceed 50 micrometers (or exceed about 50 micrometers) in their longest dimension. In some embodiments, the grain of any carbides and borides present in the microstructure may not exceed 25 micrometers (or exceed about 25 micrometers) in their longest dimension. In some embodiments, the grain of any carbides and borides present in the microstructure may not exceed 5 micrometers (or exceed about 5 micrometers) in their longest dimension. In some embodiments, all carbides and borides are below the above listed parameters. In some embodiments, substantially all carbides and borides are below the above listed parameters. In some embodiments, 90%, 95%, 98%, or 99% of all carbides and borides are below the above listed parameters.
  • alloy X22 As shown in Figures 3A-B.
  • the SEM micrograph shows a material with a very high fraction of carbides with a fine-grain size.
  • Two types of carbide dominate the microstructure, niobium carbide (301) and chromium carbide (302).
  • niobium carbide (301)
  • chromium carbide (302)
  • the chromium carbide can become coarse.
  • the chromium carbides remain fine on the order of 10 ⁇ x 1-2 ⁇ in dimension.
  • chromium carbides As previously mentioned, the formation of a high fraction of fine-grained chromium carbides is not an inherent feature of this alloy system as demonstrated by the micrograph shown in Figure 4.
  • the X24 alloy has a relatively similar composition to X22, however the microstructure possesses larger chromium carbides (401) on the order of 50-150 ⁇ known to reduce toughness.
  • This example is provided to illustrate the fact that simple alloying additions of carbide forming elements such as Nb, Ti, W, Mo, V, W, and/or Ta are not sufficient to produce the microstructural features described in this disclosure. Rather, relatively small compositional spaces exist within the greater region defined as cast irons, and computational modeling is the only effective mechanism to effectively identify this space.
  • alloy compositions which possessed the defined microstructural criteria include X21 and X22.
  • the disclosed alloys can be iron based alloys having both chromium and carbon in order to form eutectic chromium carbides.
  • chromium can be from 10-34 (or about 10 to about 34) wt. % and carbon can be form 2.2-4.02 (or about 2.2 to about 4.02) wt. %.
  • the alloy can be described by a composition in weight percent comprising the following elemental ranges which can meet certain thermodynamic criteria, and which are can be at least partially based on the compositions presented in Table 1 discussed above:
  • the disclosed alloys can be iron based alloys comprising chromium, carbon, and tungsten forming eutectic carbides of primarily the M 2 3C 6 type of at least 60 mole %, and in which the melt range is at 50K or lower.
  • the alloy range can be at least partially described by the compositions found in Table 3 and can be from C: 3.2-4%, Cr: 6-20%, W: 4-10% (or C: about 3.2 - about 4%, Cr: about 6 - about 20%, W about 4 - about 10%).
  • the alloy can be described by a composition in weight percent comprising the following elemental ranges which have been produced and evaluated experimentally, and which are at least partially based on the compositions presented in Table 4 and Table 5:
  • the alloy can be described by a composition in weight percent comprising the following elemental ranges which have been produced and evaluated experimentally and which can meet certain microstructural criteria, and which are at least partially based on the compositions presented in Table 4 and Table 5 above:
  • the alloy can be described by a composition in weight percent comprising the following elemental ranges as defined through glow discharge spectrometer readings, which have been produced and evaluated experimentally and which can meet certain microstructural criteria, and which are at least partially based on the compositions presented in Table 5 above:
  • the alloy can be described by specific compositions in weight percent comprising the following elements, which have been produced and evaluated experimentally and which can meet certain microstructural criteria, and which are at least partially based on the nominal and measured experimental compositions:
  • the Fe compositions listed above can be the balance of the alloy material. In some embodiments, minor impurities can also be found within the composition.
  • increased carbide content can be advantageous because a high fraction of primary (Nb, Ti, V) carbides can effectively increase the liquidus temperature of an alloy and decreases fluidity, which can improve casting processes.
  • Embodiments of the disclosed alloys can be used in a variety of applications and industries. Some non-limiting examples of applications of use include:
  • Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: wear resistant sleeves and/or wear resistant hardfacing for slurry pipelines, mud pump components including pump housing or impeller or hardfacing for mud pump components, ore feed chute components including chute blocks or hardfacing of chute blocks, separation screens including but not limited to rotary breaker screens, banana screens, shaker screens, liners for autogenous grinding mills and semi-autogenous grinding mills, ground engaging tools and hardfacing for ground engaging tools, wear plate for buckets and dumptruck liners, heel blocks and hardfacing for heel blocks on mining shovels, grader blades and hardfacing for grader blades, stacker reclaimers, siazer crushers, general wear packages for mining components, and other communition components.
  • Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: downhole casing and downhole casing, drill pipe and coatings for drill pipe including hardbanding, mud management components, mud motors, fracking pump sleeves, fracking impellers, tracking blender pumps, stop collars, drill bits and drill bit components, directional drilling equipment and coatings for directional drilling equipment including stabilizers and centralizers, blow out preventers and coatings for blow out preventers and blow out preventer components including the shear rams, oil country tubular goods, and coatings for oil country tubular goods.
  • Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: process vessels and coating for process vessels including steam generation equipment, amine vessels, distillation towers, cyclones, catalytic crackers, general refinery piping, corrosion under insulation protection, sulfur recovery units, convection hoods, sour stripper lines, scrubbers, hydrocarbon drums, and other refinery equipment and vessels.
  • Embodiments of the disclosed alloys can be included in following components and coatings for the following components: rolls used in paper machines including yankee dryers and other dryers, calendar rolls, machine rolls, press rolls, digesters, pulp mixers, pulpers, pumps, boilers, shredders, tissue machines, roll and bale handling machines, doctor blades, evaporators, pulp mills, head boxes, wire parts, press parts, M.G. cylinders, pope reels, winders, vacuum pumps, deflakers, and other pulp and paper equipment,
  • Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: boiler tubes, precipitators, fireboxes, turbines, generators, cooling towers, condensers, chutes and troughs, augers, bag houses, ducts, ID fans, coal piping, and other power generation components.
  • Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: chutes, base cutter blades, troughs, primary fan blades, secondary fan blades, augers, and other agricultural applications.
  • Construction applications Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: cement chutes, cement piping, bag houses, mixing equipment, and other construction applications
  • Machine element applications Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: shaft journals, paper rolls, gear boxes, drive rollers, impellers, general reclamation and dimensional restoration applications, and other machine element applications
  • Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: cold rolling mills, hot rolling mills, wire rod mills, galvanizing lines, continue pickling lines, continuous casting rolls and other steel mill rolls, and other steel applications.
  • alloys described can be produced and or deposited in a variety of techniques effectively.
  • Some non-limiting examples of processes include:
  • Thermal spray process including those using a wire feedstock such as twin wire arc, spray, high velocity arc spray, combustion spray and those using a powder feedstock such as high velocity oxygen fuel, high velocity air spray, plasma spray, detonation gun spray, and cold spray.
  • Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire.
  • Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.
  • Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire.
  • Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.
  • Casting processes including processes typical to producing cast iron including but not limited to sand casting, permanent mold casting, chill casting, investment casting, lost foam casting, die casting, centrifugal casting, glass casting, slip casting and process typical to producing wrought steel products including continuous casting processes.
  • Post processing techniques including but not limited to rolling, forging, surface treatments such as carburizing, nitriding, carbonitriding, heat treatments including but not limited to austenitizing, normalizing, annealing, stress relieving, tempering, aging, quenching, cryogenic treatments, flame hardening, induction hardening, differential hardening, case hardening, decarburization, machining, grinding, cold working, work hardening, and welding.
  • Conditional language such as “can,” “could,” “might,” or “may,” unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include or do not include, certain features, elements, and/or steps. Thus, such conditional language is not generally intended to imply that features, elements, and/or steps are in any way required for one or more embodiments.

Abstract

Embodiments of alloys having high, fine-grained carbide content, and methods of manufacturing such alloys. The alloys can be determined through the use of thermodynamic, microstructural, and compositional criterial in order to create a high strength and high toughness alloy. In some embodiments, the alloys can be used as a wear resistant component.

Description

FINE-GRAINED HIGH CARBIDE CAST IRON ALLOYS
INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS
[0001] This Application claims from the benefit of U.S. Provisional Application
No. 62/143,581, filed April 6, 2015, titled "FINE-GRAINED HIGH CARBIDE CAST IRON
ALLOYS," the entirety of which is incorporated herein by reference.
BACKGROUND
Field
[0002] The disclosure relates generally to cast iron alloys used in wear-prone environments and which are resistant to wear.
Description of the Related Art
[0003] The alloy family known as chromium white irons or chromium white cast irons can refer to alloys containing Fe, C, and Cr which can form eutectic chromium carbides. For example, alloys having chromium levels in the range from 15-30 wt. % (or about 15 to about 30 wt. %) and having carbon levels in the range of 1-3 wt. % (or about 1 to about 3 wt. %) can form such chromium white irons. For chromium white irons, formation of primary chromium carbides is typically avoided which can occur as either Cr or C content is increased. For many applications, particularly those which require a minimum level of toughness, it can be advantageous for the alloy system to be in the hypoeutectic region of the Fe-C phase field (i.e., the C level is below the eutectic point in the alloy system). Exceeding the C eutectic level in these systems can create Cr C3 carbide precipitates which are long, rod-like, and can be very embrittling to the material. Further, the addition of chromium can shift the eutectic point to more iron-rich compositions. Therefore, as Cr is added for various benefits (such as corrosion resistance), the amount of carbon which can be added before the alloy enters the hypereutectic regime drops. For example, an Fe-5Cr type alloy has a eutectic point over -4% C while an Fe-25Cr alloy has a eutectic point at around 3.3% C.
[0004] Chromium white irons are generally very useful for applications where resistance to abrasion is advantageous. The relatively high content of chromium carbides in the microstructure are very hard and thus contribute to the abrasion resistance of the material. In part, the volume fraction of carbides in the alloy can dictate the wear resistance of the material, e.g., increased carbide contents can create increased wear resistance. In some applications, the carbon beyond the eutectic point can be increased to increase the total carbide fraction. However, this is done at the expense of toughness.
[0005] International Patent No. WO 84/04760, hereby incorporated by reference in its entirety, describes a mechanism for producing both tough and wear resistant high chromium hypereutectic white irons. WO 84/04760 teaches that a minimum amount of primary M-7C3 carbides are required to achieve the tough and wear resistant high chromium hypereutectic white irons, and it is discussed that refinement of the microstructure and increased toughness can be achieved through process control. International filing WO 85/01962, hereby incorporated by reference in its entirety, also teaches improved toughness through microstructural control, utilizing super-cooling (or process control) and boron to produce globular shaped carbides. US 6,669,790, hereby incorporated by reference in its entirety, teaches that primary chromium carbides must be completely eliminated. To achieve this, vanadium, titanium, and niobium primary carbides are used to increase the total carbide content while maintaining toughness.
SUMMARY
[0006] In some embodiments, computational metallurgy can be used to explore alloy compositional ranges where the total carbide content can be increased without introducing coarse carbide structures known to embrittle the material. When considering the Fe-Cr-C system, the thermodynamic limit for hypoeutectic carbide volume fraction can be 35-40% (or about 35 - about 40%). This disclosure describes embodiments of alloys which can meet a set of thermodynamic criteria which can exceed the 40% (or about 40%) carbide content limit, but may not introduce the formation of hypereutectic M-7C3, M23C6 or generally any Fe,Cr-rich type carbides. The result is a microstructure which can have a very high level, >40% mole fraction (or > about 40% mole fraction) as defined by thermodynamic models, of fine-grained carbides. As such, this new class of materials can be defined as fine-grained high carbide content cast irons. The utility of such a material can be an increased wear resistance, while maintaining similar levels of toughness to hypoeutectic cast irons.
[0007] Disclosed herein are embodiments of an alloy, or an article of manufacture which can contain in at least a portion of its structure a component comprising Fe, Cr, and C in which the total carbide and/or boride content in the microstructure exceeds 40 volume %, and the grain size of all carbides and borides does not exceed 50 micrometers in their longest dimension.
[0008] In some embodiments, the alloy further can further comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, W: 0-9 wt%. In some embodiments, the alloy can further comprise Mn: 0-1 wt %, Mo: 0-1 wt%, Si: 0-1%, Ti: 0-0.5%, V: 0-3 wt.%. In some embodiments, the alloy further can further comprise C: 2.2-4.02 wt.%, Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, W: 4.37-9 wt%.
[0009] In some embodiments, the total carbide and/or boride content can exceed 45 volume %. In some embodiments, the total carbide and/or boride content can exceed 50 volume %.
[0010] In some embodiments, the grain size of all carbides and borides does not exceed 25 micrometers in their longest dimension. In some embodiments, the grain size of all carbides and borides does not exceed 5 micrometers in their longest dimension.
[0011] In some embodiments, the article can be produced via the casting process. In some embodiments, the article can be utilized as a wear resistant component. In some embodiments, the article can be used as a sleeve or layer in pipelines designed to carry abrasive slurries.
[0012] In some embodiments, a maximum carbide fraction can be 50% mole fraction or higher. In some embodiments, a maximum carbide fraction can be 60% mole fraction or higher.
[0013] In some embodiments, the composition can comprise, in weight %: Fe, C: 3.2 - 4% (or about 3.2 - about 4), Cr: 6-20% (or about 6 - about 20), and W: 4-10% (or about 4 - about 10). [0014] In some embodiments, the composition can comprise, in weight %: Fe, C: 2.5 - 3.8% (or about 2.5 - about 3.8), Cr: 10-28% (or about 10 - about 28), Mn: 0-1% (or about 0 to about 1), Mo: 0-1% (or about 0 to about 1), Nb: 0-5% (or about 0 to about 5), Si: 0-1% (or about 0 to about 1), Ti:0-0.5% (or about 0 to about 5), V: 0-3% (or about 0 to about 3) and W: 0-9% (or about 0 to about 9).
[0015] Further disclosed herein is an article of manufacture which can comprise Fe, Cr, and C in which the total carbide and/or boride content in the microstructure exceeds 40 volume %, and the grain size of all carbides and borides does not exceed 50 micrometers in their longest dimension.
[0016] Further disclosed herein is an article of manufacture which can contain at least a portion of a component comprising Fe, Cr, and C in which the total carbide and/or boride content in the microstructure exceeds 0.4 mole fraction, and the total volume of segregated carbides is less than 0.05 mole fraction, whereas a segregated carbide is defined as Fe or Cr - rich boride or carbide, Fe+Cr >50 wt.%, which is thermodynamically stable at a temperature above the temperature at which austenite is thermodynamically stable.
[0017] In some embodiments, the alloy can further comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, W: 0-9 wt%. In some embodiments, the alloy can further comprise Mn: 0-1 wt %, Mo: 0-1 wt%, Si: 0-1%, Ti: 0-0.5%, V: 0-3 wt.%. In some embodiments, the alloy can further comprise C: 2.2-4.02 wt.%, Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, W: 4.37-9 wt%.
[0018] In some embodiments, the total carbide and/or boride content can exceed 0.45 mole fraction. In some embodiments, the total carbide and/or boride content can exceed 0.50 mole fraction.
[0019] In some embodiments, the article can be produced via the casting process. In some embodiments, the article can be utilized as a wear resistant component. In some embodiments, the article can be used as a sleeve or layer in pipelines designed to carry abrasive slurries
[0020] Also disclosed herein is a method of forming a component which can contain in at least a portion of its structure a component comprising Fe, Cr, and C in which the total carbide and/or boride content in the microstructure exceeds 40 volume %, and the grain size of all carbides and borides does not exceed 50 micrometers in their longest dimension.
[0021] In some embodiments, the alloy can further comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, W: 0-9 wt%. In some embodiments, the alloy can further comprise Mn: 0-1 wt %, Mo: 0-1 wt%, Si: 0-1 %, Ti: 0-0.5%, V: 0-3 wt.%. In some embodiments, the alloy can further comprise C: 2.2-4.02 wt.%, Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, W: 4.37-9 wt%.
[0022] In some embodiments, the total carbide and/or boride content can exceed 0.45 mole fraction. In some embodiments, the total carbide and/or boride content can exceed 0.50 mole fraction.
[0023] In some embodiments, the article can be produced via the casting process. In some embodiments, the article can be utilized as a wear resistant component. In some embodiments, the article can be used as a sleeve or layer in pipelines designed to carry abrasive slurries.
[0024] Disclosed herein are embodiments of an article of manufacture comprising an alloy comprising Fe, Cr, and C, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %, and wherein a grain size of all carbides and borides is less than or equal to 50 micrometers in their longest dimension.
[0025] In some embodiments, the alloy can be an iron based alloy and can comprise C: 2.2-4.02 wt. % and Cr: 10-34 wt. %. In some embodiments, the alloy can comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, and W: 0-9 wt. %. In some embodiments, the alloy can further comprise Mn: 0-1 wt. %, Mo: 0-1 wt. %, Si: 0-1 wt. %, Ti: 0-0.5 wt. %, and V: 0-3 wt.%. In some embodiments, the alloy can comprise C: 2.2-4.02 wt.%. Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, and W: 4.37-9 wt. %.
[0026] In some embodiments, the total carbide and boride content can exceed 45 volume %. In some embodiments, the total carbide and boride content can exceed 50 volume %.
[0027] In some embodiments, the grain size of all carbides and borides may not exceed 25 micrometers in their longest dimension. In some embodiments, the grain size of all carbides and borides may not exceed 5 micrometers in their longest dimension. [0028] In some embodiments, the article of manufacture can comprise a sleeve or layer for use in pipelines designed to carry abrasive slurries. Also disclosed herein are embodiments of a wear resistant component comprising embodiments of the disclosed article of manufacture.
[0029] Also disclosed are embodiments of an article of manufacture comprising an alloy comprising Fe, Cr, and C, wherein a total carbide and boride content in a microstructure of the alloy exceeds 0.4 mole fraction, and wherein a total volume of segregated carbides is less than 0.05 mole fraction, segregated carbides being defined as Fe or Cr - rich boride or carbide meeting the equation: Fe+Cr >50 wt.%, wherein the segregated carbides are thermodynamically stable at a temperature above a temperature at which austenite of the alloy is thermodynamically stable.
[0030] In some embodiments, the alloy can be an iron based alloy and can comprise C: 2.2-4.02 wt. %, and Cr: 10-34 wt. %. In some embodiments, the alloy can comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, and W: 0-9 wt. %. In some embodiments, the alloy can comprise Mn: 0-1 wt. %, Mo: 0-1 wt. %, Si: 0-1 wt. %, Ti: 0-0.5 wt. %, and V: 0-3 wt.%.
[0031] In some embodiments, the alloy can comprise C: 2.2-4.02 wt.%, Cr: 12.7- 34 wt.%, Nb: 3.8-5 wt. %, and W: 4.37-9 wt. %.
[0032] In some embodiments, the total carbide and/or boride content can exceed 0.45 mole fraction. In some embodiments, the total carbide and/or boride content can exceed 0.50 mole fraction. In some embodiments, the article of manufacture can comprise a sleeve or layer used in pipelines designed to carry abrasive slurries. Also disclosed herein are embodiments of a wear resistant component which can comprise embodiments of the disclosed article of manufacture.
[0033] Also disclosed herein are embodiments of a method of forming a component comprising providing an alloy comprising Fe, Cr, and C, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %. and wherein a grain size of all carbides and borides is less than or equal to 50 micrometers in their longest dimension, and forming a component from the alloy. [0034] In some embodiments, the alloy can be an iron-based alloy and can comprise C: 2.2-4.02 wt. %, and Cr: 10-34 wt. %. In some embodiments, the alloy can comprise C: 2.5-3.8 wt.%, Cr: 10-28 wt.%, Nb: 0-5 wt. %, W: 0-9 wt. %, Mn: 0-1 wt. %, Mo: 0-1 wt. %, Si: 0-1 wt. %, Ti: 0-0.5 wt. %, and V: 0-3 wt.%. In some embodiments, the alloy can comprise C: 2.2-4.02 wt.%, Cr: 12.7-34 wt.%, Nb: 3.8-5 wt. %, and W: 4.37-9 wt. %.
[0035] In some embodiments, the total carbide and/or boride content can exceed 0.45 mole fraction. In some embodiments, the total carbide and/or boride content can exceed 0.50 mole fraction.
[0036] In some embodiments, the method can comprise forming the component via a casting process. In some embodiments, the method can comprise forming the component into a sleeve or layer.
[0037] Disclosed herein are embodiments of a chromium white iron alloy comprising a composition comprising Fe, Cr, and C, the composition being predominantly Fe, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %, and wherein a melt temperature range of the alloy is below about 300 °C.
[0038] In some embodiments, the melt temperature range can be below about 200 °C. In some embodiments, the melt temperature range can be below about 100 °C.
[0039] In some embodiments, the alloy can be formed into a sleeve or layer for use in pipelines designed to carry abrasive slurries. Also disclosed herein are embodiments of a wear resistant component comprising the chromium white iron alloy disclosed herein.
[0040] Also disclosed herein is an article of manufacture comprising an alloy having a composition comprising Fe, Cr, and C, the composition being predominantly Fe, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %, and wherein a melt temperature range of the alloy is below about 300 °C.
[0041] In some embodiments, the melt temperature range can be below about 200 °C. In some embodiments, the melt temperature range can be below about 100 °C.
[0042] In some embodiments, the article of manufacture can comprise a sleeve or layer for use in pipelines designed to carry abrasive slurries. Also disclosed herein are embodiments of a wear resistant component comprising the article of manufacture disclosed herein.
[0043] Also disclosed herein are embodiments of a method of manufacturing a chromium white iron alloy comprising providing an alloy comprising Fe, Cr, and C, the alloy being predominantly Fe, wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %, and wherein a melt temperature range of the alloy is below about 300 °C, and forming a component from the alloy.
[0044] In some embodiments, the melt temperature range can be below about 200 °C. In some embodiments, the melt temperature range can be below about 100 °C. In some embodiments, a grain size of substantially all of the carbides does not exceed 50 micrometers in their longest dimensions. In some embodiments, the total carbide content in the microstructure of the alloy may exceed 60 volume %.
[0045] In some embodiments, the composition can comprise, in weight %: Fe, C: 3.2 - 4% (or about 3.2 - about 4), Cr: 6-20% (or about 6 - about 20), and W: 4-10% (or about 4 - about 10).
[0046] In some embodiments, the composition can comprise, in weight %: Fe, C: 2.5 - 3.8% (or about 2.5 - about 3.8), Cr: 10-28% (or about 10 - about 28), Mn: 0- 1% (or about 0 to about 1), Mo: 0-1% (or about 0 to about 1), Nb: 0-5% (or about 0 to about 5), Si: 0-1 % (or about 0 to about 1), Ti:0-0.5% (or about 0 to about 5), V: 0-3% (or about 0 to about 3) and W: 0-9% (or about 0 to about 9).
[0047] In some embodiments, forming the component can comprise forming the component via a casting process. In some embodiments, forming the component can comprise forming the component into a sleeve or layer.
[0048] Also disclosed herein are embodiments of a chromium white iron alloy comprising a composition comprising Fe, Cr, and C, the composition being predominantly Fe, a maximum carbide fraction in the alloy which is thermodynamically stable at temperatures ranging from the room temperature to a temperature where the alloy is 100% liquid of 40% mole fraction, and a segregated carbide fraction, defined as Fe,Cr - rich carbides existing at a temperature above the highest temperature at which an austenite or ferrite iron based matrix phase is thermodynamically stable, of 5% mole fraction or lower. BRIEF DESCRIPTION OF THE DRAWINGS
[0049] Figure 1 illustrates a solidification diagram of an embodiment of, in wt. %, Fe: bal, Cr: 25%, C:3.6%.
[0050] Figure 2 illustrates a solidification diagram of an embodiment of, in weight %, Fe: 17%, C:3.6%, Nb 5%, W 5%.
[0051] Figures 3A-B illustrate an SEM micrograph of embodiments of alloy X22 at 1,000X magnification (Figure 3A) and 5,000X magnification (Figure 3B).
[0052] Figure 4 illustrates an SEM micrograph of embodiments of alloy X24 at 1 ,000X magnification.
[0053] Figure 5 illustrates a solidification diagram of an embodiment of an alloy having a composition of, in wt.%, Fe: bal, Cr: 8 %, C 4%, and W 10%.
DETAILED DESCRIPTION
[0054] Disclosed herein is an alloy material, such as an alloy containing Fe, C and Cr, having high carbide contents, as well as a method of increasing carbide content in an alloy. Generally as either Cr or C is increased, the alloy is pushed towards increased amounts of primary, or eutectic, chromium carbide fractions, so embodiments of the disclosed alloys may fall within the group known as chromium white irons. In some embodiments, the disclosed alloys can be "iron based," indicating that they have a composition that is predominantly iron, e.g., at least 50 wt. % iron. Also disclosed herein are different criteria that can be used for producing a high carbide content alloy. Thermodynamic, microstructural, and compositional criteria could be used to produce such an alloy. In some embodiments, only one of the criterial can be used to form the alloy, and in some embodiments multiple criteria can be used to form the alloy. As disclosed herein, the term alloy can refer to the chemical composition of powder used to form a desired component, the powder itself (such as feedstock), the composition of a metal component formed, for example, by the heating and/or deposition of the powder, and the metal component itself.
Thermodynamic Criteria: [0055] In some embodiments, an alloy can be described fully by thermodynamic models. Two thermodynamic criteria can be used to define fine-grained high carbide content cast irons as are described herein: 1) the maximum mole fraction of the carbide or boride content in the material formed during cooling from a liquid state, and 2) the mole fraction of Fe,Cr-rich type carbides formed prior to the initial formation of the austenitic or ferritic matrix.
[0056] Fe,Cr-rich type carbides are defined as those where the Fe+Cr weight percent exceeds 50% (or exceeds about 50%). An example solidification diagram is shown in Figure 1 that demonstrates embodiments of the thermodynamic criteria described in this disclosure. As shown in Figure 1, three phases can exist in the temperature range shown, Liquid, FCC_A1 (austenite), and M C3. The maximum mole fraction of carbide as shown on this plot can be 45% (or about 45%). The mole fraction of M C3 type carbide which forms prior to the formation of the austenite can be 9% (or about 9%), and thus can be defined as segregated carbides. Figure 1 shows an example within the Fe-Cr-C system where the total carbide content in the system may not exceed 40% (or about 40%) without introducing undesirable segregated M C3 type carbides. Figure 2 shows an example of an alloy system which can possess a high total carbide content (50-55% mole fraction or about 50 to about 55% mole fraction) that may not have any Fe,Cr-rich type carbide phase which forms above the liquidus temperature of the austenite. As will be described, the alloy shown as an example in Figure 2 can possess the disclosed thermodynamic criteria.
[0057] The first thermodynamic criterion (the maximum mole fraction of the carbide or boride content in the material formed during cooling from a liquid state) can be used as an indicator for the wear resistance of the material. The criterion will be abbreviated as carbide-max. Generally, increased carbide or boride contents can lead to increased wear resistance and can be desirable. The maximum mole fraction of the carbide or boride content can be calculated by evaluating the phase fractions of thermodynamically stable phases as a function of temperature over a range from room temperature to a temperature where the alloy is thermodynamically 100% liquid. The maximum content of carbides or borides at any one temperature is defined as carbide -max. Carbide-max, however, can be the sum of all types of carbide or boride phases at that temperature. In some embodiments, the carbide-max can be at least 41% (or at least about 41 %) mole fraction. In some embodiments, carbide-max can be at least 45% (or at least about 45%) mole fraction. In some embodiments, carbide- max can be at least 50% (or at least about 50%) mole fraction.
[0058] The second thermodynamic criterion (the mole fraction of Fe,Cr-rich type carbides formed prior to the initial formation of the austenitic or ferritic matrix) can be used as an indicator for the toughness of the material. The criterion will be abbreviated as segregated carbide fraction. Generally, an increased mole fraction of segregated carbides can decrease the toughness of the material and can be undesirable. The segregated carbide fraction is calculated by 1 ) identifying the highest temperature at which an iron matrix phase (austenite or ferrite) exists; and 2) calculating the total mole fraction of M-7C3 type carbides at 5K higher. In some embodiments, the segregated carbide content can be below 5% (or below about 5%). In some embodiments, the segregated carbide content can be 0% (or about 0%).
[0059] Further, in some embodiments, it may be advantageous for the alloy to have an increased resistance to corrosion. In such embodiments, an additional thermodynamic criterion can be utilized. This third criterion can be the chromium content in the Fe-based matrix phase, whether austenite or ferrite, at 1300K (or about 1300K). This criterion is thereby designated the matrix chromium content. This value has been selected as it can be similar to the value measured in casting experiments for several candidate alloys. In some embodiments, the matrix chromium content can be above 5 weight % (or above about 5 weight %). In some embodiments, the matrix chromium content can be above 9 weight % (or above about 9 weight %). In some embodiments, the matrix chromium content can be above 12 weight % (or above about 12 weight %).
[0060] Table 1 below contains a list of some, but not all, alloys which can meet the thermodynamic criteria.
Table 1 : Alloys Which Meet Thermodynamic Criteria
No C Cr Fe Mn Mo Nb Ni Si Ti V W Cr in Total Primary
Matrix Carbide CrC
Ml 3.4 15 69.6 0 0 5 0 0 0 0 7 5.0% 53.7% 0.0%
M2 3.4 15 67.6 0 0 5 0 0 0 0 9 4.9% 56.9% 0.6% M3 3.4 16 68.6 0 0 5 0 0 0 0 7 5.3% 53.8% 0.0%
M4 3.4 16 66.6 0 0 5 0 0 0 0 9 5.2% 57.4% 4.1%
M5 3.4 17 67.6 0 0 5 0 0 0 0 7 5.7% 54.1% 0.0%
M6 3.4 18 66.6 0 0 5 0 0 0 0 7 6.1% 54.6% 1.6%
M7 3.4 19 65.6 0 0 5 0 0 0 0 7 6.5% 55.1% 4.5%
M8 3.4 20 64.6 0 0 5 0 0 0 0 7 6.9% 55.7% 5.0%
M9 3.5 15 69.5 0 0 5 0 0 0 0 7 4.8% 55.0% 0.0%
M10 3.5 15 67.5 0 0 5 0 0 0 0 9 4.7% 58.8% 4.0%
Mil 3.5 16 68.5 0 0 5 0 0 0 0 7 5.1% 55.1% 0.0%
M12 3.5 17 67.5 0 0 5 0 0 0 0 7 5.5% 55.3% 1.8%
M13 3.5 18 66.5 0 0 5 0 0 0 0 7 5.8% 55.6% 2.6%
M14 3.5 20 66.5 0 0 5 0 0 0 0 5 6.7% 50.5% 1.3%
M15 3.6 15 69.4 0 0 5 0 0 0 0 7 4.6% 56.3% 0.8%
M16 3.6 15 67.4 0 0 5 0 0 0 0 9 4.6% 60.7% 5.0%
M17 3.6 16 68.4 0 0 5 0 0 0 0 7 4.9% 56.3% 1.8%
M18 3.6 17 69.4 0 0 5 0 0 0 0 5 5.2% 50.1% 0.5%
M19 3.6 17 67.4 0 0 5 0 0 0 0 7 5.3% 56.4% 2.6%
M20 3.6 18 68.4 0 0 5 0 0 0 0 5 5.6% 50.5% 1.0%
M21 3.6 19 67.4 0 0 5 0 0 0 0 5 6.0% 50.9% 2.4%
M22 3.6 20 66.4 0 0 5 0 0 0 0 5 6.4% 51.5% 3.8%
M23 3.7 15 71.3 0 0 5 0 0 0 0 5 4.4% 50.8% 0.0%
M24 3.7 15 69.3 0 0 5 0 0 0 0 7 4.5% 57.7% 1.4%
M25 3.7 16 70.3 0 0 5 0 0 0 0 5 4.7% 50.9% 1.2%
M26 3.7 16 68.3 0 0 5 0 0 0 0 7 4.8% 57.6% 2.2%
M27 3.7 17 69.3 0 0 5 0 0 0 0 5 5.0% 51.2% 1.8%
M28 3.7 18 68.3 0 0 5 0 0 0 0 5 5.4% 51.5% 3.4%
M29 3.7 19 67.3 0 0 5 0 0 0 0 5 5.8% 51.9% 3.8%
M30 3.8 15 71.2 0 0 5 0 0 0 0 5 4.3% 52.1% 1.6%
M31 3.8 15 69.2 0 0 5 0 0 0 0 7 4.3% 59.2% 2.7%
M32 3.8 16 70.2 0 0 5 0 0 0 0 5 4.5% 52.1% 2.5% M33 3.8 17 69.2 0 0 5 0 0 0 0 5 4.9% 52.3% 3.1%
M34 3.8 18 68.2 0 0 5 0 0 0 0 5 5.2% 52.6% 4.7%
M35 3.4 21 65.6 0 0 5 0 0 0 0 5 7.4% 50.4% 1.1%
M36 3.4 22 64.6 0 0 5 0 0 0 0 5 7.9% 51.1% 2.4%
M37 3.4 23 63.6 0 0 5 0 0 0 0 5 8.4% 52.0% 4.8%
M38 3.5 21 65.5 0 0 5 0 0 0 0 5 7.1% 51.2% 2.6%
M39 3.5 22 64.5 0 0 5 0 0 0 0 5 7.6% 51.9% 3.8%
M40 3.6 21 65.4 0 0 5 0 0 0 0 5 6.8% 52.1% 4.0%
M41 3 21 64 0 0 5 0 0 0 0 7 8.5% 51.1% 1.0%
M42 3 21 62 0 0 5 0 0 0 0 9 8.4% 52.4% 4.9%
M43 3 22 63 0 0 5 0 0 0 0 7 9.0% 51.5% 1.2%
M44 3 23 62 0 0 5 0 0 0 0 7 9.6% 51.8% 3.5%
M45 3 24 63 0 0 5 0 0 0 0 5 10.1% 50.9% 0.9%
M46 3 25 62 0 0 5 0 0 0 0 5 10.7% 51.2% 2.9%
M47 3 26 61 0 0 5 0 0 0 0 5 11.3% 51.5% 4.8%
M48 3 10 82 1 1 0.5 1 1 0.5 0 0 3.1% 100.0% 0.0%
M49 3 10 81 1 1 0.5 2 1 0.5 0 0 3.0% 100.0% 0.0%
M50 3 10 80 1 1 0.5 3 1 0.5 0 0 2.9% 100.0% 0.0%
M51 3.5 10 80.5 1 1 0.5 2 1 0.5 0 0 2.6% 100.0% 0.0%
M52 3.5 10 79.5 1 1 0.5 3 1 0.5 0 0 2.5% 100.0% 0.0%
M53 3.5 11 80.5 1 1 0.5 1 1 0.5 0 0 2.9% 100.0% 0.0%
M54 3.5 11 78.5 1 1 0.5 3 1 0.5 0 0 2.7% 100.0% 1.3%
M55 3.5 11 77.5 1 1 0.5 4 1 0.5 0 0 2.6% 100.0% 1.6%
M56 3.5 12 79.5 1 1 0.5 1 1 0.5 0 0 3.1% 100.0% 1.4%
M57 3.5 12 78.5 1 1 0.5 2 1 0.5 0 0 3.0% 100.0% 1.8%
M58 3.5 12 77.5 1 1 0.5 3 1 0.5 0 0 2.9% 100.0% 2.8%
M59 3.5 13 78.5 1 1 0.5 1 1 0.5 0 0 3.4% 100.0% 2.8%
M60 2.5 23 62.5 0 0 0 0 0 0 3 9 8.3% 50.2% 2.5%
M61 2.5 24 61.5 0 0 0 0 0 0 3 9 8.9% 50.4% 5.0%
M62 2.5 25 61.5 0 0 0 0 0 0 3 8 9.5% 50.2% 4.8% M63 2.5 27 60.5 0 0 0 0 0 0 3 7 10.9% 50.1% 4.6%
M64 2.5 28 59.5 0 0 0 0 0 0 3 7 11.6% 50.2% 4.9%
M65 2.6 23 67.4 0 0 0 0 0 0 0 7 8.6% 50.1% 0.9%
M66 2.6 23 66.4 0 0 0 0 0 0 0 8 8.5% 50.7% 4.1%
M67 2.6 23 65.4 0 0 0 0 0 0 1 8 8.3% 51.0% 3.5%
M68 2.6 23 64.4 0 0 0 0 0 0 2 8 8.1% 50.9% 3.1%
M69 2.6 23 63.4 0 0 0 0 0 0 3 8 8.0% 50.5% 2.8%
M70 2.6 23 63.4 0 0 1 0 0 0 2 8 8.6% 50.0% 2.8%
M71 2.6 23 62.4 0 0 1 0 0 0 3 8 8.5% 50.2% 2.8%
M72 2.6 24 66.4 0 0 0 0 0 0 0 7 9.0% 50.4% 3.2%
M73 2.6 24 65.4 0 0 0 0 0 0 1 7 8.8% 50.7% 2.8%
M74 2.6 24 64.4 0 0 0 0 0 0 1 8 8.8% 51.3% 3.8%
M75 2.6 24 64.4 0 0 0 0 0 0 2 7 8.7% 50.3% 2.6%
M76 2.6 24 63.4 0 0 0 0 0 0 2 8 8.6% 51.5% 3.5%
M77 2.6 24 63.4 0 0 0 0 0 0 3 7 8.7% 50.1% 0.5%
M78 2.6 24 62.4 0 0 0 0 0 0 3 8 8.5% 51.7% 3.4%
M79 2.6 25 66.4 0 0 0 0 0 0 0 6 9.6% 50.1% 2.0%
M80 2.6 25 64.4 0 0 0 0 0 0 1 7 9.4% 50.9% 3.0%
M81 2.6 25 63.4 0 0 0 0 0 0 2 7 9.2% 51.2% 2.9%
M82 2.6 25 62.4 0 0 0 0 0 0 3 7 9.1% 51.4% 3.0%
M83 2.6 25 62.4 0 0 1 0 0 0 2 7 9.8% 50.1% 4.7%
M84 2.6 25 61.4 0 0 1 0 0 0 3 7 9.8% 50.2% 4.8%
M85 2.6 26 65.4 0 0 0 0 0 0 0 6 10.1% 50.3% 4.1%
M86 2.6 26 64.4 0 0 0 0 0 0 1 6 9.9% 50.6% 4.1%
M87 2.6 26 63.4 0 0 0 0 0 0 2 6 9.8% 50.9% 2.1%
M88 2.6 26 62.4 0 0 0 0 0 0 3 6 9.7% 51.2% 2.3%
M89 2.6 27 65.4 0 0 0 0 0 0 0 5 10.6% 50.0% 2.5%
M90 2.6 27 64.4 0 0 0 0 0 0 1 5 10.5% 50.3% 2.8%
M91 2.6 27 63.4 0 0 0 0 0 0 1 6 10.5% 50.9% 4.2%
M92 2.6 27 63.4 0 0 0 0 0 0 2 5 10.4% 50.6% 0.9% M93 2.6 27 62.4 0 0 0 0 0 0 2 6 10.4% 51.1% 4.4%
M94 2.6 27 62.4 0 0 0 0 0 0 3 5 10.4% 50.9% 1.3%
M95 2.6 27 61.4 0 0 0 0 0 0 3 6 10.4% 51.4% 4.6%
M96 2.6 27 60.4 0 0 1 0 0 0 3 6 11.1% 50.2% 4.5%
M97 2.6 28 64.4 0 0 0 0 0 0 0 5 11.2% 50.3% 4.5%
M98 2.6 28 63.4 0 0 0 0 0 0 1 5 11.1% 50.6% 4.9%
M99 2.6 28 63.4 0 0 0 0 0 0 2 4 11.0% 50.3% 1.5%
M100 2.6 28 62.4 0 0 0 0 0 0 2 5 11.0% 50.8% 3.1%
M101 2.6 28 62.4 0 0 0 0 0 0 3 4 11.0% 50.6% 0.0%
M102 2.6 28 61.4 0 0 0 0 0 0 3 5 11.0% 51.1% 3.6%
M103 2.6 28 60.4 0 0 0 0 0 0 3 6 11.1% 51.6% 4.9%
M104 2.6 28 59.4 0 0 1 0 0 0 3 6 11.8% 50.4% 4.8%
[0061] In some embodiments, the melting behavior of alloys can be modelled to predict the casting feasibility of the alloy. For example, as the precipitation temperature of primary carbides or borides increases, the casting feasibility of the alloy may decrease. High temperature phase precipitation can reduce the fluidity of the material and thus increases manufacturing difficulty and expense.
[0062] Melt range is calculated as the difference between the formation temperature of the carbide or boride phase with the highest formation temperature and the formation temperature of the matrix phase, whether austenite or ferrite. In cases where the matrix phase forms at a higher temperature than any carbide or boride phase, the melt range is zero. The thermodynamic parameter, e.g., melt range, can be used to predict a decrease in fluidity. As the melt range parameter increases, the fluidity of the alloy can decrease and the manufacturing difficulty and cost can increase. Table 2 includes chemistries of experimental ingots which were produced and the relevant corresponding thermodynamic parameters, including melt range.
Table 2: Chemistries of Experimental Alloys and Corresponding Modelling Results Cr Cu Mn Mo Nb Ni Si Ti V W Total Cr in Liquidus Melt
Hard Matrix Range0 24.00 1.20 2.00 3.00 0.00 2.50 1.50 0.00 0.00 0.00 28.9% 12.0% 1000 550 0.00 2.00 24.00 1.20 2.00 3.00 2.00 2.50 1.50 0.00 0.00 0.00 31.6% 12.5% 1000 650
0.00 2.00 24.00 1.20 2.00 3.00 3.00 2.50 1.50 0.50 0.00 0.00 33.3% 13.2% 1600 250
0.00 2.00 24.00 1.20 2.00 3.00 4.00 2.50 1.50 4.00 0.00 0.00 23.7% 17.2% 1700 300
1.00 2.00 24.00 1.20 2.00 3.00 2.00 2.50 1.50 2.00 0.00 0.00 18.5% 13.0% 1000 950
0.50 2.00 24.00 1.20 2.00 3.00 2.00 2.50 1.50 0.00 0.00 0.00 25.2% 12.8% 1000 700
2.00 1.00 24.00 1.20 2.00 3.00 1.50 2.50 1.50 2.00 0.00 0.00 4.6% 15.3% 1600 300
0.00 1.50 24.00 1.20 2.00 3.00 2.00 2.50 1.50 2.00 0.00 0.00 6.7% 16.6% 1650 300
0.50 1.50 24.00 1.20 2.00 3.00 1.50 2.50 1.50 1.00 0.00 0.00 23.8% 14.5% 1600 250
1.00 1.00 24.00 1.20 2.00 3.00 0.50 2.50 1.50 1.50 0.00 0.00 10.0% 16.0% 1600 150
1.50 1.00 24.00 1.20 2.00 3.00 1.50 2.50 1.50 0.50 0.00 0.00 14.6% 13.9% 1600 250
0.00 3.00 24.00 1.20 2.00 3.00 2.00 2.50 1.50 1.00 0.00 0.00 36.8% 10.4% 1600 350
0.00 3.00 25.00 1.20 2.00 3.00 2.00 2.50 1.50 1.00 0.00 0.00 4.5% 11.2% 1600 350
0.00 2.00 24.00 1.20 2.00 3.00 2.00 2.50 1.50 0.50 0.00 2.00 35.3% 12.6% 1600 250
0.00 2.50 27.00 1.20 2.00 3.00 2.00 2.50 1.50 0.50 0.00 5.00 3.4% 12.1% 1600 250
0.00 2.50 24.00 1.20 2.00 3.00 2.00 2.50 1.50 0.50 2.00 0.00 34.5% 12.5% 1600 250
0.00 3.00 24.00 1.20 2.00 3.00 2.00 2.50 1.50 0.50 5.00 0.00 38.1% 12.7% 1600 250
0.00 3.40 20.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 5.00 20.5% 6.9% 1600 300
0.00 3.60 20.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 5.00 23.9% 6.4% 1550 350
0.00 3.80 20.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 5.00 27.0% 5.9% 1550 400
0.00 3.80 15.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 5.00 23.6% 4.3% 1550 450
0.00 2.60 28.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 5.00 45.0% 14.8% 1600 200
0.00 2.20 24.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 9.00 5.9% 13.1% 1600 200
0.00 3.40 34.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 5.00 60.3% 14.5% 1600 200
0.00 3.80 31.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 5.00 64.2% 10.9% 1600 250
0.00 3.80 32.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 11.00 5.7% 11.6% 1600 250
0.00 3.80 32.00 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.00 15.00 5.8% 11.9% 1600 250
0.00 2.00 30.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 37.2% 15.2% 1650 0
0.00 2.50 28.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 31.7% 13.4% 1600 0
0.00 2.50 27.00 0.00 0.00 0.00 1.00 0.00 0.00 0.00 0.00 2.00 40.4% 12.1% 1600 0
0.00 2.50 27.00 0.00 0.00 0.00 2.00 0.00 0.00 0.00 0.00 4.00 45.5% 12.3% 1600 0
0.00 3.10 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4.00 22.9% 8.2% 1600 0
0.00 2.80 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6.00 5.0% 9.0% 1600 0
0.90 2.50 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6.00 2.6% 7.8% 1550 0
0.40 2.90 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6.00 8.8% 7.8% 1550 0
1.00 2.50 18.00 0.00 0.00 0.00 1.00 0.00 0.00 0.00 0.00 8.00 1.2% 4.9% 1500 150
1.00 2.50 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 10.00 0.0% 7.4% 1550 0
0.10 2.50 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6.00 0.0% 9.7% 1600 0
0.50 2.00 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6.00 0.0% 10.7% 1550 0
1.00 1.50 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6.00 0.0% 11.6% 1550 50
0.80 0.80 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.00 16.7% 0.0% 1600 0
0.60 1.40 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.00 0.0% 13.5% 1600 0
1.60 0.60 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.00 0.0% 12.9% 1600 150
1.4 1.20 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.00 0.0% 11.8% 1550 150 2.60 25.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.00 11.2% 6.5% 1550 100
3.35 22.9 0.00 0.33 0.00 4.35 0.00 0.64 0.00 0.00 4.18 25.9% 8.7% 1600 250
3.4 22.7 0.00 0.6 0.00 0 0.00 0.6 0.00 0.00 5.4 26.2% 6.7% 1600 0
1.5 24.5 0.00 0.4 0.00 0 0.00 0.4 0.00 0.00 5.3 0.0% 11.2% 1550 100
1.6 20 0.00 0.00 0.00 0 0.00 0.00 6.00 0.00 0.00 12.1% 8.5% 1650 200
1.6 20 0.00 0.00 0.00 0 0.00 0.00 6.00 0.00 0.00 12.4% 11.6% 1650 250
0.2 10 0.00 0.00 0.00 0 0.00 0.00 0.00 0.00 0.00 0.0% 1.1% 1650 100
3.00 10.00 0.00 0.00 0.00 0 0.00 0.00 0.00 15.00 0.00 23.3% 0.5% 1450 200
2.80 10.00 0.00 0.00 0.00 0 0.00 0.00 0.00 10.00 6.00 21.3% 2.7% 1500 0
3.20 10.00 0.00 0.00 0.00 0 0.00 0.00 0.00 15.00 0.00 26.1% 4.0% 1500 50
2.80 10.00 0.00 0.00 0.00 0 0.00 0.00 0.00 10.00 6.00 22.6% 5.3% 1500 0
2.60 10.00 0.00 0.00 0.00 0 0.00 0.00 0.00 10.00 0.00 19.3% 3.6% 1500 0
1.60 14.00 0.00 0.00 0.00 0 0.00 0.00 0.00 5.00 0.00 10.8% 4.7% 1550 100
2.40 10.00 0.00 0.00 0.00 0 0.00 0.00 0.00 10.00 0.00 18.9% 5.4% 1550 0
2.29 22.20 1.41 1.59 0.64 0.00 2.52 1.51 0.00 0.00 0.00 29.4% 9.4% 1600 0
2.37 19.40 1.32 1.66 2.48 2.38 3.06 1.42 0.00 0.00 0.00 29.3% 8.8% 1600 150
2.09 22.70 1.23 1.52 2.62 2.08 3.03 1.31 0.53 0.00 0.00 16.7% 12.3% 1000 850
1.96 21.10 1.13 1.37 12.60 1.98 2.94 0.94 0.39 0.00 0.00 27.4% 12.5% 1600 200
2.13 22.50 1.09 1.21 3.13 2.70 3.28 1.14 3.31 0.00 0.00 28.7% 16.0% 1650 350
1.97 23.30 1.21 1.57 3.03 1.57 3.25 1.21 2.06 0.00 0.00 29.2% 12.5% 1000 950
2.13 22.00 1.27 1.58 1.33 1.73 3.04 1.43 0.00 0.00 0.00 26.5% 10.3% 1000 700
1.08 23.40 1.21 1.55 2.85 1.24 3.25 1.28 1.87 0.00 0.00 13.4% 16.4% 1600 250
1.50 22.80 1.10 1.57 2.84 1.41 2.95 1.20 1.94 0.00 0.00 22.0% 16.4% 1650 250
1.56 22.40 1.15 1.62 3.14 1.19 2.89 1.22 0.94 0.00 0.00 25.3% 13.2% 1600 200
0.99 23.10 1.17 1.77 3.02 0.47 2.90 1.18 1.39 0.00 0.00 14.3% 16.3% 1600 150
1.00 22.70 1.21 1.78 2.70 1.31 3.05 1.25 0.51 0.00 0.00 15.2% 14.7% 1600 100
3.24 22.10 1.29 1.37 2.19 1.57 3.15 1.36 0.97 0.00 0.00 3.9% 7.6% 1600 350
2.96 22.90 1.21 1.34 5.27 1.44 3.02 1.10 1.03 0.00 0.00 35.8% 9.9% 1600 300
2.44 21.60 1.19 1.51 3.11 1.60 2.74 1.28 0.47 0.00 1.81 35.2% 9.7% 1600 250
3.89 23.50 1.14 1.38 2.62 1.60 3.17 1.45 0.44 0.00 3.75 3.5% 6.0% 1550 350
2.64 22.50 1.20 1.43 2.66 1.54 2.96 1.32 0.51 1.74 0.00 33.4% 10.9% 1600 200
3.00 22.90 1.27 1.40 3.37 1.52 3.04 1.27 0.54 4.11 0.00 38.4% 11.0% 1550 300
4.35 16.20 0.00 0.73 0.00 3.77 0.30 0.77 0.00 0.00 4.55 40.5% 3.8% 1550 400
3.14 16.50 0.00 0.59 0.00 4.81 0.24 0.60 0.00 0.00 4.51 22.0% 6.2% 1600 350
4.32 14.90 0.00 0.68 0.00 5.21 0.28 0.75 0.00 0.00 4.57 38.1% 3.7% 1550 450
3.43 17.00 0.00 0.64 0.00 4.42 0.25 0.63 0.00 0.00 4.53 26.8% 5.6% 1550 400
4.65 16.40 0.00 0.76 0.00 4.56 0.28 0.81 0.00 0.00 4.34 45.9% 3.6% 1550 450
3.62 16.90 0.00 0.69 0.00 3.73 0.23 0.67 0.00 0.00 4.58 29.9% 5.0% 1550 350
4.02 12.70 0.00 0.73 0.00 3.83 0.24 0.70 0.00 0.00 4.39 31.4% 3.3% 1550 450
3.13 25.00 0.00 0.58 0.00 4.47 0.30 0.64 0.00 0.00 4.37 17.5% 10.6% 1600 250
2.60 28.20 0.00 0.52 0.00 4.64 0.31 0.59 0.00 0.00 4.18 44.8% 15.0% 1600 200
2.60 28.20 0.00 0.52 0.00 4.64 0.31 0.59 0.00 0.00 4.18
2.62 28.00 0.00 0.54 0.00 4.82 0.30 0.58 0.00 0.00 4.35 45.0% 14.9% 1600 200 2.62 28.00 0.00 0.54 0.00 4.82 0.30 0.58 0.00 0.00 4.35
2.73 27.60 0.00 0.53 0.00 4.82 0.33 0.60 0.00 0.00 4.19 46.8% 13.9% 1600 200
2.73 27.60 0.00 0.53 0.00 4.82 0.33 0.60 0.00 0.00 4.19
2.70 28.30 0.00 0.55 0.00 4.37 0.30 0.60 0.00 0.00 4.29 46.9% 14.2% 1600 200
2.70 28.30 0.00 0.55 0.00 4.37 0.30 0.60 0.00 0.00 4.29
3.35 22.90 0.00 0.33 0.00 4.35 0.52 0.64 0.00 0.00 4.18 26.4% 8.6% 1600 250
2.42 21.20 0.00 0.52 0.00 4.77 0.36 0.52 0.00 0.00 9.49 5.7% 11.1% 1600 250
2.42 24.80 0.00 0.51 0.00 4.51 0.26 0.53 0.00 0.00 4.51 41.0% 13.4% 1600 200
2.31 23.80 0.00 0.46 0.00 4.77 0.36 0.50 0.00 0.00 8.90 5.6% 13.5% 1600 200
2.31 23.80 0.00 0.46 0.00 4.77 0.36 0.50 0.00 0.00 8.90
2.35 23.70 0.00 0.47 0.00 4.49 0.34 0.51 0.00 0.00 8.05 5.2% 13.2% 1600 200
2.35 23.70 0.00 0.47 0.00 4.49 0.34 0.51 0.00 0.00 8.05
2.24 24.00 0.00 0.49 0.00 4.36 0.31 0.51 0.00 0.00 8.09 5.1% 13.8% 1600 200
2.24 24.00 0.00 0.49 0.00 4.36 0.31 0.51 0.00 0.00 8.09
2.36 23.70 0.00 0.48 0.00 4.32 0.34 0.52 0.00 0.00 8.42 5.0% 13.0% 1600 200
2.36 23.70 0.00 0.48 0.00 4.32 0.34 0.52 0.00 0.00 8.42
2.34 19.60 0.00 0.48 0.00 4.52 0.59 0.51 0.00 0.00 9.05 5.4% 10.2% 1600 250
3.86 29.10 0.00 0.65 0.00 4.71 0.35 0.75 0.00 0.00 4.27 30.8% 10.6% 1600 250
4.07 28.50 0.00 0.64 0.00 5.27 0.37 0.79 0.00 0.00 4.32 35.4% 9.8% 1600 300
3.71 30.60 0.00 0.54 0.00 5.39 0.50 0.64 0.00 0.00 10.70 6.2% 12.0% 1600 300
3.73 30.70 0.00 0.48 0.00 4.74 0.53 0.58 0.00 0.00 11.50 5.5% 11.6% 1600 250
2.05 31.40 0.00 0.36 0.00 0.11 0.26 0.45 0.00 0.00 0.15 38.5% 16.1% 1650 0
2.51 28.70 0.00 0.45 0.00 0.09 0.28 0.55 0.00 0.00 0.14 32.0% 14.1% 1600 0
2.79 26.70 0.00 0.46 0.00 0.87 0.17 0.58 0.00 0.00 1.66 38.5% 11.4% 1600 -50
2.85 25.80 0.00 0.45 0.00 2.03 0.23 0.56 0.00 0.00 4.59 47.2% 10.7% 1600 50
3.74 24.10 0.00 0.62 0.00 0.00 0.25 0.64 0.00 0.00 3.67 38.7% 6.4% 1600 0
2.84 25.20 0.00 0.57 0.00 0.00 0.12 0.54 0.00 0.00 3.82 20.7% 9.5% 1600 0
3.36 22.70 0.00 0.58 0.00 0.00 0.26 0.58 0.00 0.00 5.44 25.5% 6.8% 1600 0
2.07 25.90 0.00 0.52 0.00 0.00 0.14 0.47 0.00 0.00 5.55 40.4% 12.7% 1600 0
2.88 23.50 0.00 0.52 0.00 0.00 0.33 0.57 0.00 0.00 5.41 18.2% 6.4% 1550 0
2.88 22.60 0.00 0.59 0.00 0.00 0.25 0.60 0.00 0.00 5.44 17.7% 7.1% 1550 0
2.79 18.30 0.00 0.52 0.00 1.09 0.31 0.53 0.00 0.00 7.26 5.5% 4.8% 1500 200
2.41 22.60 0.00 0.48 0.00 0.00 0.39 0.55 0.00 0.00 9.13 0.0% 7.0% 1550 50
3.25 21.50 0.00 0.61 0.00 0.00 0.25 0.57 0.00 0.00 5.60 22.7% 6.3% 1550 50
2.08 21.40 0.00 0.52 0.00 0.00 0.25 0.46 0.00 0.00 5.95 0.0% 8.4% 1550 0
1.53 24.50 0.00 0.43 0.00 0.00 0.27 0.45 0.00 0.00 5.33 0.0% 11.0% 1550 100
1.19 25.4 0.00 0.353 0.00 0.00 0.228 0.31 0.00 0.00 4.72 0.0% 13.5% 1600 50
1.55 22.9 0.00 0.411 0.00 0.00 0.218 0.396 0.00 0.00 4.69 0.0% 9.9% 1550 50.799 23.6 0.00 0.299 0.00 0.00 0.238 0.276 0.00 0.00 4.44 0.0% 11.0% 1600 250
1.37 24.7 0.00 0.277 0.00 0.00 0.219 0.357 0.00 0.00 3.05 23.2% 10.2% 1600 150
2.01 18.4 0.00 0.57 0.00 0.00 0.259 0.95 0.00 0.00 3.33 13.0% 5.2% 1550 150
3.96 21.3 0.00 0.421 0.00 3.99 0.779 0.714 0.00 0.00 3.73 39.9% 6.0% 1600 300
4.06 20.8 0.00 0.587 0.00 0 0.717 0.628 0.00 0.00 5.24 37.7% 4.7% 1550 50 24.9 0.00 0.373 0.00 0 0.766 0.414 0.00 0.00 5.09 0.0% 12.4% 1550 0
21.6 0.00 0 0.00 0.00 0.00 0.4 4.93 0.00 0.00 12.7% 13.8% 1650 200
10.5 0.00 0 0.00 0.00 0.00 0.22 0.00 0.00 0.00 0.0% 1.8% 1650 100
13.30 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.67 0.00 39.2% 2.5% 1500 50
21.90 0.00 0.61 0.00 0.00 0.00 0.66 0.00 0.00 5.37 39.5% 4.9% 1550 100
12.3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9.53 4.1 21.1% 3.5% 1500 50
14.4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 11.7 0 24.6% 7.6% 1500 0
11.9 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9.32 4.42 26.3% 4.5% 1500 0
10.80 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.78 0.00 13.7% 2.9% 1500 50
16.60 0.00 0.45 0.00 0.00 0.00 0.48 0.00 4.02 0.00 16.3% 5.4% 1550 150
13.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9.79 0.00 20.1% 7.9% 1550 0
[0063] Table 3 details embodiments of alloys where a total carbide fraction exceeds 60 mole %, and the primary CrC level is still at 5% or lower, and the melt range is still at 50K or lower. An example embodiment is shown in the solidification diagram of Figure 5 for the Ml 05 alloy. As shown, the alloy has a 75.46% M23C6 mole fraction [501] when measured at 1300K. However, no phase is thermodynamically stable in substantial quantity (>5%) at a temperature above the austenite formation temperature [502], which is about 1500K for this alloy. Thus, this alloy is expected to form a very high fraction, >60wt.%, of hard eutectic carbides, be able to cast easily due to the low melt range, and remain relatively tough due to the lack of segregated carbides.
Table 3: Alloys, given in wt.% with Fe balance, which can meet thermodynamic criteria of
>60% total carbide, and 50K or lower melt range.
No C Cr w Primary CrC Total Carbide Melt Range
M105 4 8 10 0.0069 0.7546 50
M106 4 13 8 0.0353 0.7525 50
M107 3.8 14 10 0.0465 0.727 50
M108 3.8 13 10 0.0241 0.7242 50
M109 4 7 10 0 0.7224 0
MHO 4 9 8 0.0241 0.715 50
Mill 3.8 8 10 0 0.709 0
M112 3.8 13 8 0.0099 0.7077 50
M113 3.8 7 10 0 0.7048 0
M114 3.8 12 8 0 0.7046 0
M115 3.8 14 8 0.0325 0.7033 50
M116 4 8 8 0 0.703 0
M117 3.8 10 8 0.0311 0.6967 50 M118 4 7 8 0 0.6912 0
M119 3.6 15 10 0.0402 0.6868 50
M120 4 13 6 0.021 0.6857 50
M121 3.6 14 10 0.0199 0.6836 50
M122 3.8 9 8 0.0014 0.6833 50
M123 3.6 13 10 0 0.6802 0
M124 3.6 12 10 0 0.6767 0
M125 4 10 6 0.0396 0.6752 50
M126 3.6 11 10 0 0.673 0
M127 3.8 8 8 0 0.6705 0
M128 3.6 9 10 0.0375 0.6653 50
M129 3.8 12 6 0 0.6642 0
M130 3.6 13 8 0 0.6638 0
M131 4 9 6 0.0115 0.6636 50
M132 3.6 14 8 0.0067 0.6618 50
M133 4 14 6 0.0443 0.6615 50
M134 3.6 8 10 0 0.6612 0
M135 3.6 12 8 0 0.6599 0
M136 3.8 7 8 0 0.6578 0
M137 3.8 11 6 0.0425 0.6578 50
M138 3.6 11 8 0 0.6559 0
M139 3.6 7 10 0 0.6526 0
M140 4 8 6 0 0.6524 0
M141 3.6 10 8 0.0304 0.6517 50
M142 3.6 15 8 0.0272 0.6483 50
M143 3.6 9 8 0 0.6474 0
M144 3.4 15 10 0.0296 0.645 50
M145 3.8 10 6 0.0172 0.6446 50
M146 3.4 14 10 0 0.6411 0
M147 4 7 6 0 0.641 0
M148 3.8 13 6 0 0.6384 0
M149 3.6 16 8 0.0463 0.6384 50
M150 3.6 8 8 0 0.6379 0
M151 3.4 13 10 0 0.6371 0
M152 3.4 12 10 0 0.6329 0
M153 3.8 9 6 0 0.6321 0
M154 4 6 10 0 0.6289 0
M155 3.6 11 6 0 0.6288 0
M156 3.4 11 10 0 0.6286 0
M157 4 12 4 0 0.6285 0
M158 3.6 7 8 0 0.6245 0
M159 3.4 10 10 0 0.624 0
M160 3.4 14 8 0 0.623 0
M161 4 10 4 0.0278 0.623 50
M162 3.2 20 10 0 0.6225 0 M163 3.4 13 8 0 0.6207 0
M164 3.8 14 6 0.0191 0.6201 50
M165 3.8 8 6 0 0.62 0
M166 3.4 9 10 0 0.6192 0
M167 3.8 6 10 0 0.6183 0
M168 3.4 12 8 0 0.6162 0
M169 3.6 12 6 0 0.6153 0
M170 3.6 10 6 0 0.6144 0
M171 3.4 8 10 0 0.6142 0
M172 4 6 8 0 0.6136 0
M173 3.4 15 8 0.001 0.6128 50
M174 4 9 4 0 0.6127 0
M175 3.4 11 8 0 0.6114 0
M176 3.8 7 6 0 0.6079 0
M177 3.6 6 10 0 0.6077 0
M178 3.8 15 6 0.0403 0.6065 50
M179 3.4 10 8 0 0.6064 0
M180 3.4 16 8 0.0196 0.6056 50
M181 3.8 11 4 0 0.6041 0
M182 3.2 15 10 0.014 0.6041 50
M183 3.8 6 8 0 0.6032 0
M184 4 8 4 0 0.6023 0
M185 3.4 7 10 0 0.6015 0
M186 3.4 9 8 0 0.6012 0
M187 3.4 17 8 0.0371 0.601 50
M188 3.6 9 6 0 0.6008 0
Microstructural Criteria:
[0064] In some embodiments, the alloy can be described by the microstructural features it possesses. Similar to the concepts described as the thermodynamic criteria, it can be advantageous to have a high fraction of carbides (40% volume fraction or higher, or about 40% volume fraction or higher) to increase hardness and wear resistance. For example, embodiments of the disclosed alloys can have a hardness between 55-70 HRC (or between about 50 and about 70 HRC). In some embodiments, the disclosed alloys can have a hardness between 60-65 HRC (or between about 60 and about 65 HRC). In some embodiments, the disclosed alloys can have high abrasion resistance as classified by ASTM 65 testing of at least below 0.2 grams lost (or below about 0.2 grams lost). In some embodiments, the disclosed alloys can have high abrasion resistance as classified by ASTM 65 testing of at least below 0.15 grams lost (or below about 0.15 grams lost). In some embodiments, the disclosed alloys can have high abrasion resistance as classified by ASTM 65 testing of at least below 0.2 grams lost (or below about 0.2 grams lost). However, it can be also advantageous for these carbides to be relatively fine-grained in order for the structure to maintain a minimum toughness.
[0065] In some embodiments, the measured volume fraction of the carbides or borides in the alloy can exceed 40 volume % (or exceed about 40 volume %). In some embodiments, the measured volume fraction of the carbides can exceed 45 volume % (or exceed about 45 volume %). In some embodiments, the measured volume fraction in the alloy can exceed 50 volume % (or exceed about 50 volume %). In some embodiments, the measured volume fraction in the alloy can exceed 50 volume % (or exceed about 60 volume %).
[0066] In some embodiments, the grain size of any carbides and borides present in the microstructure may not exceed 50 micrometers (or exceed about 50 micrometers) in their longest dimension. In some embodiments, the grain of any carbides and borides present in the microstructure may not exceed 25 micrometers (or exceed about 25 micrometers) in their longest dimension. In some embodiments, the grain of any carbides and borides present in the microstructure may not exceed 5 micrometers (or exceed about 5 micrometers) in their longest dimension. In some embodiments, all carbides and borides are below the above listed parameters. In some embodiments, substantially all carbides and borides are below the above listed parameters. In some embodiments, 90%, 95%, 98%, or 99% of all carbides and borides are below the above listed parameters.
[0067] An example of a candidate microstructure which meets the above specified criteria is alloy X22 as shown in Figures 3A-B. The SEM micrograph shows a material with a very high fraction of carbides with a fine-grain size. Two types of carbide dominate the microstructure, niobium carbide (301) and chromium carbide (302). Generally, in alloys with excess carbide content, commonly done through increasing the carbon above the eutectic point, the chromium carbide can become coarse. However, as demonstrated in this example, the chromium carbides remain fine on the order of 10μ x 1-2μ in dimension.
[0068] As previously mentioned, the formation of a high fraction of fine-grained chromium carbides is not an inherent feature of this alloy system as demonstrated by the micrograph shown in Figure 4. The X24 alloy has a relatively similar composition to X22, however the microstructure possesses larger chromium carbides (401) on the order of 50-150 μπι known to reduce toughness. This example is provided to illustrate the fact that simple alloying additions of carbide forming elements such as Nb, Ti, W, Mo, V, W, and/or Ta are not sufficient to produce the microstructural features described in this disclosure. Rather, relatively small compositional spaces exist within the greater region defined as cast irons, and computational modeling is the only effective mechanism to effectively identify this space.
[0069] Based on scanning electron microscopy the alloy compositions which possessed the defined microstructural criteria include X21 and X22.
Table 4: Experimental Alloy Chemistries Produced in Ingot Form
Figure imgf000025_0001
X27 2.20 24.00 59.80 0.00 5.00 0.00 0.00 9.00
X28 3.40 34.00 52.60 0.00 5.00 0.00 0.00 5.00
X29 3.80 31.00 55.20 5.00 5.00
X30 3.80 32.00 48.20 5.00 11.00
X31 3.80 32.00 44.20 5.00 15.00
X32 2.00 30.00 68.00
X33 2.50 28.00 69.50
X34 2.50 27.00 67.50 1.00 2.00
X35 2.50 27.00 64.50 2.00 4.00
X36 3.10 25.00 67.90 4.00
X36 3.10 25.00 67.90 4.00
X37 2.80 25.00 66.20 6.00
X38 0.90 2.50 25.00 65.60 6.00
X39 0.40 2.90 25.00 65.70 6.00
X40 1.00 2.50 18.00 69.50 1.00 8.00
X41 1.00 2.50 25.00 61.50 10.00
X42 0.10 2.50 25.00 66.40 6.00
X43 0.50 2.00 25.00 66.50 6.00
X44 1.00 1.50 25.00 66.50 6.00
X45 0.80 0.80 25.00 68.40 5.00
X46 0.60 1.40 25.00 68.00 5.00
X47 1.60 0.60 25.00 67.80 5.00
X48 1.4 1.20 25.00 67.4 5.00
X49 1.4 2.60 25.00 66 5.00
X50 2.6 1.6 20 69.80 6.00
X51 2 1.6 20 70.40 6.00
X52 2.4 0.2 10 87.40
X53 4.00 3.00 10.00 68.00 15.00
X54 1.80 2.80 10.00 69.40 10.00 6.00
X55 1.40 3.20 10.00 70.40 15.00
X56 1.00 2.80 10.00 70.20 10.00 6.00
X57 1.40 2.60 10.00 76.00 10.00
X58 2.00 1.60 14.00 77.40 5.00
X59 1.00 2.40 10.00 76.60 10.00
Table 5: Measured Alloy Chemistries, via Glow Discharge Spectrometry, for Selected
Experimental Ingots
Figure imgf000026_0001
X3 0.00 2.09 22.70 1.23 61.80 1.52 2.62 2.08 3.03 1.31 0.53 41.60
X4 0.00 1.96 21.10 1.13 53.80 1.37 12.60 1.98 2.94 0.94 0.39 42.20
X5 0.00 2.13 22.50 1.09 57.20 1.21 3.13 2.70 3.28 1.14 3.31 34.20
X6 0.56 1.97 23.30 1.21 58.80 1.57 3.03 1.57 3.25 1.21 2.06 61.60
X7 0.28 2.13 22.00 1.27 63.40 1.58 1.33 1.73 3.04 1.43 0.00 52.80
X8 1.08 1.08 23.40 1.21 59.90 1.55 2.85 1.24 3.25 1.28 1.87 52.20
X9 0.00 1.50 22.80 1.10 61.30 1.57 2.84 1.41 2.95 1.20 1.94 34.00
X10 0.30 1.56 22.40 1.15 62.50 1.62 3.14 1.19 2.89 1.22 0.94 34.20
Xll 0.57 0.99 23.10 1.17 62.40 1.77 3.02 0.47 2.90 1.18 1.39 50.40
X12 0.84 1.00 22.70 1.21 62.60 1.78 2.70 1.31 3.05 1.25 0.51 55.20
X13 3.24 22.10 1.29 61.60 1.37 2.19 1.57 3.15 1.36 0.97 50.40
X14 2.96 22.90 1.21 58.40 1.34 5.27 1.44 3.02 1.10 1.03 50.60
X15 2.44 21.60 1.19 61.60 1.51 3.11 1.60 2.74 1.28 0.47 1.81 42.80
X16 3.89 23.50 1.14 56.10 1.38 2.62 1.60 3.17 1.45 0.44 3.75 50.20
X17 2.64 22.50 1.20 60.30 1.43 2.66 1.54 2.96 1.32 0.51 1.74 51.00
X18 3.00 22.90 1.27 56.20 1.40 3.37 1.52 3.04 1.27 0.54 4.11 52.20
X19 4.35 16.20 67.60 0.73 3.77 0.30 0.77 4.55 58.80
X20 3.14 16.50 67.50 0.59 4.81 0.24 0.60 4.51 51.40
X21 4.32 14.90 67.10 0.68 5.21 0.28 0.75 4.57 57.50
X22 3.43 17.00 67.20 0.64 4.42 0.25 0.63 4.53 53.70
X23 4.65 16.40 66.20 0.76 4.56 0.28 0.81 4.34 57.10
X24 3.62 16.90 68.00 0.69 3.73 0.23 0.67 4.58 55.30
X25 4.02 12.70 71.80 0.73 3.83 0.24 0.70 4.39 57.60
X26 3.13 25.00 59.50 0.58 4.47 0.30 0.64 4.37 54.60
X26 2.60 28.20 56.60 0.52 4.64 0.31 0.59 4.18 41.80
X26 2.60 28.20 56.60 0.52 4.64 0.31 0.59 4.18 59.80
X26 2.62 28.00 56.40 0.54 4.82 0.30 0.58 4.35 47.20
X26 2.62 28.00 56.40 0.54 4.82 0.30 0.58 4.35 45.40
X26 2.73 27.60 56.70 0.53 4.82 0.33 0.60 4.19 47.80
X26 2.73 27.60 56.70 0.53 4.82 0.33 0.60 4.19 49.60
X26 2.70 28.30 56.70 0.55 4.37 0.30 0.60 4.29 62.40
X26 2.70 28.30 56.70 0.55 4.37 0.30 0.60 4.29 64.10
X26 3.35 22.90 61.80 0.33 4.35 0.52 0.64 4.18 53.80
X26 3.96 21.3 62.6 0.421 3.99 0.779 0.714 3.73 51.90
X27 2.42 21.20 58.60 0.52 4.77 0.36 0.52 9.49
X27 2.42 24.80 60.40 0.51 4.51 0.26 0.53 4.51 42.60
X27 2.31 23.80 56.60 0.46 4.77 0.36 0.50 8.90 45.00
X27 2.31 23.80 56.60 0.46 4.77 0.36 0.50 8.90 41.60
X27 2.35 23.70 57.90 0.47 4.49 0.34 0.51 8.05 41.20
X27 2.35 23.70 57.90 0.47 4.49 0.34 0.51 8.05 41.40
X27 2.24 24.00 57.90 0.49 4.36 0.31 0.51 8.09 40.20 X27 2.24 24.00 57.90 0.49 4.36 0.31 0.51 8.09 56.60
X27 2.36 23.70 57.70 0.48 4.32 0.34 0.52 8.42 60.20
X27 2.36 23.70 57.70 0.48 4.32 0.34 0.52 8.42 51.40
X27 2.34 19.60 60.90 0.48 4.52 0.59 0.51 9.05 56.80
X28 3.86 29.10 54.10 0.65 4.71 0.35 0.75 4.27 56.60
X29 4.07 28.50 53.50 0.64 5.27 0.37 0.79 4.32 51.00
X30 3.71 30.60 45.10 0.54 5.39 0.50 0.64 10.70 59.80
X31 3.73 30.70 45.20 0.48 4.74 0.53 0.58 11.50 44.80
X32 2.05 31.40 64.00 0.36 0.11 0.26 0.45 0.15 51.00
X33 2.51 28.70 66.10 0.45 0.09 0.28 0.55 0.14 50.20
X34 2.79 26.70 65.60 0.46 0.87 0.17 0.58 1.66 52.60
X35 2.85 25.80 62.10 0.45 2.03 0.23 0.56 4.59 55.40
X36 3.74 24.10 66.00 0.62 0.25 0.64 3.67 52.00
X36 2.84 25.20 65.70 0.57 0.12 0.54 3.82 57.20
X37 3.36 22.70 66.00 0.58 0.26 0.58 5.44 50.40
X37 2.07 25.90 64.00 0.52 0.14 0.47 5.55 65.40
X37 4.06 20.8 66.6 0.587 0.717 0.628 5.24 60.40
X37 4.23 21.90 64.80 0.61 0.66 5.37 67.80
X38 0.96 2.88 23.50 64.60 0.52 0.33 0.57 5.41 65.80
X39 0.44 2.88 22.60 66.20 0.59 0.25 0.60 5.44 58.20
X40 1.10 2.79 18.30 67.00 0.52 1.09 0.31 0.53 7.26 62.00
X41 1.05 2.41 22.60 62.10 0.48 0.39 0.55 9.13 67.00
X42 0.14 3.25 21.50 67.00 0.61 0.25 0.57 5.60 48.80
X43 0.59 2.08 21.40 67.60 0.52 0.25 0.46 5.95
X44 1.11 1.53 24.50 65.20 0.43 0.27 0.45 5.33 61.00
X44 0.851 1.46 24.9 64.5 0.373 0.766 0.414 5.09 65.00
X45 1.09 1.19 25.4 65.5 0.353 0.228 0.31 4.72 66.00
X46 1.06 1.55 22.9 67.7 0.411 0.218 0.396 4.69 55.80
X47 1.93 0.799 23.6 67.4 0.299 0.238 0.276 4.44 54.20
X48 1.65 1.37 24.7 67.3 0.277 0.219 0.357 3.05 62.80
X49 1.53 2.01 18.4 72 0.57 0.259 0.95 3.33 68.40
X50 64.60
X51 1.68 1.65 21.6 64.80 0.4 4.93 63.20
X52 2.31 0.59 10.5 85.00 0.22 65.80
X53 0.01 6.12 13.30 66.00 8.67 57.00
X54 1.93 2.88 12.3 64.2 9.53 4.1 67.20
X55 1.2 2.87 14.4 63.2 11.7 61.00
X56 1.1 3.12 11.9 65 9.32 4.42 68.00
X57 1.75 2.32 10.80 75 5.78 66.00
X58 1.80 1.79 16.60 71.90 0.45 0.48 4.02 64.80
X59 0.97 2.36 13.10 68.1 9.79 56.60 Metal Alloy Composition
[0070] In some embodiments, the disclosed alloys can be iron based alloys having both chromium and carbon in order to form eutectic chromium carbides. In some embodiments, chromium can be from 10-34 (or about 10 to about 34) wt. % and carbon can be form 2.2-4.02 (or about 2.2 to about 4.02) wt. %. In some embodiments, the alloy can be described by a composition in weight percent comprising the following elemental ranges which can meet certain thermodynamic criteria, and which are can be at least partially based on the compositions presented in Table 1 discussed above:
Fe, C: 2.5 - 3.8%, Cr: 10-28%, Mn: 0- 1%, Mo: 0- 1%, Nb: 0-5%, Si: 0- 1%, Ti:0- 0.5%, V: 0-3%, W: 0-9%; or Fe, C: about 2.5 - about 3.8%, Cr: about 10 - about 28%, Mn: about 0 - about 1 %, Mo: about 0 - about 1 %, Nb: about 0 - about 5%, Si: about 0 - about 1 %, Ti: about 0 - about 0.5%, V: about 0 - about 3%, W: about 0 - about 9%
[0071] In some embodiment, the disclosed alloys can be iron based alloys comprising chromium, carbon, and tungsten forming eutectic carbides of primarily the M23C6 type of at least 60 mole %, and in which the melt range is at 50K or lower. In some embodiments the alloy range can be at least partially described by the compositions found in Table 3 and can be from C: 3.2-4%, Cr: 6-20%, W: 4-10% (or C: about 3.2 - about 4%, Cr: about 6 - about 20%, W about 4 - about 10%).
[0072] In some embodiments, the alloy can be described by a composition in weight percent comprising the following elemental ranges which have been produced and evaluated experimentally, and which are at least partially based on the compositions presented in Table 4 and Table 5:
Fe, B: 0-2%, C: 1 - 3.8%, Cr: 15-34%, Cu:0-1.2%, Mn: 0-2%, Mo: 0-3%, Nb: 0.5- 5%, Si: 0-1.5%, Ni:0-2.5%, Ti:0-4%, V: 0-5%, W: 0-15%; or Fe, B: about 0 - about 2%, C: about 1 - about 3.8%, Cr: about 15 - about 34%, Cu: about 0 - about 1.2%, Mn: about 0 - about 2%, Mo: about 0 - about 3%, Nb: about 0.5 - about 5%, Si: about 0 - about 1.5%, Ni: about 0 - about 2.5%, Ti: about 0 - about 4%, V: about 0 - about 5%, W: about 0 - about 15%.
[0073] In some embodiments, the alloy can be described by a composition in weight percent comprising the following elemental ranges which have been produced and evaluated experimentally and which can meet certain microstructural criteria, and which are at least partially based on the compositions presented in Table 4 and Table 5 above:
Fe, C: 2.2-4.02%, Cr: 12.7-34%, Mn: 0-0.73%, Nb: 3.83-5%, Ni:0-0.3%, Si:0-0.7%, W: 4.37-9%; or Fe, C: about 2.2 - about 4.02%, Cr: about 12.7 - about 34%, Mn: about 0 - about 0.73%, Nb: about 3.83 - about 5%, Ni: about 0 - about 0.3%, Si: about 0 - about 0.7%, W: about 4.37 - about 9%.
[0074] In some embodiments, the alloy can be described by a composition in weight percent comprising the following elemental ranges as defined through glow discharge spectrometer readings, which have been produced and evaluated experimentally and which can meet certain microstructural criteria, and which are at least partially based on the compositions presented in Table 5 above:
Fe, C: 3.1-4.02%, Cr: 12.7-25%, Mn: 0.58-0.73%, Nb: 3.83-4.5%, Ni:0.24-0.3%, Si:0.64-0.7%, W: 4.37-9%; or Fe, C: about 3.1 - about 4.02%, Cr: about 12.7 - about 25%, Mn: about 0.58 - about 0.73%, Nb: about 3.83 - about 4.5%, Ni: about 0.24 - about 0.3%, Si: about 0.64 - about 0.7%, W: about 4.37 - about 9%.
[0075] In some embodiments, the alloy can be described by specific compositions in weight percent comprising the following elements, which have been produced and evaluated experimentally and which can meet certain microstructural criteria, and which are at least partially based on the nominal and measured experimental compositions:
Fe, C:2.2, Cr:24, Nb: 5, W: 9; or Fe, C: about 2.2, Cr: about 24, Nb: about 5, W: about 9
Fe, C:3.4, Cr:34, Nb: 5, W: 5; or Fe, C: about 3.5, Cr: about 34, Nb: about 5, W: about 5 Fe, C:4, Cr: 12.7, Mn:0.7, Nb: 3.8, Ni: 2.4, Si:0.7, W: 4.4; or Fe, C: about 4, Cr: about 12.7, Mn: about 0.7, Nb: about 3.8, Ni: about 2.4, Si: about 0.7, W: about 4.4
Fe, C:3.1, Cr:25, Mn:0.6, Nb: 4.5, Ni: 0.3, Si:0.6, W: 4.4; or Fe, C: about 3.1 , Cr: about 25, Mn: about 0.6, Nb: about 4.5, Ni: about 0.3, Si: about 0.6, W: about 4.4
[0076] In some embodiments, the Fe compositions listed above can be the balance of the alloy material. In some embodiments, minor impurities can also be found within the composition.
[0077] As an example of embodiments of the above alloys, increased carbide content can be advantageous because a high fraction of primary (Nb, Ti, V) carbides can effectively increase the liquidus temperature of an alloy and decreases fluidity, which can improve casting processes.
Applications and Processes for Use
[0078] Embodiments of the disclosed alloys can be used in a variety of applications and industries. Some non-limiting examples of applications of use include:
[0079] Surface mining applications: Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: wear resistant sleeves and/or wear resistant hardfacing for slurry pipelines, mud pump components including pump housing or impeller or hardfacing for mud pump components, ore feed chute components including chute blocks or hardfacing of chute blocks, separation screens including but not limited to rotary breaker screens, banana screens, shaker screens, liners for autogenous grinding mills and semi-autogenous grinding mills, ground engaging tools and hardfacing for ground engaging tools, wear plate for buckets and dumptruck liners, heel blocks and hardfacing for heel blocks on mining shovels, grader blades and hardfacing for grader blades, stacker reclaimers, siazer crushers, general wear packages for mining components, and other communition components.
[0080] Downstream oil and gas applications: Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: downhole casing and downhole casing, drill pipe and coatings for drill pipe including hardbanding, mud management components, mud motors, fracking pump sleeves, fracking impellers, tracking blender pumps, stop collars, drill bits and drill bit components, directional drilling equipment and coatings for directional drilling equipment including stabilizers and centralizers, blow out preventers and coatings for blow out preventers and blow out preventer components including the shear rams, oil country tubular goods, and coatings for oil country tubular goods.
[0081] Upstream oil and gas applications: Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: process vessels and coating for process vessels including steam generation equipment, amine vessels, distillation towers, cyclones, catalytic crackers, general refinery piping, corrosion under insulation protection, sulfur recovery units, convection hoods, sour stripper lines, scrubbers, hydrocarbon drums, and other refinery equipment and vessels.
[0082] Pulp and paper applications: Embodiments of the disclosed alloys can be included in following components and coatings for the following components: rolls used in paper machines including yankee dryers and other dryers, calendar rolls, machine rolls, press rolls, digesters, pulp mixers, pulpers, pumps, boilers, shredders, tissue machines, roll and bale handling machines, doctor blades, evaporators, pulp mills, head boxes, wire parts, press parts, M.G. cylinders, pope reels, winders, vacuum pumps, deflakers, and other pulp and paper equipment,
[0083] Power generation applications: Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: boiler tubes, precipitators, fireboxes, turbines, generators, cooling towers, condensers, chutes and troughs, augers, bag houses, ducts, ID fans, coal piping, and other power generation components.
[0084] Agriculture applications: Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: chutes, base cutter blades, troughs, primary fan blades, secondary fan blades, augers, and other agricultural applications.
[0085] Construction applications: Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: cement chutes, cement piping, bag houses, mixing equipment, and other construction applications [0086] Machine element applications: Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: shaft journals, paper rolls, gear boxes, drive rollers, impellers, general reclamation and dimensional restoration applications, and other machine element applications
[0087] Steel applications: Embodiments of the disclosed alloys can be included in the following components and coatings for the following components: cold rolling mills, hot rolling mills, wire rod mills, galvanizing lines, continue pickling lines, continuous casting rolls and other steel mill rolls, and other steel applications.
[0088] Further, embodiments of the alloys described can be produced and or deposited in a variety of techniques effectively. Some non-limiting examples of processes include:
[0089] Thermal spray process, including those using a wire feedstock such as twin wire arc, spray, high velocity arc spray, combustion spray and those using a powder feedstock such as high velocity oxygen fuel, high velocity air spray, plasma spray, detonation gun spray, and cold spray. Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire. Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.
[0090] Welding processes, including those using a wire feedstock including but not limited to metal inert gas (MIG) welding, tungsten inert gas (TIG) welding, arc welding, submerged arc welding, open arc welding, bulk welding, laser cladding, and those using a powder feedstock including but not limited to laser cladding and plasma transferred arc welding. Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire. Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.
[0091] Casting processes, including processes typical to producing cast iron including but not limited to sand casting, permanent mold casting, chill casting, investment casting, lost foam casting, die casting, centrifugal casting, glass casting, slip casting and process typical to producing wrought steel products including continuous casting processes. [0092] Post processing techniques, including but not limited to rolling, forging, surface treatments such as carburizing, nitriding, carbonitriding, heat treatments including but not limited to austenitizing, normalizing, annealing, stress relieving, tempering, aging, quenching, cryogenic treatments, flame hardening, induction hardening, differential hardening, case hardening, decarburization, machining, grinding, cold working, work hardening, and welding.
[0093] From the foregoing description, it will be appreciated that an inventive material and methods of manufacturing are disclosed. While several components, techniques and aspects have been described with a certain degree of particularity, it is manifest that many changes can be made in the specific designs, constructions and methodology herein above described without departing from the spirit and scope of this disclosure.
[0094] Certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations, one or more features from a claimed combination can, in some cases, be excised from the combination, and the combination may be claimed as any subcombination or variation of any subcombination.
[0095] Moreover, while methods may be depicted in the drawings or described in the specification in a particular order, such methods need not be performed in the particular order shown or in sequential order, and that all methods need not be performed, to achieve desirable results. Other methods that are not depicted or described can be incorporated in the example methods and processes. For example, one or more additional methods can be performed before, after, simultaneously, or between any of the described methods. Further, the methods may be rearranged or reordered in other implementations. Also, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described components and systems can generally be integrated together in a single product or packaged into multiple products. Additionally, other implementations are within the scope of this disclosure.
[0096] Conditional language, such as "can," "could," "might," or "may," unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include or do not include, certain features, elements, and/or steps. Thus, such conditional language is not generally intended to imply that features, elements, and/or steps are in any way required for one or more embodiments.
[0097] Conjunctive language such as the phrase "at least one of X, Y, and Z," unless specifically stated otherwise, is otherwise understood with the context as used in general to convey that an item, term, etc. may be either X, Y, or Z. Thus, such conjunctive language is not generally intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.
[0098] Language of degree used herein, such as the terms "approximately," "about," "generally," and "substantially" as used herein represent a value, amount, or characteristic close to the stated value, amount, or characteristic that still performs a desired function or achieves a desired result. For example, the terms "approximately", "about", "generally," and "substantially" may refer to an amount that is within less than or equal to 10% of, within less than or equal to 5% of, within less than or equal to 1 % of, within less than or equal to 0.1 % of, and within less than or equal to 0.01 % of the stated amount.
[0099] Some embodiments have been described in connection with the accompanying drawings. The figures are drawn to scale, but such scale should not be limiting, since dimensions and proportions other than what are shown are contemplated and are within the scope of the disclosed inventions. Distances, angles, etc. are merely illustrative and do not necessarily bear an exact relationship to actual dimensions and layout of the devices illustrated. Components can be added, removed, and/or rearranged. Further, the disclosure herein of any particular feature, aspect, method, property, characteristic, quality, attribute, element, or the like in connection with various embodiments can be used in all other embodiments set forth herein. Additionally, it will be recognized that any methods described herein may be practiced using any device suitable for performing the recited steps. [0100] While a number of embodiments and variations thereof have been described in detail, other modifications and methods of using the same will be apparent to those of skill in the art. Accordingly, it should be understood that various applications, modifications, materials, and substitutions can be made of equivalents without departing from the unique and inventive disclosure herein or the scope of the claims.

Claims

WHAT IS CLAIMED IS:
1. A chromium white iron alloy comprising:
a composition comprising Fe, Cr, and C, the composition being predominantly
Fe;
wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume % ; and
wherein a melt temperature range of the alloy is below about 200 °C.
2. The chromium white iron alloy of Claim 1, wherein the melt temperature range is below about 300 °C.
3. The chromium white iron alloy of Claim 1, wherein the melt temperature range is below about 100 °C.
4. The chromium white iron alloy of Claim 1, wherein the alloy can be formed into a sleeve or layer for use in pipelines designed to carry abrasive slurries.
5. The chromium white iron alloy of Claim 1, wherein a maximum carbide fraction is 50% mole fraction or higher.
6. The chromium white iron alloy of Claim 1, wherein a maximum carbide fraction is 60% mole fraction or higher.
7. The chromium white iron alloy of Claim 1, wherein the composition comprises, in weight %:
Fe;
C: 3.2 - 4%;
Cr: 6-20%; and
W: 4-10%.
8. The chromium white iron alloy of Claim 1, wherein the composition comprises, in weight %:
Fe;
C: about 2.5 - about 3.8%;
Cr: about 10 - about 28%;
Mn: about 0 - about 1%;
Mo: about 0 - about 1%;
Nb: about 0 - about 5%;
Si: about 0 - about 1%;
Ti: about 0 - about 0.5%;
V: about 0 - about 3%; and
W: about 0 - about 9%.
9. A wear resistant component comprising the chromium white iron alloy Claim 1.
10. A method of manufacturing a chromium white iron alloy comprising:
providing an alloy comprising Fe, Cr, and C, the alloy being predominantly
Fe;
wherein a total carbide and boride content in a microstructure of the alloy exceeds 40 volume %; and
wherein a melt temperature range of the alloy is below about 300 °C; and forming a component from the alloy.
11. The method of Claim 10, wherein a grain size of substantially all of the carbides does not exceed 50 micrometers in their longest dimension.
12. The method of Claim 10, wherein a total carbide content in the microstructure of the alloy exceeds 60 volume %.
13. The method of Claim 10, wherein the melt temperature range is below about
100 °C.
14. The method of Claim 10, wherein forming the component comprises forming the component via a casting process.
15. The method of Claim 10, wherein the composition comprises, in weight %:
Fe;
C: about 3.2 - about 4%;
Cr: about 6 - about 20%; and
W: about 4 - about 10%.
16. The method of Claim 10, wherein the composition comprises in weight %:
Fe;
C: about 2.5 - about 3.8%;
Cr: about 10 - about 28%;
Mn: about 0 - about 1%;
Mo: about 0 - about 1%;
Nb: about 0 - about 5%;
Si: about 0 - about 1%;
Ti: about 0 - about 0.5%;
V: about 0 - about 3%; and
W: about 0 - about 9%.
17. A chromium white iron alloy comprising:
a composition comprising Fe, Cr, and C, the composition being predominantly
Fe;
a maximum carbide fraction in the alloy which is thermodynamically stable at temperatures ranging from the room temperature to a temperature where the alloy is 100% liquid of 40% mole fraction; and a segregated carbide fraction, defined as Fe,Cr - rich carbides existing at a temperature above the highest temperature at which an austenite or ferrite iron based matrix phase is thermodynamically stable, of 5% mole fraction or lower.
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