EP3438304B1 - Alliage biphasé à base de chrome et son produit - Google Patents

Alliage biphasé à base de chrome et son produit Download PDF

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Publication number
EP3438304B1
EP3438304B1 EP17773605.5A EP17773605A EP3438304B1 EP 3438304 B1 EP3438304 B1 EP 3438304B1 EP 17773605 A EP17773605 A EP 17773605A EP 3438304 B1 EP3438304 B1 EP 3438304B1
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phase
alloy
mass
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alloys
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EP3438304A1 (fr
EP3438304A4 (fr
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Tomonori Kimura
Masafumi Noujima
Yasuhisa Aono
Makoto Ogata
Naoya Tokoo
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Hitachi Ltd
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Hitachi Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/022—Casting heavy metals, with exceedingly high melting points, i.e. more than 1600 degrees C, e.g. W 3380 degrees C, Ta 3000 degrees C, Mo 2620 degrees C, Zr 1860 degrees C, Cr 1765 degrees C, V 1715 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon

Definitions

  • the present invention relates to a two-phase alloy containing a Cr (chromium).
  • Materials for apparatus for oil wells or natural gas wells are often exposed to an extremely severe acidified corrosion atmosphere containing a chloride ion, or containing a corrosive gas of carbon dioxide (CO 2 ) or hydrogen sulfide (H 2 S) .
  • Materials exposed to such a severe corrosion atmosphere are also found in those of apparatus constituting, for example, a waste product plant, a chemical plant, an atomic power plant, and a nuclear fuel reprocessing facility.
  • Properties required for these materials for apparatus generally include good corrosion resistance and strength.
  • abrasion resistance is additionally required.
  • Ni based alloys As materials for apparatus having such properties, for example, low-alloy steels, stainless steels, and Ni based alloys have been used in accordance with severity of a corrosion atmosphere. In choosing materials, when better strength properties (maintaining high proof stress and toughness) and cost advantage are required in addition to a higher corrosion resistance, stainless steels are more advantageous. Ni based alloys are inferior in cost advantage because it is mainly composed of costly Ni. When abrasion resistance is required, alloys, in which a hard phase is precipitated in its corrosion resistance matrix phase, such as Stellite(R) of Co based alloys are widely used as, for example, cladding materials.
  • Stellite(R) of Co based alloys are widely used as, for example, cladding materials.
  • a two-phase stainless steel is advantageous in balance between corrosion resistance and strength properties.
  • the two-phase stainless steel generally contains Cr, Ni, Mo, and N to maintain corrosion resistance.
  • two-phase stainless steels containing Cu to improve the corrosion resistance are disclosed (see, e.g., PTL 1 and PTL 2).
  • PTL 1 and PTL 2 two-phase stainless steels containing Cu to improve the corrosion resistance.
  • further enhancement and improvement of the corrosion resistance and strength of the two-phase stainless steel are required.
  • sufficient abrasion resistance of the two-phase stainless steel cannot be expected as a slide member used under a corrosion atmosphere.
  • Cr based alloys which contains more than 60% by mass of Cr and includes a ferrite single phase having a crystalline structure of the body-centered cubic structure to improve corrosion resistance and heat resistance are disclosed (see PTL 3, PTL 4, and PTL 5).
  • corrosion resistance and abrasion resistance can be expected.
  • they lack ductility and are very brittle.
  • an object of the present invention is to provide a two-phase alloy including a ferrite phase and an austenite phase, which is superior in strength properties such as corrosion resistance, proof stress, and toughness, and in abrasion resistance to conventional materials of a two-phase stainless steel and a Cr based single phase alloy even under a severe corrosion atmosphere, and which contains inexpensive Cr as a main component, by adding an element such as Cu which is effective for further improving the high corrosion resistance achieved by enrichment of the Cr.
  • the present inventors produced a Cr based two-phase alloy which has a main composition of Cr-Ni-Fe containing 33% by mass or more of Cr, and which contains Cu and others using different production processes. That is, an alloy having a two-phase structure including ferrite and austenite which contains Cu is produced by using an ingot produced in a melting-casting step as a master ingot followed by steps of 1) a step of heat treatment including a hot forging-solution treatment of the master ingot, 2) a step of re-melting-casting the master ingot, and 3) a step of re-melting-gas atomization of the master ingot. Then, the present inventors evaluated corrosion resistance, mechanical properties, and abrasion resistance of the alloy to accomplish the present invention.
  • the present invention according to claim 1 is a Cr based two-phase alloy including two phases of a ferrite phase and an austenite phase in a mixed state, in which a chemical composition of the Cr based two-phase alloy consists of a major component, an accessory component, impurities, a first optional accessory component, and a second optional accessory component;
  • the major component consists of 33% by mass or more and 65% by mass or less of Cr (chromium), 18% by mass or more and 40% by mass or less of Ni (nickel), and 10% by mass or more and 33% by mass or less of Fe (iron);
  • the accessory component consists of 0.1% by mass or more and 2% by mass or less of Mn (manganese), 0.1% by mass or more and 1.0% by mass or less of Si (silicon), 0.005% by mass or more and 0.05% by mass or less of Al (aluminum), and 0.1% by mass or more and 5.0% by mass or less of Cu (copper); and the impurities contain more than 0% by mass
  • a two-phase alloy which contains inexpensive Cr as a main component, and which is superior in strength properties such as corrosion resistance and toughness, and in abrasion resistance to conventional ones under a high corrosion circumstance can be provided.
  • a two-phase alloy of an embodiment of the present invention is described in detail below.
  • a two-phase alloy of an embodiment of the present invention is a two-phase alloy which has a composition of Cr-Ni-Fe containing Cr as a main component, and which contains Cu and other elements to further improve corrosion resistance.
  • This two-phase alloy is formed of two phases including a ferrite phase and an austenite phase as a main phase structure, and contains Ni, Fe, Mn, Si, Al, Cu, Mo, and others in predetermined amounts, and the remnants consisting of Cr and unavoidable impurities.
  • at least one of V, Nb, Ta, and Ti is added. Each of the constituents of the two-phase alloy is described below.
  • a material structure in s two-phase alloy of the present embodiments is a two-phase structure including a ferrite phase and an austenite phase.
  • the two-phase structure is formed by different production methods described below, that is, via the steps of thermal processing, casting, or gas atomizing a master ingot. Then, a material structure of hot working materials differs from a material structure of cast materials or cladding materials using a gas atomized powder.
  • the former basically facilitates sufficient elimination of segregation of components, and micronization of the structure. However, the latter basically has a solidified structure which allows segregation of components.
  • Cr based alloys including a ferrite single phase having a crystalline structure of the body-centered cubic structure has higher mechanical strength and superior in abrasion resistance, but is inferior in toughness. In particular, it is characterized in that when contents of C, N, and O increase, plastic deformation properties decrease sensitively.
  • Ni based alloys including an austenite single phase having a face-centered cubic structure is ductile and superior in toughness, but is costly.
  • a two-phase alloy of the present embodiments contains Cr as a main component, and consists of a ferrite phase and an austenite phase.
  • the two-phase alloy has a high corrosion resistance due to high Cr concentration and addition of Cu, and is superior in strength including toughness and in abrasion resistance, and also is economical.
  • An occupation ratio of the ferrite phase in a two-phase alloy of the present embodiments (hereinafter simply referred to as a "ferrite ratio”) can be set to in a range of 10% or more and 95% or less, and the occupation ratio of the austenite phase can be set to in a range of 5% or more and 90% or less in accordance with the ferrite ratio.
  • the reason why the ferrite ratio is set to 95% or less so that the austenite phase is contained is to maintain toughness.
  • a structure having a higher ferrite ratio contains a higher concentration of Cr in the composition, and is observed in a quench-solidified structure, for example, in cladding welding.
  • a range of chemical compositions of a two-phase alloy of the present embodiments is defined.
  • the range of the chemical compositions is especially controlled between contents of Cr and Ni, which are the main components.
  • the ferrite ratio further increases in a high Cr content two-phase alloy. Accordingly, in order to maintain the above-described predetermined ferrite ratio of 95% or less, decreasing the Cr content ratio to increase the Ni content is generally required as shown in the following ⁇ chemical composition>.
  • phase ratio control controlling the ratio between a ferrite and an austenite phases (phase ratio control) in a range of 800 to 1000°C, the ferrite ratio of 95% or less can certainly be maintained.
  • the "ferrite ratio” in the present embodiments refers to an occupation ratio of ferrite [%] obtained by EBSP (Electron BackScattering Pattern) analysis.
  • a ferrite ratio in a two-phase alloy of the present embodiments is more preferably 20% or more and 70% or less.
  • the two-phase alloy in the present embodiments is preferably a two-phase alloy containing no hard different phase such as a sigma ( ⁇ ) phase which is precipitated by phase-transition from a ferrite phase.
  • ⁇ sigma
  • the hard phase is tolerated when it is contained to such an extent that diverse properties such as mechanical properties are not considerably impaired.
  • Cr is a component of remnants, and its concentration is the highest in those of constituent components of the two-phase alloy.
  • Cr is a Cr based ferrite phase-forming element with a high mechanical strength as a material, and it improves corrosion resistance as a solid solution element.
  • the Cr content is set so that a two-phase structure including a ferrite phase and an austenite phase may be formed as a thermal equilibrium state structure of the major ternary system at a solution treatment temperature of 1050 to 1250°C as described below.
  • the content of Cr is 33% or more in consideration of an amounts of the major components including Ni and Fe, an amounts of minor components such as active elements including Mn, Si, Al, Cu, Mo, P, S, C, N, O, and V, and amounts of unavoidable impurities.
  • amount of Cr is set to 33% or more, a high concentration of Cr is achieved to result in further improvement in corrosion resistance of the two-phase alloy.
  • the content of Cr is 65% or less.
  • the content of Cr is set to 65% or less, superior toughness can be imparted to the two-phase alloy while high proof stress and high hardness are maintained.
  • the content of Cr is reduced to maintain a ferrite ratio of 95% or less, and is preferably 60% or less.
  • a chemical composition of the Cr based two-phase alloy consists of a major component, an accessory component, impurities, a first optional accessory component, and a second optional accessory component.
  • the major component is composed of Cr, Ni, and Fe;
  • the accessory component is composed of Mn, Si, Al, and Cu;
  • the impurities is composed of P, S, C, N, and O;
  • the first optional accessory component is composed of Mo (molybdenum); and the second optional accessory component is composed of V (vanadium), Nb (niobium), Ta (tantalum), and Ti (titanium).
  • Ni stabilizes an austenite phase and maintains a two-phase state with a ferrite phase in a solution treatment. In addition, Ni ensures and imparts corrosion resistance, and also ductility and toughness to the two-phase alloy.
  • the content of Ni is set to 18% or more. This results in the occupation ratio of the austenite phase of 10% or more at solution treatment temperature described below, and contributes to further improving toughness of the structure.
  • a structure with a high ferrite ratio is formed as described above, the content of Ni is increased to maintain a ferrite ratio of 95% or less, and is preferably 23% or more.
  • the content of Ni is set to 40% or less. This results in a ferrite ratio of 10% or more at solution treatment temperature described below.
  • the content of Fe is set to 10% or more. This reduces the contents of Ni and Cr, which are more expensive than Fe, and suppresses production of an intermetallic compound which may exert a harmful effect on strength properties in a melt extraction process of a two-phase alloy.
  • the content of Fe is set to 33% or less.
  • a ⁇ phase is produced at temperature range around 800°C as the center.
  • the content of Fe is set to 33% or less, production of the ⁇ phase is suppressed.
  • the total content ratio of Ni component and Fe component is preferably 37% by mass or more and 65% by mass or less. When the total content ratio becomes less than 37% by mass, ductility/toughness of the two-phase alloy becomes insufficient. On the other hand, when the total content ratio becomes more than 65% by mass, mechanical strength is significantly reduced.
  • the content of Mn is set to 0.1% or more. This allows desulfurization and deoxidation of the two-phase alloy to improve strength and toughness of the two-phase alloy.
  • Preferred lower limit is 0.3%.
  • the content of Mn is set to 2.0% or less. This prevents deterioration of corrosion resistance and strength caused by formation of bulky MnS, and maintains preferred resistance properties of the two-phase alloy against corrosion by carbon dioxide gas.
  • the content of Si is set to 0.1% or more. This allows deoxidation of the two-phase alloy, and improves strength and toughness of the two-phase alloy. Preferred lower limit is 0.3%.
  • the content of Si is set to 1.0% or less. This brings about sufficient effects of a hot forging step described below, and maintains a preferred toughness of the two-phase alloy.
  • the content of Al is set to 0.005% or more. This improves a deoxidation effect in conjunction with Mn and Si. More preferred lower limit is 0.008%.
  • the content of Al is set to 0.05% or less. Reduction of the amount of oxygen in a Cr based two-phase alloy of the present invention is indispensable for maintaining hot forging properties and toughness of an alloy of the present invention. The content of oxygen is reduced as low as possible during production. On the other hand, Al 2 O 3 and AlN, which are produced when a lot of Al is contained, impair toughness of the alloy, and thus the production should be suppressed as low as possible.
  • the content of Al is preferably 0.05% or less.
  • Cu is an element which increases corrosion resistance of a Cr based two-phase alloy of the present invention similarly to Mo, and can be included together as required to enhance the effect cooperatively.
  • the content is set to 0.1% or more.
  • an austenite phase is stabilized.
  • the amount included is excessive, Cu precipitates are produced during hot working specifically in a ferrite phase, leading to decreased processability. Accordingly, it is desirably 5.0% or less, and preferably 3.0% or less.
  • Mo is an element which increases corrosion resistance of the Cr based two-phase alloy, is effective specifically in stabilization of passivation film, and raises an increased expectation of pitting resistance properties.
  • Mo can be included together as required to enhance the effect cooperatively.
  • the content is set to 0.1% or more.
  • Mo is included, a ferrite phase is stabilized.
  • it is desirably 3% or less, and preferably 2% or less.
  • the content of P is set to 0.04% or less.
  • P is an element which deteriorates corrosion resistance, weldability, and processability, and thus it should be limited as low as possible in production.
  • the content of P is set to 0.04% or less, segregation of P at the crystal grain boundary is prevented, and preferred toughness of the two-phase alloy and corrosion resistance at the grain boundary are maintained.
  • the lower limit of P is the detection limit of an analysis or less, and it must not be included in the two-phase alloy, that is, may be 0%.
  • the content of S is set to 0.01% or less.
  • S is an element which produces a sulfide such as MnS to deteriorate corrosion resistance and processability, and thus it should be limited as low as possible in production.
  • the content of S is set to 0.01% or less, the amount of a sulfide is reduced, and preferred pitting resistance properties and toughness are maintained.
  • the lower limit of S is the detection limit of an analysis or less, and it must not be included in the two-phase alloy, that is, may be 0%.
  • C provides, when its concentration is increased, solid solution hardening of C at a low concentration, and significantly prevents plastic deformation specifically in a ferrite phase. At a high concentration, specifically, it causes formation of a Cr carbide and reduces local Cr concentration around it, leading to decrease in corrosion resistance. Large amount of the carbide causes decrease in toughness.
  • active elements of V, Nb, Ta, and Ti are added, in order to reduce formation of their carbides, the content of C is desirably reduced, and is preferably 0.03% or less.
  • the lower limit of C is the detection limit of an analysis or less, and it must not be included in the two-phase alloy, that is, may be 0%.
  • N improves, when its concentration is increased, solid solution hardening and corrosion resistance of N. However, at a higher concentration, there is a concern that toughness may be decreased by formation of a nitride such as Cr.
  • the content of N is desirably 0.02% or less. Furthermore, when cleaner refine and production processes are used, the content of N can be further reduced. Accordingly, the lower limit of N is the detection limit of an analysis or less, and it must not be contained in the two-phase alloy, that is, may be 0%.
  • the content of O is desirably 0.03% or less. Furthermore, when cleaner refine and production processes are used, the content of O can be further reduced. Accordingly, the lower limit of O is the detection limit of an analysis or less, and it must not be contained in the two-phase alloy, that is, may be 0%.
  • V binds to gaseous impurities of C, N, and O to form respective compounds, and then gaseous impurities are gathered and immobilized. This effect of cleaning substrate materials is effective for improving toughness.
  • a preferred amount of V added in production in which an amount of V in excess of that used for immobilization is reduced as low as possible is, in atomic % (at%), preferably in a range between 0.8 times or more and 2 times or less of the total at% of C, N, and O.
  • the total amount including V is also preferably in a range between 0.8 times or more and 2 times or less.
  • Nb binds to gaseous impurities of C, N, and O to form respective compounds, and then gaseous impurities are gathered and immobilized. This effect of cleaning substrate materials is effective for improving toughness.
  • a preferred amount of Nb added in production in which an amount of Nb in excess of that used for immobilization is reduced as low as possible is, in atomic % (at%), preferably in a range between 0.8 times or more and 2 times or less of the total at% of C, N, and O.
  • the total amount including Nb is also preferably in a range between 0.8 times or more and 2 times or less.
  • Ta binds to gaseous impurities of C, N, and O to form respective compounds, and then gaseous impurities are gathered and stabilized. This effect of cleaning substrate materials is effective for improving toughness.
  • Ta when Ta is added excessively, Ta readily reacts with other component elements to form respective intermetallic compounds, leading to concern about decrease in toughness.
  • a preferred amount of Ta added in production in which an amount of Ta in excess of that used for immobilization is reduced as low as possible is, in atomic % (at%), preferably in a range between 0.8 times or more and 2 times or less of the total at% of C, N, and O.
  • the total amount including Ta is also preferably in a range between 0.8 times or more and 2 times or less.
  • Ti binds to gaseous impurities of C, N, and O to form respective compounds, and then gaseous impurities are gathered and stabilized. This effect of cleaning substrate materials is effective for improving toughness.
  • Ti when Ti is added excessively, Ti readily reacts with other component elements to form respective intermetallic compounds, leading to concern about decrease in toughness.
  • a preferred amount of Ti added in production in which an amount of Ti in excess of that used for immobilization is reduced as low as possible is, in atomic % (at%), preferably in a range between 0.8 times or more and 2 times or less of the total at% of C, N, and O.
  • the total amount including Ti is also preferably in a range between 0.8 times or more and 2 times or less.
  • a two-phase alloy of the present invention is provided, as the final product form, as hot working materials produced in a series of production steps of, for example, melting-ingot forming-hot forging-solution treatment steps, a cast material from re-melting of the master ingot, and a powder from an atomizing process.
  • Fig. 1 is an operation flowchart for illustrating a method for producing a two-phase alloy according to the present embodiments.
  • the above-described Cr, Ni, Fe, Mn, Si, Al, Cu, and Mo as the materials, and as required, at least one or more of V, Nb, Ta, and Ti in predetermined amounts are melted in a high frequency vacuum melting furnace to form an alloy (step F1).
  • the melting furnace used in this step is not limited to the high frequency vacuum melting furnace, but other melting furnaces can be used in the present invention.
  • an ingot is formed by casting using a predetermined die (step F2).
  • the resulting ingot can be also used as a cast material of the two-phase alloy and a master ingot for powder production as described below.
  • the ingot is subjected to hot forging treatment (step F3).
  • hot forging can be performed on the ingot using a press forging machine or a hammer forging machine to provide a required product shape.
  • the temperature for hot forging is set to about 1050 to 1250°C. The hot forging can prevent component segregation and facilitate structure micronization in the ingot.
  • hot rolling can be performed at a temperature in a range of 1050°C or more if a plate-shaped two-phase alloy is desired, and hot extrusion can be performed at the above-described temperature range if a tube-shaped two-phase alloy is desired.
  • step F4 structure of the two-phase alloy is basically defined.
  • the temperature of the solution heat treatment is, in order to sufficiently produce solid solution of constituent atoms and eliminate lattice defects such as dislocation which remains after hot working, desirably in a range of 1050 to 1250°C, and preferably 1100 to 1200°C.
  • the ferrite ratio of the two-phase alloy of 10 to 95% can be adequately achieved.
  • step F5 a so-called an aging heat treatment is performed (step F5) to facilitate phase-transition from a ferrite phase to an austenite phase, and from an austenite phase to a ferrite phase in high Ni conditions.
  • the phase ratio can be controlled to be a desired value in a range of 10 to 95%.
  • Conditions of the aging heat treatment desirably include, in accordance with an extent of the phase ratio control, a solution treatment temperature of 1050 to 1250°C, an aging treatment temperature of 800 to 1000°C, and an aging time of 0.5 to 6 hours
  • a solution treatment temperature of 1050 to 1250°C an aging treatment temperature of 800 to 1000°C
  • an aging time of 0.5 to 6 hours In a two-phase alloy with higher Cr concentration, although it is expected that at a solution treatment temperature of 1150°C or more the ferrite ratio may be more than 90%, a phase ratio can be controlled within the above-defined phase ratio by an aging heat treatment.
  • the ferrite phase when the two-phase alloy has a ferrite ratio of about 30% or more, the ferrite phase can be decreased and an austenite phase can be increased in amounts to improve elongation and toughness of the two-phase alloy.
  • an alloy having a ferrite ratio of about 30% or less in which an austenite phase is fairly dominant when an austenite phase is decreased and a ferrite phase is increased by aging, proof stress and tensile strength can be improved.
  • an active element-added two-phase alloy is subjected to a solution heat treatment, and then subjected to an aging heat treatment step similar to that described above is performed (step F5) to complete a series of the method for producing the two-phase alloy.
  • the aging heat treatment can cause an appropriate aging reaction between the active element and C, N, and O, that is, it can produce precipitates of these compounds.
  • the above-described phase ratio control can be achieved.
  • Conditions of the aging heat treatment desirably include a solution treatment temperature of 1050 to 1250°C, an aging treatment temperature of 800 to 1000°C, and an aging time of 0.5 to 6 hours.
  • the final heat treatment step in such a method for producing the two-phase alloy may, in accordance with desired corrosion resistance and strength properties, be a solution heat treatment step, or the method may be carried out including an aging heat treatment step subsequent to the solution heat treatment.
  • a hot forging step of an ingot and a subsequent heat treatment step are performed, which leads to elimination of casting defects and destruction of a bulky two-phase cast solidified structure containing segregates of alloy elements and having a high ferrite phase occupation ratio. Accordingly, a two-phase alloy of the present embodiments having a two-phase structure which is homogeneous in chemical composition and structure, and thermodynamically more stable can be obtained.
  • a two-phase alloy according to the present embodiments which is obtained by hot forging and heat treating an ingot consisting of the above-specified chemical composition under the above-specified conditions, includes two phases of a ferrite phase containing Cr as a main component and an austenite phase.
  • Such a two-phase alloy of the present embodiments contains inexpensive Cr as a main component, and is superior in strength properties such as corrosion resistance and toughness to conventional ones even under a high corrosion circumstance such as in an oil well.
  • Fig. 2 is an operation flowchart for illustrating a method for producing a two-phase alloy cast material according to the present embodiments.
  • a master ingot casted in step F2 of the steps in Fig. 1 is used as a raw material.
  • the master ingot is re-melted in a melting furnace such as a high frequency or induction furnace (step C1), and then casted in a mold (step C2) to produce a cast material.
  • An atmosphere for melting and casting may be the air, an inert gas, or a vacuum depending on purposes. In order to prevent pollution such as oxidation as low as possible, a clean casting in an inert gas or vacuum is preferred.
  • the cast material has a solidified structure.
  • An additional heat treatment can be further performed after the casting to improve segregation of component elements. Accordingly, desired corrosion resistance and strength properties can be achieved.
  • the cast material can be subjected to a solution treatment for, for example, homogenization of constituent components, and subsequently subjected to a heat treatment including aging (step C3).
  • the temperature of the solution heat treatment is desirably about 1050 to 1250°C, and preferably 1100 to 1200°C.
  • phase ratio control is carried out and an active element-added two-phase alloy is subjected to an aging heat treatment to facilitate an appropriate aging reaction between the active element and C, N, and O
  • solution treatment temperature 1050 to 1250°C
  • an aging treatment temperature of 800 to 1000°C 800 to 1000°C
  • an aging time of 0.5 to 6 hours are preferred.
  • Fig. 5 is an optical microscope photograph of a two-phase alloy produced by casting.
  • Fig. 3 is an operation flowchart for illustrating a method for producing a two-phase alloy powder according to the present embodiments.
  • a master ingot casted in step F2 of the steps in Fig. 1 is used as a raw material.
  • the master ingot is re-melted in a melting furnace such as a high frequency or induction furnace (step A1), and then subjected to a gas atomization method using an inert gas of Ar or He to obtain a two-phase alloy powder containing lower amount of oxygen (step A2).
  • step A3 the powders were classified into a range of about 50 to 200 (step A3), and used as a two-phase alloy powder of the present invention.
  • the range of size of the two-phase alloy powder can be changed in accordance with purposes by controlling the classification.
  • a structure of the two-phase alloy powder is a solidified structure by quenching from about liquid phase temperature.
  • the alloy powder having a high Cr (55% or more) and low Ni (25% or less) composition a ferrite phase is likely to be enriched, and thus the above-defined range of the ferrite ratio of 95% or less can not necessarily be satisfied.
  • the alloy powder having a ferrite ratio of 95% or more is acceptable.
  • the alloy powder can be provided as a two-phase alloy powder for purposes including, for example, cladding, 3D printing, or sintering.
  • Fig. 6 is an optical microscope photograph of a powder cladding welded two-phase alloy.
  • Such a two-phase alloy can preferably be used as a component material of apparatuses such as compressors and pumps used under a high corrosion circumstance in an oil well, for example, as a slide part. Furthermore, the two-phase alloy can be used not only as such materials for apparatus, but also as structural materials used in a sea water environment such as umbilical, a sea water purification plant, and a LNG vaporizer, and structural materials of, for example, various chemical plants.
  • the resulting ingots were subjected to hot forging.
  • the hot forging was carried out at a temperature in a range of 1250 to 1050°C at which reduction in area in a tensile test becomes 60% or more. No forging crack was formed.
  • These forging conditions also applied to all alloys of Examples and Comparative Examples concerning the following hot forging.
  • a solution treatment was carried out, in most two-phase alloys, under the following conditions: holding at 1100°C for 60 minutes, followed by water cooling.
  • alloys of A6 Examples 7 to 9
  • A11 Examples 15 to 17
  • A15 Examples 21
  • the solution treatment was carried out at 1100, 1200, or 1250°C
  • additional aging heat treatments were carried out for phase ratio control under the following conditions: holding at 900 to 1000°C for 60 minutes, followed by water cooling.
  • the alloys of alloy numbers A1 to A16 having chemical compositions shown in Table 1 were produced by the steps described above.
  • the alloys of alloy numbers A1 to A16 were Cr based alloys containing Cr as a main component and Cu in an amount of 0.11 to 4.65% by mass, and were two-phase alloys consisting of a ferrite phase and an austenite phase.
  • the alloys of alloy numbers A14 to A16 further contained Mo.
  • Ferrite ratios of the alloys of Examples 1 to 22 are shown in Table 2.
  • the ferrite ratios in the present embodiments are shown in ferrite ratios [%] obtained by EBSP analysis.
  • the ferrite ratios had a tendency to increase with increase in Cr concentration.
  • ferrite ratios were decreased by aging, which leads to structures in which secondary austenite phases were minutely precipitated in ferrite phases by phase-transition.
  • Fig. 4 is an optical microscope photograph of the two-phase alloy of alloy number A10 produced in Examples 13. This optical microscope photograph was taken after the surface of the two-phase alloy of Examples 13 was subjected to mirror polishing and electric field etching in an aqueous oxalic acid solution.
  • the structure of the alloy of Examples 13 which was subjected to a solution treatment at 1100°C after hot forging consisted of an austenite phase P1 having a light color and a ferrite phase P2 having a dark color, and the phases contain minute ferrite and austenite phase, respectively.
  • Similar structures were observed in other two-phase alloys of the present invention which was subjected to thermal processing.
  • Alloys of alloy numbers A9 and A11 which have higher Fe contents and in which a ⁇ phase might be generated were subjected to a heat treatment at 800°C for 60 minutes to study whether ⁇ phase generation occurred or not. These alloys after the heat treatment were analyzed by X-ray diffraction to verify that no ⁇ phase was generated.
  • Vickers hardness and tensile tests were performed to measure 0.2% proof stress, tensile strength, and plastic elongation. Vickers hardness was obtained by performing 5 measurements using a Vickers hardness meter under conditions of load of 1 kg and load application time of 15 seconds and averaging the values.
  • a tensile test was performed using a test piece having a size of 4.0 mm in diameter and 20 mm in length of the parallel portion at room temperature of 23°C. Strain rate was 3 ⁇ 10 -4 /s. In the tensile test, 3 specimens of each alloy were tested to obtain the average value of the measurements. In a stress-strain curve, when brittle fracture of a test piece occurred before a yield point of stress-strain curve or in a midpoint of a flow stress having positive work hardening, a breaking stress was defined instead of a proof stress or tensile strength. The results of these measurements are shown in Table 2. In Table 2, the symbol "*" represents that the value refers to a breaking stress obtained instead of a proof stress or tensile strength. Plastic elongation was evaluated as follows and the results are shown in Table 2: A: 15% or more, B: 5 to less than 15%, C: 0.2 to less than 5.0%, and D: less than 0.2%.
  • a corrosion test was performed with respect to pitting resistance properties and oxidation resistance properties.
  • pitting resistant properties were evaluated according to JIS G0577 (2005). Specifically, 2 polarized test pieces having an area of 10 mm ⁇ 10 mm were obtained from each of the alloys of Examples 1 to 22, and subjected to the following test to evaluate pitting resistance properties.
  • a polarized test piece was installed on a gap corrosion-preventing electrode.
  • An anode polarization curve was obtained using a gap corrosion-preventing electrode to give an average electric potential corresponding to a corrosion current density of 100 ⁇ A/cm 2 .
  • a saturated calomel electrode was used as a reference electrode. After the measurement, observation using an optical microscope was carried out to study whether pitting was generated or not.
  • oxidation resistance properties were evaluated by corrosion rate in sulfuric acid according to JIS G0591 (2000).
  • 2 test pieces having dimensions of 3 mm (thickness) ⁇ 1.30 mm (width) ⁇ 40 mm (length) were obtained, and subjected to an immersion test in 5% boiling sulfuric acid for 6 hours to evaluate sulfuric acid resistance.
  • Each test piece was weighted before and after the measurement to evaluate an average rate of weight loss by corrosion m [g/(m 2 ⁇ h)].
  • Abrasion resistance was evaluated by an abrasive wear test. From each of the alloys of Examples 1 to 22, 2 test pieces having a cylindrical pin shape of 10 mm (diameter) ⁇ 20 mm (length) were obtained, and subjected to an abrasion test. The abrasion test was carried out using a Pin-on-Disk abrasion tester. The test method is described below.
  • the abrasion test was performed as follows: fixing waterproof abrasive paper having grit size of 240 (fixed piece) on a disk, rotating the disk at a rotation rate of 200 rpm, pressing a pin of a test piece (movable piece) against the waterproof abrasive paper under a load of 4 kgf, and moving the waterproof abrasive paper from the outermost circumference to the center. Similar tests were performed sequentially using 3 pieces of waterproof abrasive paper. The outmost grinding diameter was 156 mm, and the total moving distance of the pin was 6 m. Accordingly, an average length of decrease in pin length by abrasion in two specimens was measured as an amount of abrasion under conditions of at room temperature of 22 ⁇ 2°C in an atmospheric environment.
  • the alloys of alloy numbers A17 and A18 are Cr based two-phase alloys containing no Cu.
  • the alloys of alloy numbers A19 and 20 contain no Cu and are a ferrite single phase Cr based alloy containing Cr as a main component and an austenite single phase Ni based alloy containing Ni as a main component, respectively.
  • the alloy of alloy number A21 is a two-phase stainless steel containing Cu. Ferrite ratios of these alloys were measured similarly to the two-phase alloys of alloy numbers 1 to 16 of Examples. The results of the measurements are shown in Table 2.
  • Comparative Examples 3 As shown in Table 2, it was found that a ferrite ratio of the alloy of Comparative Examples 3 (alloy numbers A19) was 100% and had a ferrite single phase, and a ferrite ratio of the alloy of Comparative Examples 4 (alloy numbers A20) was 0% and had a austenite single phase.
  • Comparative Examples 5 (alloy numbers A21) was a two-phase steel having a ferrite ratio of 43%.
  • hot working alloys of the present invention containing active elements such as V were studied.
  • Chemical compositions of alloys of alloy numbers B1 to B14 used in Examples 23 to 38 are shown in Table 3, wherein alloy number B6 is an example useful to understand the present invention.
  • Each of the master ingots of alloys of alloy numbers B1 to B14 was produced by melting using a high frequency vacuum melting furnace.
  • the number in parentheses in Table 3 represents a rate of each of the V, Nb, Ta, and Ti as compared to the total atomic % of C, N, and O.
  • Nb and Ti were added together, and the rates of the amounts added were 0.51 and 0.49 respectively, and the total rate was 1.00.
  • the aging heat treatment was carried out, as shown in Table 4, under the following conditions: holding at temperatures of 800, 900, and 1000°C in the alloy number B6 or at 900°C in all the other alloys for 60 minutes, followed by water cooling. Consequently, C, N, and O were stabilized by reactions with active elements of V, Nb, Ta, and Ti, and at the same time, phase ratio control occurred to result in Examples 23 to 38 of alloys of alloy numbers B1 to B14.
  • the alloys of alloy numbers B1 to B14 stabilized by active elements were Cr based alloys containing Cr as a main component and containing 0.11 to 4.53% by mass of Cu, and were two-phase alloys consisting of a ferrite phase and an austenite phase.
  • the alloy of alloy numbers B14 further contained Mo. Ferrite ratios of the alloys of alloy numbers B1 to B14 are shown in Table 4. The ferrite ratios of the present embodiments were obtained by EBSP analysis similarly to Examples 1 to 22.
  • the alloys of alloy numbers B12 and B13 which had a higher Fe content and in which ⁇ phase could be generated were subjected to a heat treatment at 800°C for 60 minutes to study whether ⁇ phase generation occurred or not.
  • a cast material of an alloy of each of the alloy numbers C1 to C4 was produced by adding minute amounts of Cu and Al, and Mo formulated as required to a master ingot of an alloy of each of the alloy numbers A4, 5, and 8 under Ar atmosphere, re-melting them, and casting the liquid material into a water-cooling cupper die equipped with an inlet for liquid materials in the upper portion.
  • the size of the casted ingot was 40 mm in outer diameter and 100 mm in length.
  • alloy cast materials of alloy numbers C5 to C8 were produced by adding at least one or more of V, Nb, Ta, and Ti formulated with minute amounts of Cu and Al together when re-melting the master ingots of the alloys of alloy numbers A4, 5, 8, and 10, melting them, and casting in the same size as that described above.
  • the alloy of alloy numbers C5 was subjected to a solution treatment at 1100°C for 1 hour
  • the alloy of alloy numbers C8 is subjected to a solution treatment at 1200°C for 1 hour followed by an aging treatment at 900°C for 1 hour to produce Examples 43 and 46, respectively.
  • Test pieces were obtained from lower and center portion of the prepared ingot and were subjected to a structure examination, a Vickers hardness measurement, a strength test, a corrosion test, and an abrasion test.
  • the results of ferrite ratios, Vickers hardness, strength properties, strength properties, and results of the corrosion test and the abrasion test of alloys of Examples 39 to 46(alloy numbers C1 to 8) are shown in Table 6.
  • alloys of alloy numbers C9 to C13 which are powder alloys of two-phase alloys of the present invention used in Examples 47 to 51 are shown in Table 5.
  • powder alloys of alloy numbers C9 and C10 were obtained by adding minute amounts of Cu and Al to master ingots of alloys of alloy numbers A4 and 5 under Ar atmosphere, re-melting them, and powderizing by a gas atomization method.
  • powder alloys of alloy numbers C11 to C13 were obtained by adding minute amounts of Cu and Al, and Mo formulated as required and further at least one or more of V, Nb, Ta, and Ti together to master ingots of alloys of alloy numbers A4, 5, and 10, melting them, and powderizing by a gas atomization method.
  • Each of the powder alloys having a particle diameter in a range of 50 to 200 ⁇ m was obtained by classification. These powders alloys were built-up on a surface of commercially available SUS 304 steel by a powder plasma cladding welding method up to about a thickness of 5 mm. The cladding welding conditions were arc current of 120 A, voltage of 25 V, and a welding rate of 9 cm/minutes.
  • Test pieces for a structure examination, a Vickers hardness measurement, a corrosion test, and an abrasion test were obtained from a surface of the built-up portion of the two-phase alloys of the present invention, and properties of the test pieces were evaluated.
  • the results of the evaluation of the above-described properties of alloys of Examples 47 to 51 are shown in Table 6.
  • compositions of alloys of alloy numbers C14 to C19 used in Comparative Examples 6 to 11 corresponding to Examples 39 to 51 are shown in Table 5.
  • the alloys of alloy numbers C14 to C16 were produced by a casting step similar to that described above using a Cr based two-phase alloy of alloy numbers A17 containing no Cu, a Cr based single-phase ferrite alloy of A19, and a two-phase steel of A21 containing Cu as master ingots.
  • Powder alloys of alloy numbers C17 to C19 were produced by a gas atomization step similar to that described above by re-melting the same master ingots of the alloys of alloy numbers A17 and A19, and the commercially available Stellite(R) No. 6.
  • Vickers hardness was linearly increased in accordance with increase in the ferrite ratio.
  • the Vickers hardness became 400 or more when the ferrite ratio became about 40% or more.
  • Two-phase alloys in which an amount of Cr was decreased or an amount of the ferrite phase was decreased by an aging heat treatment at 800 to 1000°C showed elongation exceeding 20%.
  • Comparative Examples 5 and 8 of Cu-added two-phase stainless steels were rated as class B and C, respectively.
  • the rate of weight loss was 152 g/(m 2 ⁇ h) and was unfavorable in sulfuric acid resistance.
  • Abrasion resistance was expressed in a relative value based on the amount of abrasion of Stellite(R) No. 6 as 100, and decreased generally in inverse proportion to increase in hardness, that is, increase in the amount of a ferrite phase. All alloys except for Comparative Examples 4 (alloy numbers A20), which is a single-phase austenite alloy, are superior to Stellite(R) No. 6 in abrasion resistance.
  • each of the two-phase alloys of hot working materials, cast materials, and cladding materials formed with powders of the present invention contains a hard ferrite phase, which can lead to improvement of abrasive resistance effectively.
  • Such a two-phase alloy having versatile and various favorable properties can be used as a hot working material, a cast material, and a cladding material formed from powders, and is specifically appropriate for a materials for apparatus subjected to severe corrosion atmosphere.
  • the above-described two-phase alloys of Examples of the present invention contains inexpensive Cr as a main component, and it is confirmed that the two-phase alloys are superior in overall strength, corrosion resistance, and abrasion resistance to conventional ones even under a high corrosion circumstance such as in an oil well.

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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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Claims (9)

  1. Alliage biphasé à base de Cr comprenant deux phases d'une phase de ferrite (P2) et d'une phase d'austénite (P1) dans un état mélangé, dans lequel
    une composition chimique de l'alliage biphasé à base de Cr est constituée d'un composant principal, d'un composant accessoire, d'impuretés, d'un premier composant accessoire en option, et d'un second composant accessoire en option,
    le composant principal est constitué de 33 % en masse ou plus et de 65 % en masse ou moins de Cr, de 18 % en masse ou plus et de 40 % en masse ou moins de Ni, et de 10 % en masse ou plus et de 33 % en masse ou moins de Fe,
    le composant accessoire est constitué de 0,1 % en masse ou plus et de 2 % en masse ou moins de Mn, de 0,1 % en masse ou plus et de 1,0 % en masse ou moins de Si, de 0,005 % en masse ou plus et de 0,05 % en masse ou moins d'Al, et de 0,1 % en masse ou plus et de 5,0 % en masse ou moins de Cu,
    les impuretés contiennent plus que 0 % en masse et 0,04 % en masse ou moins de P, plus que 0 % en masse et 0,01 % en masse ou moins de S, plus que 0 % en masse et 0,03 % en masse ou moins de C, plus que 0 % en masse et 0,02 % en masse ou moins de N, et plus que 0 % en masse et 0,03 % en masse ou moins de O, dans lequel
    le premier composant accessoire en option est 0,1 % en masse ou plus et 3,0 % en masse ou moins de Mo, et dans lequel
    le second composant accessoire en option est constitué d'au moins un élément parmi V, Nb, Ta et Ti, et
    un rapport de la teneur atomique totale des éléments V, Nb, Ta et Ti est dans une plage allant de 0,8 fois ou plus à 2 fois ou moins un rapport de teneur atomique totale des éléments C, N et O.
  2. Alliage biphasé à base de Cr selon la revendication 1, dans lequel un taux d'occupation de la phase de ferrite (P2) est 10 % ou plus et 95 % ou moins.
  3. Alliage biphasé à base de Cr selon la revendication 1, dans lequel le composant Ni est dans une plage allant de 23 % en masse ou plus à 40 % en masse ou moins.
  4. Alliage biphasé à base de Cr selon la revendication 3, dans lequel un taux d'occupation de la phase de ferrite (P2) est de 10% ou plus et de 95 % ou moins.
  5. Produit d'alliage biphasé qui est un produit utilisant un alliage biphasé, dans lequel l'alliage biphasé est l'alliage biphasé à base de Cr selon la revendication 1.
  6. Produit d'alliage biphasé qui est un produit utilisant un alliage biphasé, dans lequel l'alliage biphasé est l'alliage biphasé à base de Cr selon la revendication 3.
  7. Produit d'alliage biphasé selon la revendication 5, dans lequel le produit est un corps moulé ayant une structure forgée.
  8. Produit d'alliage biphasé selon la revendication 6, dans lequel le produit est un corps moulé ayant une structure de fonderie.
  9. Produit d'alliage biphasé selon la revendication 6, dans lequel le produit est une poudre.
EP17773605.5A 2016-03-30 2017-01-30 Alliage biphasé à base de chrome et son produit Active EP3438304B1 (fr)

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WO2016052445A1 (fr) * 2014-09-29 2016-04-07 株式会社日立製作所 Alliage à deux phases, produits obtenus à l'aide dudit alliage à deux phases et procédé de fabrication dudit produit
JP2020015925A (ja) * 2016-10-03 2020-01-30 株式会社日立製作所 Ｃｒ基二相合金製造物およびその製造方法
US20190125660A1 (en) * 2017-10-31 2019-05-02 Calitas Therapeutics, Inc Orally dissolving mucoadhesive films utilizing menthol and l-arginine to enhance the bioavailability of cannabinoids
CN110016602B (zh) * 2019-04-22 2020-06-02 陕西科技大学 一种Laves相Cr2Nb基高温合金
WO2021251423A1 (fr) * 2020-06-09 2021-12-16 株式会社日立製作所 Élément résistant à l'usure et dispositif mécanique l'utilisant
CN112391566A (zh) * 2020-11-13 2021-02-23 杭州微熔科技有限公司 一种低温微熔焊防腐耐磨材料及其制备方法
CN113215464A (zh) * 2021-05-17 2021-08-06 山东四通石油技术开发有限公司 一种防腐耐磨抗冲击合金材料及其制备方法

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JPH0770681A (ja) * 1993-09-03 1995-03-14 Sumitomo Metal Ind Ltd 高クロムオーステナイト耐熱合金
DE4342188C2 (de) * 1993-12-10 1998-06-04 Bayer Ag Austenitische Legierungen und deren Verwendung
JPH07216511A (ja) * 1994-01-31 1995-08-15 Sumitomo Metal Ind Ltd 高温強度に優れた高クロムオーステナイト耐熱合金
JPH10140290A (ja) * 1996-11-08 1998-05-26 Sumitomo Metal Ind Ltd 耐硫化水素腐食性に優れた高Ｃｒ−高Ｎｉ合金
JP3650951B2 (ja) * 1998-04-24 2005-05-25 住友金属工業株式会社 耐応力腐食割れ性に優れた油井用継目無鋼管
JP2006152412A (ja) * 2004-12-01 2006-06-15 Mitsubishi Heavy Ind Ltd 耐食、耐酸化性鋳造合金
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JP5682602B2 (ja) * 2012-08-09 2015-03-11 新日鐵住金株式会社 内面品質に優れたＮｉ含有高合金丸ビレットの製造方法
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