WO2018104179A1 - Stainless steel powder for producing duplex sintered stainless steel - Google Patents

Stainless steel powder for producing duplex sintered stainless steel Download PDF

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Publication number
WO2018104179A1
WO2018104179A1 PCT/EP2017/081234 EP2017081234W WO2018104179A1 WO 2018104179 A1 WO2018104179 A1 WO 2018104179A1 EP 2017081234 W EP2017081234 W EP 2017081234W WO 2018104179 A1 WO2018104179 A1 WO 2018104179A1
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Prior art keywords
stainless steel
powder
microns
sintered
steel powder
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PCT/EP2017/081234
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English (en)
French (fr)
Inventor
Sunil BADWE
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Höganäs Ab (Publ)
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Priority to KR1020197019317A priority Critical patent/KR102408835B1/ko
Application filed by Höganäs Ab (Publ) filed Critical Höganäs Ab (Publ)
Priority to EP17808459.6A priority patent/EP3551775B1/en
Priority to JP2019530467A priority patent/JP7028875B2/ja
Priority to AU2017370993A priority patent/AU2017370993B2/en
Priority to BR112019011395-9A priority patent/BR112019011395B1/pt
Priority to RU2019121005A priority patent/RU2753717C2/ru
Priority to US16/467,267 priority patent/US20190309399A1/en
Priority to CA3046282A priority patent/CA3046282A1/en
Priority to MX2019006609A priority patent/MX2019006609A/es
Priority to CN201780082430.4A priority patent/CN110168122A/zh
Publication of WO2018104179A1 publication Critical patent/WO2018104179A1/en
Priority to ZA2019/03576A priority patent/ZA201903576B/en
Priority to US18/541,524 priority patent/US20240117478A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12Both compacting and sintering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0264Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
    • C22C33/0271Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5% with only C, Mn, Si, P, S, As as alloying elements, e.g. carbon steel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/08Ferrous alloys, e.g. steel alloys containing nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/12Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0824Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
    • B22F2009/0828Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid with water
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00Metallic composition of the powder or its coating
    • B22F2301/05Light metals
    • B22F2301/058Magnesium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00Metallic composition of the powder or its coating
    • B22F2301/10Copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00Metallic composition of the powder or its coating
    • B22F2301/15Nickel or cobalt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00Physical aspects of the powder
    • B22F2304/10Micron size particles, i.e. above 1 micrometer up to 500 micrometer

Definitions

  • Embodiments of the present invention may provide a new stainless steel powder suitable for manufacturing of duplex sintered stainless steels.
  • Embodiments of the present invention may also relate to a method for producing the stainless steel powder, the duplex sintered stainless steel as well as methods for producing the duplex sintered stainless steel.
  • Duplex stainless steels have been known to the industry for more than 60 years. They are widely used in heat-treated cast, wrought and gas atomized powder forms, in many applications that require a combination of high strength and high corrosion resistance. However, they are unavailable today, in the water atomized powder form for use in press and sinter applications. Common uses for duplex stainless steels include chemical process plants pipeline, petrochemical industry, power plants and automobiles. They are also used in food processing industry, pharmaceutical process components, paper and pulp industry, in desalination plants and in the mining industry. Duplex stainless steels are known for their high resistance to inter granular corrosion (IGC) and stress corrosion cracking (SCC) in chloride media. Chloride is severe challenge that leads to rapid corrosion media for iron-based alloys.
  • IRC inter granular corrosion
  • SCC stress corrosion cracking
  • High strength and high corrosion resisting properties in duplex stainless steel are believed to be acquired due to a presence of ferrite and austenite phases in equal amounts.
  • Such structure is generally achieved by using a balance of austenite stabilizers, e.g., nickel (Ni), manganese (Mn), carbon (C), nitrogen (N), copper (Cu) and cobalt (Co), and ferrite stabilizers, e.g., chromium (Cr), silicon (Si), molybdenum (Mo), tungsten (W), titanium (Ti) and niobium (Nb).
  • austenite stabilizers e.g., nickel (Ni), manganese (Mn), carbon (C), nitrogen (N), copper (Cu) and cobalt (Co
  • ferrite stabilizers e.g., chromium (Cr), silicon (Si), molybdenum (Mo), tungsten (W), titanium (Ti) and niobium (Nb).
  • N is a strong austenite stabilizer.
  • N when present in the alloy along with Cr, poses problem of forming nitrides which are deleterious to the properties such as strength and corrosion resistance.
  • an intermetallic phase known as "Sigma” is formed in a heat affected zone (HAZ) due to slower cooling rates.
  • HZ heat affected zone
  • This Sigma phase is a hard, supersaturated, intermetallic phase containing Cr and Mo.
  • the area around the Sigma phase is depleted of Cr and Mo and becomes weak and less resistant to corrosion.
  • duplex stainless steels need annealing and quenching process to reduce or eliminate this Sigma phase.
  • the steel In wrought or cast duplex stainless steels, the steel is solidified as ferritic steel and the austenite phase is precipitated out from ferrite during cooling of the alloy.
  • the cooling rate is critical after casting or at any heat treatment, as the cooling rate determines the percentage of austenite and any intermetallic phases, precipitated within the structure.
  • These alloys form intermetallic phases known as sigma, chi and gamma prime which are rich in Mo, W, N, Ni and Cr and reduce both mechanical properties and corrosion properties.
  • Sigma phase forms in a temperature range 700°C to 1000°C whereas Chi phase forms within range 300°C to 450°C.
  • the Gamma (austenite) phase may start forming at around 600°C.
  • Typical composition of wrought duplex stainless steel is Fe with 21 -23wt% Cr, 4.5-6.5wt% Ni, 2.5-3.5wt% Mo, and 0.08-0.2wt% N, such as for SAF 2205.
  • duplex stainless steel composition close to this composition. Almost all of the duplex stainless steels rely on the N content for increased corrosion resistance and increased strength. So far the commercial uses of sintered powder metallurgy (PM) duplex stainless steels are limited to the use of gas atomized fine powders that can be used for mainly HIP process. The main obstacle in using low cost water atomized powders for conventional
  • SE538577C2 discloses a sintered duplex stainless steel made from gas atomized powder and having a chemical composition with a max 0.030wt% C, 4.5-6.5wt% Ni, 0.21 -0.29wt% N, 3.0-3.5wt% Mo, 21 -24wt% Cr, and optionally one or more of 0-1 .0wt% Cu, 0-1 .0wt% W, 0-2.0wt% Mn, 0-1 .0wt% Si wherein N is equal or greater than 0.01 * wt%Cr and the remaining elements are Fe and unavoidable impurities.
  • EP0167822A1 discloses a sintered stainless steel comprising a matrix phase and a dispersed phase and a process for manufacturing.
  • the dispersed phase is an austenite metallurgical structure and is dispersed throughout the matrix phase, which is comprised of an austenitic metallurgical structure having a steel composition different from that of the dispersed phase or a ferritic-austenitic duplex stainless steel.
  • JP5263199A discloses production of a sintered stainless steel comprising a matrix phase and a dispersing phase.
  • the method includes mixing a ferritic stainless steel powder with a powder selected from an austenitic stainless steel powder, an austenitic-ferritic duplex stainless steel powder, an austenitic-martensitic duplex stainless steel powder and austen itic-ferritic- martensitic stainless triple phase stainless steel powder.
  • the powder mixture being compacted and sintered.
  • EP0534864B1 discloses a sintered stainless steel having a content of N of 0.10-0.35wt% and made from gas atomized steel powder having the same chemical composition as the sintered stainless steel.
  • N content helps the above properties, it can pose hurdles in post processing, such as heat treatment and welding operations, by forming chromium nitrides, which limits the use of duplex stainless steels in many applications.
  • N increases the powder hardness making it less suitable for press and sinter applications.
  • Embodiments of the invention overcome the problem with nitrides by avoiding the use of N in the chemistry, for example, having less than 0.10 wt% N or less than 0.07 wt% N, or less than 0.06 wt% N, or less than 0.05 wt% N, or less 0.04 wt% N, or less than 0.03 wt% N, and achieving phase balance and strength by alternative elements.
  • Embodiments of the invention may enable production of water atomized powder with moderate compressibility for use in conventional press and sinter applications.
  • Embodiments of this composition may also reduce precipitation of a deleterious 'Sigma' phase; irrespective of rate of cooling during sintering or annealing, mainly due to lower Mo content. Thus, minimizing post sintering heat treatments necessary to eliminate "Sigma" phase and minimizing sigma phase precipitation during welding.
  • Embodiments of the composition may offer similar advantages when formed by gas atomization.
  • compositions yield similar properties when processed with casting, direct metal deposition and additive manufacturing techniques.
  • Another object of certain embodiments of the present invention is to obtain at least 35% higher tensile strength than ferritic steels such as 430L and double the corrosion resistance compared to austenitic steels such as 31 6L.
  • Still another object of certain embodiments of the present invention is to provide a method for producing a duplex sintered stainless steel without the need of post sintering heat treatment.
  • a stainless steel powder comprising, or consisting of, in weight percent:
  • up to 0.004% B up to 1 % Nb, up to 0.5% Hf, up to 1 % Ti, up to 1 % Co,
  • the unavoidable impurities do not include the listed elements of C, Si, Mn, Cr, Ni, Mo, W, N, Cu, P, S, B, Nb, Hf, Ti, or Co.
  • Unavoidable impurities may include impurities that cannot be controlled, or controlled with difficulty, during
  • manufacture of steels can come from the raw materials used and also from the process. These include, Al, O, Mg, Ca, Ta, V, Te, or Sn.
  • unavoidable impurities may be up to 0.8%, up to 0.6%, up to 0.3%.
  • An unavoidable impurity may be O.
  • O may be present up to 0.6%, up to 0.4%, or up to 0.3%.
  • Another unavoidable impurity may be Sn present up to 0.2%, content of Sn above 0.2% is in this context not regarded as an unavoidable impurity and thus will be regarded as intentionally added.
  • a stainless steel powder consisting of, in weight percent:
  • up to 0.004% B up to 1 % Nb, up to 0.5% Hf, up to 1 % Ti, up to 1 % Co,
  • the powder is ferritic.
  • ferritic For example, 99.5% ferritic. Slight amounts of austenite, e.g., up to 0.5% may be tolerated.
  • the powder is produced by water atomization.
  • the powder is produced by gas atomization.
  • the particle size of the powder is between 53 microns and 18 microns such that at least 80wt% of the particles are less than 53 microns and at most 20wt% of the particles are less than 18 microns.
  • the particle size of the powder is between 26 microns and 5 microns such that at least 80wt% of the particles are less than 26 microns and at most 20wt% of the particles are less than 5 microns.
  • the particle size of the powder is between 150 microns and 26 microns such that at least 80wt% of the particles are less than 150 microns and at most 20wt% of the particles are less than 26 microns.
  • a method of producing a stainless steel powder according to the first aspect comprising the steps of: providing a molten metal of having a chemical composition corresponding to the chemical composition of the stainless steel powder according to the first aspect;
  • a sintered duplex stainless steel having a chemical composition according to the first aspect and embodiments thereof.
  • Ni equivalent (Nieq) is such that 5 ⁇ Ni eq ⁇ 1 1 and the Cr equivalent (Cr eq ) is such that 27 ⁇ Cr eq ⁇ 38.
  • the pitting resistance equivalent number is 28 ⁇ PREN ⁇ 33.
  • the microstructure of the sintered duplex stainless steel is characterized by austenite phase precipitated within ferrite phase.
  • the microstructure of the sintered duplex stainless steel contains 30-70% austenite and 30-70% ferrite. In embodiments of the third aspect, the microstructure of the sintered duplex stainless steel contains at least 99.5% austenite and ferrite, for example, at least 99.8% austenite and ferrite. The percentage of austenite and ferrite may be determined by ASTM E 562-1 1 and ASTM E 1245 -03.
  • the microstructure of the sintered duplex stainless steel is characterized by being free from sigma phases and nitrides, for example, having less than 1 % of sigma phases and nitrides.
  • Examples of an inert atmosphere include nitrogen, argon, and vacuum with argon backfill.
  • An example of a reducing atmosphere is a hydrogen atmosphere, an
  • said consolidation process includes the steps of:
  • said consolidation process includes one of: Metal Injection Molding (MIM), Hot Isostatic Pressing (HIP) or Additive
  • Methods according to the fourth aspect may include one of Laser Powder Bed Fusion (L-PBF), Direct Metal Laser Sintering (DMLS) or Direct Metal Deposition (DMD).
  • L-PBF Laser Powder Bed Fusion
  • DMLS Direct Metal Laser Sintering
  • DMD Direct Metal Deposition
  • forced cooling or quenching is excluded from the cooling step.
  • Cr is a major element in stainless steels which forms a Cr203 layer on the surface which then prevents further oxygen passing the layer, therefore providing an increased corrosion resistance.
  • Ni is another major element which affects the properties of stainless steel. Ni increases the strength and toughness of the steel and also when present with Cr, enhances the corrosion resistance. Mo and W both impart the strength and toughness when present along with Ni. Mo also enhances the corrosion resistance along with Cr and Ni.
  • Si acts as deoxidizer preventing O combining in the steel during melting, Si is also a strong ferrite former.
  • Cu is austenite stabilizer. Cu also increases the corrosion resistance of stainless steel. Especially in conventional PM, Cu helps sintering by promoting liquid phase sintering.
  • Embodiments of the invention provide a powder suitable for producing sintered duplex stainless steel, as well as the sintered stainless steel.
  • the powder and the sintered stainless steel having a low or neglectable content of N. This eliminates the problem of formation of deleterious nitrides during fabrication of the sintered stainless steel.
  • the sintered stainless steel is preferably produced from a compacted and sintered water-atomized powder since the low N content makes it possible to produce water-atomized powder with reasonable
  • Mo is normally present in stainless steel as it strongly promotes the resistance to both uniform and localized corrosion. Mo strongly stabilizes ferritic
  • Ni promotes an austenitic microstructure and generally increases ductility and toughness. Ni has also a positive effect as it reduces the corrosion rate of stainless steels.
  • Cu promotes an austenitic microstructure.
  • the presence of Cu in the powder of the present invention facilitates the sintering process by enabling liquid phase sintering. W is expected to improve the resistance against pitting corrosion.
  • Si increases strength and promotes a ferritic microstructure. It also increases oxidation resistance at high temperatures and in strongly oxidizing solutions at lower temperatures.
  • B, Nb, Hf, Ti, Co may enhance the properties.
  • B when added in small % may help in liquid phase sintering.
  • excess B, if present, may form borides, which are deleterious to both mechanical, and corrosion properties.
  • Nb and Hf when present may stabilize the microstructure by preferentially combining with carbon forming fine carbides freeing Cr for the corrosion resistance.
  • Ti in stainless steels may increase the tensile strength and toughness.
  • Co increases the high temperature mechanical properties.
  • Elements such as C, Mn, S and P should be kept at a level as low as possible in the powder of embodiments of the present invention as they may have a negative effect to various extent on compressibility of the powder and/or mechanical and corrosion preventive properties of the sintered component.
  • Other elements, here designated as unavoidable impurities, may be tolerated up to a content of 0.8% by weight of the powder according to the present invention.
  • composition of the powder according to embodiments of the present invention is designed such that the produced powder will have fully (e.g., at least 99.5%) ferritic structure in the powder form and austenitic phase is precipitated out during sintering cycle. This will allow controlling the ratio of ferrite and austenite by adjusting the sintering parameters.
  • Ni and Cr equivalents are calculated based on following empirical formulae:
  • the composition is targeted such that 5 ⁇ Ni eq ⁇ 1 1 and 27 ⁇ Cr eq ⁇ 38. This places the alloy in at the border of Ferritic - Duplex region on Schaeffler
  • the powder of embodiments of the present invention may be produced by conventional powder manufacturing processes. Such processes may
  • prealloyed powder in contrast to a premixed powder, wherein two or more powders are mixed together, is that segregation is avoided. Such segregation may cause variation in mechanical properties, corrosion resistance etc.
  • embodiments of the present invention may be compacted in a conventional uniaxial compaction equipment at a compaction pressure up to 900 MPa.
  • Suitable particle size distribution of the stainless steel powder to be used at conventional uniaxial compaction is such that the particle size of the powder is between 53 microns and 18 microns such that at least 80wt% of the particles are less than 53 microns and at most 20wt% of the particles are less than 18 microns.
  • the powder of embodiments of the present invention may be mixed with conventional lubricants, such as, but not limited to, Acrawax, Lithium Stearate, Intralube at a content up to 1 wt%.
  • additives mixed in, up to 0.5wt% may be machinability enhancing agents such as CaF2, muscovite, bentonite or MnS.
  • Other methods of consolidation techniques may be utilized such as Metal Injection Molding (MIM), Hot Isostatic Pressing (HIP), extrusion or Additive Manufacturing techniques such as Binder Jetting, Laser Powder Bed Fusion (L- PBF), Direct Metal Laser Sintering (DMLS) or Direct Metal Deposition (DMD)
  • MIM Metal Injection Molding
  • HIP Hot Isostatic Pressing
  • Additive Manufacturing techniques such as Binder Jetting, Laser Powder Bed Fusion (L- PBF), Direct Metal Laser Sintering (DMLS) or Direct Metal Deposition (DMD)
  • suitable particle size distribution of the stainless steel powder to be used is such that the particle size of the powder is between 26 microns and 5 microns such that at least 80wt% of the particles are less than 26 microns and at most 20wt% of the particles are less than 5 microns.
  • suitable particle size distribution of the stainless steel powder to be used is such that the particle size of the powder is between 150 microns and 26 microns such that at least 80wt% of the particles are less than 150 microns and at most 20wt% of the particles are less than 26 microns.
  • the particle size distribution may be measured by a conventional sieving operation according to ISO 4497:1983 or by laser diffraction (Sympatec) according to ISO 13320:1999.
  • the compacted or consolidated body is subjected to a sintering process at sufficiently high temperatures in the range of 1 150°C to 1450°C, preferably at sufficiently high temperatures in the range of 1275°C to 1400°C for a period of time of 5 minutes to 120 minutes.
  • a sintering process at sufficiently high temperatures in the range of 1 150°C to 1450°C, preferably at sufficiently high temperatures in the range of 1275°C to 1400°C for a period of time of 5 minutes to 120 minutes.
  • other period of sintering time such as 10 minutes to 90 minutes or 15 minutes to 60 minutes may be applied.
  • the sintering atmosphere may be vacuum, inert or reducing such as a hydrogen atmosphere, an atmosphere of a mixture of hydrogen and nitrogen or dissociated ammonia.
  • the supersaturated elements in ferrite matrix precipitate out as an austenitic phase. Austenite will start precipitating out at the grain boundaries, will grow with further sintering and will precipitate within the grain itself.
  • the composition of embodiments of the present invention should not form sigma phases or other hard and deleterious phases, e.g., Chi phase and nitrides, during cooling from an elevated temperature, irrespective of the cooling rate.
  • the amount of sigma phase or other hard and deleterious phases is less than 0.5%.
  • Forced cooling or quenching is thus not necessary to apply.
  • forced cooling means that the sintered parts are subjected to a cooling gas at a pressure above atmospheric pressure. Quenching means that the sintered parts are submerged into a liquid cooling media.
  • a microstructure as shown in Figure 1 will typically be formed containing ferrite and austenite. Presence of both phases is responsible for elevated mechanical and corrosion properties. No, or significantly limited amounts of, deleterious phases such as sigma and chi are formed during cooling which are normal for current known duplex stainless steels. As another consequence, this property will reduce or eliminate the formation of such phases during welding where the heat affected zone (HAZ) experience varying cooling rates.
  • HAZ heat affected zone
  • Embodiments of the invented alloy has shown mechanical and corrosion properties that are comparable to or exceeding the wrought and PM products manufactured with known duplex stainless steel alloys.
  • certain advantages of embodiments of this invention may include fewer tendencies to precipitate deleterious sigma and chi phases that affect the mechanical and corrosion properties. This is particularly of interest in welding.
  • Most of the duplex stainless steel components are welded after they are formed. Welding imparts different cooling rates in different parts of HAZ. These cooling rates tend to precipitate sigma and chi phases along with nitrides due to nitrogen present in the current known alloys. Absence of these phases may eliminate the post heat treatments, which normally involve annealing at temperatures above 1200°C followed by rapid cooling. This will in most cases becomes difficult when parts are welded to a bigger structure, limiting use of duplex stainless steel.
  • Figure 1 shows the microstructure of invented sintered stainless steel, austenite and ferrite phases are present in equal proportions in as sintered condition, black spots are porosity.
  • Figure 2 discloses a comparison of ultimate tensile strength (UTS) and corrosion properties of the invented sintered stainless steel compared to 300 and 400 alloys, (SAE grades).
  • Figure 3 shows a comparison of mechanical properties of the invented sintered stainless steel at different sintering conditions
  • a stainless steel powder having a particle size below 325 mesh, i.e. 95wt% of the particles passed 45 ⁇ sieve, was mixed with 0.75wt% of Acrawax as a lubricant.
  • the chemical analysis of the stainless steel powder was 0.01 wt% C, 1 .52wt% Si, 0.2wt% Mn, 0.013wt% P, 0.008wt% S, 24.9wt% Cr, 2.0wt% Cu, 1 .3wt% Mo, 1 .0wt% W, 0.05wt%N, balance Fe.
  • the obtained powder mixture was pressed in a uniaxial press and compacted into transverse rapture strength (TRS) bars, according to ASTM B528-1 6 at a compaction pressure of 750 MPa.
  • TRS transverse rapture strength
  • the pressed TRS bars were then sintered in 100% hydrogen atmosphere at 1343°C with ramp rate of 7°C/minute for 45 minutes. This was followed by furnace cooling at rate 5°C/minute.
  • the samples were then mounted and polished for microstructure examination.
  • the polished samples were then electro-etched with 33%NaOH at 3V for 15 sec. Electro-etch with NaOH reveals the ferrite phase as tan, austenite as white (unaffected) and sigma phases in dark orange at grain boundaries within ferrite matrix.
  • the microstructure observed is as shown in Figure 1 .
  • the microstructure shows approximately 50/50 mixture of ferrite (tan) and austenite (white). There is no sign of any sigma phase (dark orange) in the microstructure.
  • the chemical composition of the stainless steel powders are shown in table 1 .
  • Stainless steel melts having various chemical compositions were melted in an induction furnace, the molten metal was subjected to water stream to obtain steel powder.
  • the obtained powders was then dried and screened to -325 mesh.
  • the screened powder was -45 microns i.e. 95wt% of the powder particles were less than 45 microns.
  • the powders were then mixed with 0.75wt% of the lubricant Acrawax.
  • the mechanical properties i.e.
  • Table 2 shows that the stainless steel powders according to the present invention can be used for producing sintered duplex stainless steel having desired mechanical properties.
  • Table 1 chemical compositions of various stainless steel powders, there production method and type of process or producin sintered samples
  • An embodiment of the invented powder with composition as in Example 1 was also sintered at various temperatures and atmospheres below, to show the effect on mechanical properties. Such data is plotted in Figure 3.
  • EXAMPLE 3 In order to perform corrosion test, TRS bars as in Example 1 were produced along with bars for 31 6L and 434L as representatives from austenitic and ferritic grades. The samples were then tested for corrosion in 5% NaCI solution at room temperature per ASTM B895-1 6. The corrosion was compared by the hours takes for onset of corrosion on the samples. The comparative data is plotted in Figure 2 along with the UTS and YS for these samples. The diameter of the bubbles in the Figure 3 represents the number of hours taken for the start of the corrosion on the samples. The corrosion test for the invented powder was discontinued after 3700 hours as there was no sign of corrosion and it already exceeded 3 times that of 31 6L samples.

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RU2019121005A RU2753717C2 (ru) 2016-12-07 2017-12-01 Порошок нержавеющей стали для получения дуплексной спеченной нержавеющей стали
EP17808459.6A EP3551775B1 (en) 2016-12-07 2017-12-01 Stainless steel powder for producing duplex sintered stainless steel
JP2019530467A JP7028875B2 (ja) 2016-12-07 2017-12-01 二相ステンレス鋼焼結体を製造するためのステンレス鋼粉末
AU2017370993A AU2017370993B2 (en) 2016-12-07 2017-12-01 Stainless steel powder for producing duplex sintered stainless steel
BR112019011395-9A BR112019011395B1 (pt) 2016-12-07 2017-12-01 Pó de aço inoxidável ferrítico pré-ligado e método para a produção de um aço inoxidável duplex sinterizado
KR1020197019317A KR102408835B1 (ko) 2016-12-07 2017-12-01 듀플렉스 소결된 스테인리스 강을 제조하기 위한 스테인리스 강 분말
US16/467,267 US20190309399A1 (en) 2016-12-07 2017-12-01 Stainless steel powder for producing duplex sintered stainless steel
CN201780082430.4A CN110168122A (zh) 2016-12-07 2017-12-01 用于生产双相烧结不锈钢的不锈钢粉末
MX2019006609A MX2019006609A (es) 2016-12-07 2017-12-01 Polvo de acero inoxidable para producir acero inoxidable sinterizado duplex.
CA3046282A CA3046282A1 (en) 2016-12-07 2017-12-01 Stainless steel powder for producing duplex sintered stainless steel
ZA2019/03576A ZA201903576B (en) 2016-12-07 2019-06-04 Stainless steel powder for producing duplex sintered stainless steel
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111057963A (zh) * 2018-10-17 2020-04-24 山特维克材料技术公司 生产双相不锈钢管的方法
TWI727414B (zh) * 2018-08-31 2021-05-11 日商大同特殊鋼股份有限公司 合金粉末組成物

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN117867412B (zh) * 2024-03-08 2024-05-10 东北大学 一种燃料电池双极板高耐蚀性不锈钢

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5263199A (en) 1975-09-29 1977-05-25 Montedison Spa Process for preparing thermally stable iron oxide base pigment from acidic solution containing ferrous sulfate
EP0167822A1 (en) 1984-06-06 1986-01-15 Sumitomo Metal Industries, Ltd. Sintered stainless steel and production process therefor
US4581202A (en) * 1984-03-12 1986-04-08 Sumitomo Metal Industries, Ltd. Sintered stainless steel and production process therefor
EP0534864B1 (en) 1991-09-30 1995-11-02 Sumitomo Metal Industries, Ltd. Duplex stainless steel having improved corrosion resistance and process for the production thereof
EP1561834A1 (en) * 2003-08-07 2005-08-10 Sumitomo Metal Industries, Ltd. Duplex stainless steel and method for production thereof
SE538577C2 (sv) 2014-05-16 2016-09-27 Pulvermetallurgiskt duplext rostfritt stål

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3696486A (en) * 1969-08-25 1972-10-10 Int Nickel Co Stainless steels by powder metallurgy
BE793539A (fr) * 1971-12-30 1973-06-29 Int Nickel Ltd Perfectionnements relatifs a la compression des poudres
AT360061B (de) * 1976-01-13 1980-12-29 Graenges Nyby Ab Verfahren zur herstellung von stabilisierten, ferritischen, rostfreien chromstaehlen
CA1103482A (en) * 1977-11-29 1981-06-23 Brian M. Armstrong Niobium stabilised sintered products
JPS6152302A (ja) * 1984-08-20 1986-03-15 Daido Steel Co Ltd 粉末冶金用合金鋼粉末
US4708741A (en) * 1986-06-13 1987-11-24 Brunswick Corporation Rapid sintering feedstock for injection molding of stainless steel parts
US5302214A (en) * 1990-03-24 1994-04-12 Nisshin Steel Co., Ltd. Heat resisting ferritic stainless steel excellent in low temperature toughness, weldability and heat resistance
JPH0663055B2 (ja) 1990-12-20 1994-08-17 住友金属工業株式会社 焼結ステンレス鋼
FI100422B (fi) * 1994-07-11 1997-11-28 Metso Paper Inc Telan valmistus
JPH08246008A (ja) * 1995-03-08 1996-09-24 Daido Steel Co Ltd 金属粉末および水噴霧によるその製造方法
SE9702299D0 (sv) * 1997-06-17 1997-06-17 Hoeganaes Ab Stainless steel powder
JP4975916B2 (ja) * 2001-09-21 2012-07-11 株式会社日立製作所 高靭性高強度フェライト鋼とその製法
JP3856294B2 (ja) * 2001-11-30 2006-12-13 セイコーエプソン株式会社 焼結用ステンレス鋼粉末、焼結ステンレス鋼製造用造粒粉末および焼結ステンレス鋼
US20050129563A1 (en) * 2003-12-11 2005-06-16 Borgwarner Inc. Stainless steel powder for high temperature applications
SE529041C2 (sv) * 2005-08-18 2007-04-17 Erasteel Kloster Ab Användning av ett pulvermetallurgiskt tillverkat stål
SE528991C2 (sv) * 2005-08-24 2007-04-03 Uddeholm Tooling Ab Ställegering och verktyg eller komponenter tillverkat av stållegeringen
TWI394848B (zh) * 2007-10-10 2013-05-01 Nippon Steel & Sumikin Sst 雙相不銹鋼線材、鋼線及螺釘以及其製造方法
US8313691B2 (en) * 2007-11-29 2012-11-20 Ati Properties, Inc. Lean austenitic stainless steel
JP4531118B2 (ja) * 2008-05-27 2010-08-25 新日鐵住金ステンレス株式会社 凝固結晶粒を微細にする二相ステンレス鋼溶接用フラックス入りワイヤ
CN101338385A (zh) * 2008-08-29 2009-01-07 安泰科技股份有限公司 一种含氮/高氮不锈钢制品及其制备方法
RU2553794C2 (ru) * 2009-10-16 2015-06-20 Хеганес Актиеболаг (Пабл) Азотсодержащая, низконикелевая спеченная нержавеющая сталь
KR20120132691A (ko) * 2010-04-29 2012-12-07 오또꿈뿌 오와이제이 높은 성형성을 구비하는 페라이트-오스테나이트계 스테인리스 강의 제조 및 사용 방법
US20130136646A1 (en) * 2010-06-04 2013-05-30 Hoganas Ab (Publ) Nitrided sintered steels
EP2511031A1 (en) * 2011-04-12 2012-10-17 Höganäs Ab (publ) A powder metallurgical composition and sintered component
FI126574B (fi) * 2011-09-07 2017-02-28 Outokumpu Oy Dupleksinen ruostumaton teräs
CN104919072B (zh) * 2013-01-15 2017-07-14 株式会社神户制钢所 双相不锈钢钢材和双相不锈钢钢管
KR101496000B1 (ko) * 2013-05-03 2015-02-25 주식회사 포스코 린 듀플렉스 스테인리스 열연강판 제조 방법
JP6152302B2 (ja) * 2013-06-04 2017-06-21 錦城護謨株式会社 ドレーン材用アンカー取付装置
JP6378517B2 (ja) * 2014-03-27 2018-08-22 山陽特殊製鋼株式会社 焼結割れ防止性に優れ焼結−時効処理後に高強度が得られる析出硬化型ステンレス鋼粉末およびその焼結体。

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5263199A (en) 1975-09-29 1977-05-25 Montedison Spa Process for preparing thermally stable iron oxide base pigment from acidic solution containing ferrous sulfate
US4581202A (en) * 1984-03-12 1986-04-08 Sumitomo Metal Industries, Ltd. Sintered stainless steel and production process therefor
EP0167822A1 (en) 1984-06-06 1986-01-15 Sumitomo Metal Industries, Ltd. Sintered stainless steel and production process therefor
EP0534864B1 (en) 1991-09-30 1995-11-02 Sumitomo Metal Industries, Ltd. Duplex stainless steel having improved corrosion resistance and process for the production thereof
EP1561834A1 (en) * 2003-08-07 2005-08-10 Sumitomo Metal Industries, Ltd. Duplex stainless steel and method for production thereof
SE538577C2 (sv) 2014-05-16 2016-09-27 Pulvermetallurgiskt duplext rostfritt stål

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A. LAWLEY; E. WAGNER; C.T. SCHADE, ADVANCES IN POWDER METALLURGY AND PARTICULATE MATERIALS, vol. 7, 2005, pages 78 - 89
L.A. DOBRZANSKI; Z. BRYTAN; M. ACTIS GRANDE; M. ROSSO, ARCHIVES OF MATERIALS SCIENCE AND ENGINEERING, vol. 28, no. 4, April 2007 (2007-04-01), pages 217 - 223
L.A. DOBRZANSKI; Z. BRYTAN; M. ACTIS GRANDE; M. ROSSO, JOURNAL OF ACHIEVEMENTS IN MATERIALS AND MANUFACTURING ENGINEERING, vol. 17, no. 1-2, pages 317 - 320

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI727414B (zh) * 2018-08-31 2021-05-11 日商大同特殊鋼股份有限公司 合金粉末組成物
CN111057963A (zh) * 2018-10-17 2020-04-24 山特维克材料技术公司 生产双相不锈钢管的方法

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