US20080019858A1 - Iron-based powder - Google Patents

Iron-based powder Download PDF

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Publication number
US20080019858A1
US20080019858A1 US11/767,643 US76764307A US2008019858A1 US 20080019858 A1 US20080019858 A1 US 20080019858A1 US 76764307 A US76764307 A US 76764307A US 2008019858 A1 US2008019858 A1 US 2008019858A1
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United States
Prior art keywords
powder
max
iron
weight
content
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US11/767,643
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English (en)
Inventor
Ove H. Mars
Ingrid Hauer
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Hoganas AB
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Hoganas AB
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Priority to US11/767,643 priority Critical patent/US20080019858A1/en
Assigned to HOGANAS AKTIEBOLAG (PUBL) reassignment HOGANAS AKTIEBOLAG (PUBL) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HAUER, INGRID, MARS, OVE H.
Publication of US20080019858A1 publication Critical patent/US20080019858A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making 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
    • B22F9/082—Making 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making 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%
    • C22C33/0285—Making 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%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making 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
    • B22F9/082—Making 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
    • B22F2009/0824—Making 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
    • B22F2009/0828—Making 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
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the invention concerns atomised iron based powders having good high temperature oxidation resistance, more particular powders which are pre-alloyed with chromium and aluminium.
  • FeCrAl-alloys Conventional iron based alloys containing typically Fe and 10-30% Cr and 1-10% Al, so-called FeCrAl-alloys, have been found highly useful in various high temperature applications, due to their good oxidation resistance and can be used at temperatures as high as 1200-1400° C. Thus, such materials have been used in the production of electrical resistance elements and as carrier materials in motor vehicle catalysts. As a result of its aluminium content, the alloy is able to form at high temperatures and in the majority of atmospheres an impervious and adhesive surface oxide consisting substantially of Al2O3. This oxide protects the metal against further oxidation and also against many other forms of corrosion, such as carburization, sulphuration etc.
  • U.S. Pat. No. 5,970,306 describes a method for manufacturing high temperature resistant shaped parts from a FeCrAl-powder by hot isostatically pressing (HIP).
  • HIP hot isostatically pressing
  • DE4235141 describes a method of producing a part made from hot pressed powder based on a FeCrAl-alloy in which the powder is initially exposed to an oxygen-contg. atmos. to produce an chromium oxide protective layer around the particles.
  • U.S. Pat. No. 6,761,751 describes a method of producing an FeCrAl material by gas atomization, wherein in addition to containing iron (Fe), chromium (Cr) and aluminium (Al) the material also contains minor fractions of one or more of the materials molybdenum (Mo), hafnium (Hf), zirconium (Zr), yttrium (Y), nitrogen (N), carbon (C) and oxygen (O).
  • Mo molybdenum
  • Ha hafnium
  • Zr zirconium
  • Y yttrium
  • nitrogen nitrogen
  • C carbon
  • O oxygen
  • This object is solved by an atomised iron based powder pre-alloyed with 10.5-30 wt % Cr, 3-15 wt % Al and 5-20 wt % Cu.
  • pre-alloying the powder with Cu it is possible to sinter a component in conventional sintering processes and maintaining satisfactory material properties of the sintered component which component also have excellent high temperature oxidation resistance.
  • an iron based powder pre-alloyed with 10.5-30 wt % Cr, 3-15 wt % All, 5-20 wt % Cu and 8-20 wt % Ni is proposed.
  • the powders of the invention are preferably produced by providing a melt of iron and the alloying elements, water atomizing the melt whereby the powder forms from atomized droplets upon solidification.
  • a sintered component can be produced from the powders of the invention by a) providing a sintering material comprising the powder of the invention; b) forming a green body from the sintering material; and c) sintering the green body in a reducing or neutral atmosphere, at an atmospheric pressure or below, and at a temperature above 1100° C.
  • the sintering material could e.g. be loose sintered, cold compacted or warm compacted.
  • the sintering material is a mixture between a binder and/or a lubricant with the powder of the invention.
  • Cold compaction is performed at temperatures below 100° C., preferably at a compaction pressure within the range of 100-1000 MPa.
  • Warm compaction is performed at temperatures within the range of 100-200° C., preferably at a compaction pressure within the range of 300-1000 MPa.
  • the sintering material could be a mixture between a binder and/or a lubricant with the powder of the invention, but also the powder it self i.e. without mixing the powder with a binder and/or a lubricant.
  • the sintering material could be poured into a form where after the form containing the sintering material is inserted into the sintering furnace. For instance filters having excellent high temperature oxidation resistance can be produced by loose sintering the powder of the invention.
  • a sintered component which exhibits excellent high temperature oxidation resistance may be produced from the powder of the invention which sintered component has a sintered density above 6.5 g/cm 3 , a tensile strength above 500 MPa and a yield strength above 400 MPa.
  • FIG. 1 shows a Fe—Cu phase diagram
  • FIG. 2A shows metallographic picture of a test bar comprising Cr, Al, Cu and Fe, and
  • FIG. 2B shows metallographic picture of a test bar comprising Cr, Al and Fe, and
  • FIG. 3A shows metallographic picture of a test bar comprising Cr, Al, Cu, Ni and Fe, and
  • FIG. 3B shows metallographic picture of a test bar comprising Cr, Al, Ni and Fe.
  • the invention concerns pre-alloyed iron based powders comprising more than 10.5 wt % chromium, as well as certain amounts of aluminium and copper.
  • FeCrAl-alloys have been shown to exhibit excellent oxidation resistance at high temperatures, but are unfortunately difficult to sinter under atmospheric pressure or below (vacuum). That is the reason why compounds based on FeCrAl powders are produced by the HIP-process (as described in e.g. U.S. Pat. No. 5,970,306).
  • pre-alloying with copper was reduced with an improved sintered structure as the outcome—compared to a reference material without copper.
  • the copper content is shown to facilitate the formation of sintering necks as can be seen from the accompanying metallographic pictures. We believe that this effect occurs due to a break-up of the aluminium oxide layer by liquidised copper. Admixing copper and a FeCrAl-powder were also tested but sintering did not significantly improve in that case.
  • the powders of the invention are made by making a melt of iron and the desired alloying elements.
  • the melt is thereafter atomised whereby the powder is formed from the atomized droplets upon solidification.
  • the atomization is performed according to conventional technology, e.g. gas or water atomization.
  • the melt blend is water atomized, since a water atomised powder is easier to compact than a gas atomized powder.
  • the powder forms due to the water atomization the powder is oxidized and thin chromium and aluminium oxide layers forms on the surface of the powder particles.
  • the aluminium content should be above 3%, preferably the aluminium content should be above 5%, in order to obtain the desired oxidation resistance.
  • the upper limit for the aluminium content is set to 15 wt %, and in fact it is preferred to have the aluminium content below 12 wt %.
  • the boundaries for the copper content were derived from the tests described below. Accordingly it the copper content should be above 5 wt % to facilitate the formation of sintering necks and providing a sintered component having good high temperature oxidation resistance. Further the Cu-content should be below 20 wt %, powders having higher Cu-content may very well be useful for certain applications, but they are not within the scope of the present invention.
  • FIG. 1 shows the Fe—Cu phase diagram, but it is believed that that Cu will influence a system in a similar way.
  • a certain amount of liquid phase must be formed, i.e. the area of ( ⁇ Fe+L) is of interest. Since the diagram is for the pure Fe—Cu system the information retrieved from it can only be used as a guideline.
  • the amount of liquid phase formed during the sintering is required to break up the aluminium oxides but excess amounts of liquid phase collapses the structure during sintering.
  • the amount of liquid phase formed is related to the chemical composition and the sintering temperature. The element having the strongest influence of the formation of liquid is copper. That is why different sintering temperatures depending of copper content of the samples were applied before the oxidation test.
  • the powder can also be pre-alloyed with austenite-forming elements in particular nickel, but also the nickel equivalent manganese.
  • austenite-forming elements nickel is also known to have a beneficial effect on the oxidation resistance which of course is desirable in the applications intended for the powders of the invention.
  • nickel is to be included in the powder it is preferred that the nickel content is in the interval of 8-20 wt %.
  • Manganese can also be an additional austenite forming alloying element, preferably the manganese content is below 3 wt %.
  • Cobalt is normally not used since it is comparably expensive.
  • the carbon content is low, since carbon has a tendency to cause intergranular corrosion why preferably the carbon content should be less than 0.1 wt % carbon.
  • the carbon content was about 0.02 wt % or lower.
  • the nitrogen content is kept as low as possible, preferably the nitrogen content is below 0.2 wt %.
  • test samples and the reference sample were produced by filling a form (10 mm diameter and 2 mm thickness) with the powder of interest, followed by smoothing out the surface without compacting the powder. This procedure provides samples with high specific area (ca 45% porosity).
  • test samples were sintered in a 100% hydrogene atmosphere for 30 minutes at a temperature depending of the Cu content according to the following table:
  • the reference sample was sintered in a 100% hydrogen atmosphere for 30 minutes at 1320° C.
  • the oxidation tests were carried out in a laboratory furnace, a Lenton 12/50/300, at a temperature of 800° C. in air.
  • Six samples could be tested at the same time by placing them on a sample holder and at each test run two of the samples were reference samples.
  • the samples were weighted before they were introduced in the furnace. Short term cycles were performed, each cycle consisting of 2 min heating and 30 sec cooling, which is sufficient for the samples to cool down below 150° C. This cycle was repeated 15 times, resulting in 30 minutes in the furnace. After every 30 minutes in the heating zone, the samples were weighted and the gain-in-weight for each of them was saved. The tests were stopped after 20 hours in the heating zone.
  • Powder 2 and 3 were further tested at different oxidation temperatures.
  • the following table shows the increase in weight relative to the reference 310B.
  • Table 2 shows that difference in oxidation resistance between samples containing Cu and Al and reference samples is further pronounced at temperatures above 800° Celcius. Furthermore, the composition having a Al content of 5.5% and a Cu content of 15% seems to have better oxidation resistance compared to the composition having 10 Al and 10% Cu.
  • the table 3 shows that the density and the mechanical properties of Al-containing Cr or Cr—Ni stainless steel powders increases considerably if the powder are pre-alloyed with Cu. This indicates much improved sintering activity.
  • FIG. 2A shows metallographic picture of a test bar comprising 22Cr+5.5Al+10Cu+bal.
  • FIG. 2B shows metallographic picture of a corresponding reference test bar comprising 22Cr+5.5Al+bal.
  • FIG. 3A shows metallographic picture of a test bar comprising 22Cr+5.5Al+18Ni+8Cu+ bal.
  • Fe and FIG. 2B shows metallographic picture of a corresponding reference test bar comprising 22Cr+5.5Al+18Ni+bal. Fe.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Soft Magnetic Materials (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US11/767,643 2006-07-21 2007-06-25 Iron-based powder Abandoned US20080019858A1 (en)

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US11/767,643 US20080019858A1 (en) 2006-07-21 2007-06-25 Iron-based powder

Applications Claiming Priority (4)

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SESE0601601-8 2006-07-21
SE0601601 2006-07-21
US84045706P 2006-08-28 2006-08-28
US11/767,643 US20080019858A1 (en) 2006-07-21 2007-06-25 Iron-based powder

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US (1) US20080019858A1 (ja)
EP (1) EP2051826B1 (ja)
JP (1) JP2009544841A (ja)
CN (1) CN101516549A (ja)
AT (1) ATE525156T1 (ja)
DK (1) DK2051826T3 (ja)
ES (1) ES2375159T3 (ja)
TW (1) TW200808982A (ja)
WO (1) WO2008010767A1 (ja)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110206305A1 (en) * 2008-10-29 2011-08-25 Ntn Corporation Sintered bearing
CN102554216A (zh) * 2012-02-07 2012-07-11 建德市易通金属粉材有限公司 一种水雾化铁铜合金粉末及制造方法
CN106222566A (zh) * 2016-08-23 2016-12-14 秦皇岛市雅豪新材料科技有限公司 一种超硬材料制品专用稀土调节水雾化Fe‑Cu预合金粉末及其制备方法
US11098619B2 (en) * 2018-11-16 2021-08-24 Mhale International GmbH Method for producing a copper-infiltrated valve seat ring
US11512372B2 (en) 2015-02-03 2022-11-29 Höganäs Ab (Publ) Powder metal composition for easy machining

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201140139A (en) 2010-03-11 2011-11-16 Pacific Biosciences California Micromirror arrays having self aligned features
JP6384752B2 (ja) * 2014-07-15 2018-09-05 日立金属株式会社 磁心およびそれを用いたコイル部品
US20200216935A1 (en) * 2019-01-04 2020-07-09 Tenneco Inc. Hard powder particles with improved compressibility and green strength
KR102352433B1 (ko) * 2020-04-16 2022-01-19 김재곤 동 합금판 및 그의 제조방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4992233A (en) * 1988-07-15 1991-02-12 Corning Incorporated Sintering metal powders into structures without sintering aids
US5427601A (en) * 1990-11-29 1995-06-27 Ngk Insulators, Ltd. Sintered metal bodies and manufacturing method therefor
US5970306A (en) * 1995-04-26 1999-10-19 Kanthal Ab Method of manufacturing high temperature resistant shaped parts
US20040112173A1 (en) * 2001-01-24 2004-06-17 Paritosh Maulik Sintered ferrous material contaning copper

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4758272A (en) * 1987-05-27 1988-07-19 Corning Glass Works Porous metal bodies
JP3091246B2 (ja) * 1990-04-03 2000-09-25 日本碍子株式会社 耐熱性金属質モノリス及びその製造方法
US5292485A (en) * 1990-04-03 1994-03-08 Ngk Insulators, Ltd. Heat-resistant metal monolith
JPH04116103A (ja) * 1990-09-05 1992-04-16 Daido Steel Co Ltd 軟質磁性合金粉末
JPH08120435A (ja) 1994-10-19 1996-05-14 Nippon Steel Corp ガラス成形金型用溶射材料およびその金型
SE0000002L (sv) * 2000-01-01 2000-12-11 Sandvik Ab Förfarande för tillverkning av ett FeCrAl-material och ett sådant marerial
JP2005220438A (ja) * 2004-01-06 2005-08-18 Hitachi Metals Ltd Ｆｅ−Ｃｒ−Ａｌ系磁性粉末と、Ｆｅ−Ｃｒ−Ａｌ系磁性粉末成形体およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4992233A (en) * 1988-07-15 1991-02-12 Corning Incorporated Sintering metal powders into structures without sintering aids
US5427601A (en) * 1990-11-29 1995-06-27 Ngk Insulators, Ltd. Sintered metal bodies and manufacturing method therefor
US5970306A (en) * 1995-04-26 1999-10-19 Kanthal Ab Method of manufacturing high temperature resistant shaped parts
US20040112173A1 (en) * 2001-01-24 2004-06-17 Paritosh Maulik Sintered ferrous material contaning copper

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110206305A1 (en) * 2008-10-29 2011-08-25 Ntn Corporation Sintered bearing
CN102554216A (zh) * 2012-02-07 2012-07-11 建德市易通金属粉材有限公司 一种水雾化铁铜合金粉末及制造方法
US11512372B2 (en) 2015-02-03 2022-11-29 Höganäs Ab (Publ) Powder metal composition for easy machining
CN106222566A (zh) * 2016-08-23 2016-12-14 秦皇岛市雅豪新材料科技有限公司 一种超硬材料制品专用稀土调节水雾化Fe‑Cu预合金粉末及其制备方法
US11098619B2 (en) * 2018-11-16 2021-08-24 Mhale International GmbH Method for producing a copper-infiltrated valve seat ring

Also Published As

Publication number Publication date
JP2009544841A (ja) 2009-12-17
ATE525156T1 (de) 2011-10-15
TW200808982A (en) 2008-02-16
CN101516549A (zh) 2009-08-26
DK2051826T3 (da) 2012-01-09
EP2051826B1 (en) 2011-09-21
WO2008010767A1 (en) 2008-01-24
EP2051826A1 (en) 2009-04-29
ES2375159T3 (es) 2012-02-27

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