EP3470542A1 - Kobaltfreie legierungen - Google Patents
Kobaltfreie legierungen Download PDFInfo
- Publication number
- EP3470542A1 EP3470542A1 EP18196212.7A EP18196212A EP3470542A1 EP 3470542 A1 EP3470542 A1 EP 3470542A1 EP 18196212 A EP18196212 A EP 18196212A EP 3470542 A1 EP3470542 A1 EP 3470542A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- percent
- alloy
- chromium
- carbon
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 41
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 239000011651 chromium Substances 0.000 claims abstract description 37
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 33
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910001566 austenite Inorganic materials 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 150000001247 metal acetylides Chemical class 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- -1 chromium carbides Chemical class 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 229910001347 Stellite Inorganic materials 0.000 description 3
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 3
- 238000009689 gas atomisation Methods 0.000 description 3
- 238000005552 hardfacing Methods 0.000 description 3
- 238000001513 hot isostatic pressing Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000012358 sourcing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- 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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- 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
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
-
- 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
- C22C38/56—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.7% by weight of carbon
-
- 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
- This disclosure relates to cobalt-free alloys.
- Cobalt-base alloys such as the Stellites (RTM) have been used extensively to form components or to provide hardfacing due to their high wear resistance, especially at high temperatures, with very good corrosion resistance.
- RTM Stellites
- One application of such cobalt-base alloys is as a hardfacing on valve seats.
- the invention is directed towards cobalt-free alloys.
- One such alloy consists essentially of, by weight:
- the alloy of the present invention has an iron base.
- the iron is, in the solid form of the alloy, in a predominantly austenitic crystallographic matrix. This is achieved by a depression of the martensite start temperature. By selecting a predominantly austenitic matrix, the formation of low-temperature phases which may occur in duplex matrixes is inhibited.
- the alloy further comprises carbon and chromium.
- an appropriately-controlled cooling rate will allow the chromium to diffuse into chromium-depleted zones formed by the carbide precipitation. This is aided by the provision of a sufficient quantity of the chromium to, at meta-equilibrium, form a first population dissolved in the austenite for corrosion resistance, and a second population in the form of carbides.
- the carbides may be either of the form Cr 7 C 3 . They may alternatively be in the form of Cr 23 C 6 . Alternatively there could be combination of those carbides. Other forms of chromium carbide may also be selectively formed.
- the carbon is provided at an effective concentration of up to 2.5 percent by weight.
- the chromium is provided at a concentration of between 12 and 58 percent by weight. The lower bound of the chromium concentration is selected so as to ensure a sufficient quantity (a first population) is dissolved in the austenitic matrix for corrosion resistance.
- a second population of chromium combines with the carbon to form chromium carbides.
- the chromium carbides are provided at an effective concentration for galling resistance. They also provide general wear resistance.
- the first population of chromium is provided at a concentration of 16 percent by weight.
- the second population of chromium is provided at a concentration such that the molar ratio between chromium and carbon is 7:3. This allows the formation of Cr 7 C 3 .
- the second population of chromium is provided at a concentration such that the molar ratio between chromium and carbon is 23:6. This allows the formation of Cr 23 C 6 .
- the alloy has, by weight, 0.8 to 1.2 percent carbon. This produces an alloy which has comparable carbide content to Stellite 6. In another embodiment, the alloy has, by weight, 1.7 to 2.0 percent carbon. This produces an alloy which has comparable carbide content to Stellite 12. In another embodiment, the alloy has, by weight, 2.2 to 2.5 percent carbon. This produces an alloy which has comparable carbide content to Stellite 3.
- chromium is a ferrite stabiliser, and indeed in high concentrations can completely eliminate the austenitic phase. This effect is offset however by provision of a sufficient concentration of austenite stabilisers to ensure the austenitic matrix is metastable at all temperatures that the alloy will be exposed to during service.
- the austenite stabilisers maintain a predominantly austenitic crystallographic matrix in a metastable condition so as to prevent formation of ferrite during service. In this way, the quantity of dissolved chromium remains sufficient to maintain corrosion resistance.
- the austenite stabilisers are nickel, manganese and nitrogen, with the overall concentration of these elements being selected so as to effect the required degree of austenite stabilisation.
- the concentration of nickel required to depress the martensite start temperature sufficiently also increases the stacking fault energy of the austenitic matrix.
- the increase in stacking fault energy results in the matrix having a lower tolerance to defects introduced by deformation, such as galling.
- the nickel-equivalents manganese and nitrogen are also used so as to reduce the required nickel concentration.
- Nitrogen also operates to reduce stacking fault energy throughout the entire austenitic matrix. This complements the carbide population in terms of providing resistance to galling.
- chromium and manganese both increase the solubility of the nitrogen in the austenite, whilst having only a moderate propensity to form nitrides, and/or carbonitrides, compared with, for example, titanium which is a strong nitride former. In this way, higher concentrations of nitrogen may be used, thereby further reducing the amount of nickel required and further reducing stacking fault energy.
- manganese not only acts as an austenite stabiliser and as a nitrogen solubility modifier, but it also acts to increase the hardenability of the alloy. Again, this acts to increase the galling resistance of the alloy.
- Nickel also improves the corrosion resistance of the alloy over and above that achievable by provision of solely chromium for such a purpose.
- Manganese is abundant, as is nitrogen, thereby reducing difficulties in terms of sourcing supply of nickel.
- the austenite stabilisers are provided in the following concentrations by weight: 7 to 9 percent manganese; 4 to 6 percent nickel; 0.08 to 0.2 percent nitrogen.
- Additional carbide formers may be provided to assist in maintaining the concentration of chromium dissolved in the matrix constant.
- one or more additional carbide formers over and above the chromium are included whose carbides have a temperature of formation greater than that of chromium carbide.
- the one or more additional carbide formers are selected from the group consisting of titanium and vanadium.
- Other additional carbide formers are possible singularly or in combination, for example hafnium. The provision of additional carbide formers may reduce the degree of sensitisation.
- the carbide population is solely chromium-based. It has been found that whilst this may require measures to be taken to reduce sensitisation, it increases the corrosion resistance of the alloy relative to those embodiments where the additional carbide formers are provided.
- a melt fluidity promotor is included in the form of silicon at a concentration of 4 to 5 percent by weight.
- the powdered form of the alloy may be produced by gas atomisation.
- the alloys described herein may be provided in powdered form. Thus they may be used in, for example, a HIP process or a weld deposition process.
- the alloys may be used in a component part of a nuclear reactor. More generally, the alloys may constitute an article, or may constitute a coating of an article, for example a hardfacing. Additional heat treatments may be performed, for example to increase the quantity of austenite.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Coating By Spraying Or Casting (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB1716640.6A GB201716640D0 (en) | 2017-10-11 | 2017-10-11 | Cobalt-free alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3470542A1 true EP3470542A1 (de) | 2019-04-17 |
| EP3470542B1 EP3470542B1 (de) | 2023-11-01 |
Family
ID=60326771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP18196212.7A Active EP3470542B1 (de) | 2017-10-11 | 2018-09-24 | Kobaltfreie legierungen |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20190106776A1 (de) |
| EP (1) | EP3470542B1 (de) |
| CN (1) | CN109652693A (de) |
| GB (1) | GB201716640D0 (de) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2799577A (en) * | 1953-02-18 | 1957-07-16 | Crucible Steel Co America | Age hardening austenitic steel |
| GB1459255A (en) * | 1973-05-14 | 1976-12-22 | Armco Steel Corp | Galling resistant austenitic stainless steel |
| GB1595755A (en) * | 1978-01-23 | 1981-08-19 | Armco Inc | Galling resistant austenitic stainless steel |
| US4494988A (en) * | 1983-12-19 | 1985-01-22 | Armco Inc. | Galling and wear resistant steel alloy |
| US4814140A (en) * | 1987-06-16 | 1989-03-21 | Carpenter Technology Corporation | Galling resistant austenitic stainless steel alloy |
| JPH11226778A (ja) * | 1998-02-09 | 1999-08-24 | Ing Shoji Kk | 肉盛り溶接材料及び肉盛りクラッド材 |
| WO2002002830A1 (fr) * | 2000-07-04 | 2002-01-10 | Societe Industrielle De Metallurgie Avancee (S.I.M.A) | Compositions d'acier, procede pour son obtention et pieces fabriquees a partir de ces compositions |
| US20150368766A1 (en) * | 2014-06-19 | 2015-12-24 | The Ohio State University | Cobalt-free, galling and wear resistant austenitic stainless steel hard-facing alloy |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4803045A (en) * | 1986-10-24 | 1989-02-07 | Electric Power Research Institute, Inc. | Cobalt-free, iron-base hardfacing alloys |
-
2017
- 2017-10-11 GB GBGB1716640.6A patent/GB201716640D0/en not_active Ceased
-
2018
- 2018-09-19 US US16/135,531 patent/US20190106776A1/en not_active Abandoned
- 2018-09-24 EP EP18196212.7A patent/EP3470542B1/de active Active
- 2018-10-11 CN CN201811183479.1A patent/CN109652693A/zh active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2799577A (en) * | 1953-02-18 | 1957-07-16 | Crucible Steel Co America | Age hardening austenitic steel |
| GB1459255A (en) * | 1973-05-14 | 1976-12-22 | Armco Steel Corp | Galling resistant austenitic stainless steel |
| GB1595755A (en) * | 1978-01-23 | 1981-08-19 | Armco Inc | Galling resistant austenitic stainless steel |
| US4494988A (en) * | 1983-12-19 | 1985-01-22 | Armco Inc. | Galling and wear resistant steel alloy |
| US4814140A (en) * | 1987-06-16 | 1989-03-21 | Carpenter Technology Corporation | Galling resistant austenitic stainless steel alloy |
| JPH11226778A (ja) * | 1998-02-09 | 1999-08-24 | Ing Shoji Kk | 肉盛り溶接材料及び肉盛りクラッド材 |
| WO2002002830A1 (fr) * | 2000-07-04 | 2002-01-10 | Societe Industrielle De Metallurgie Avancee (S.I.M.A) | Compositions d'acier, procede pour son obtention et pieces fabriquees a partir de ces compositions |
| US20150368766A1 (en) * | 2014-06-19 | 2015-12-24 | The Ohio State University | Cobalt-free, galling and wear resistant austenitic stainless steel hard-facing alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3470542B1 (de) | 2023-11-01 |
| CN109652693A (zh) | 2019-04-19 |
| GB201716640D0 (en) | 2017-11-22 |
| US20190106776A1 (en) | 2019-04-11 |
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