EP1664362A1 - Ods-molybdän-silizium-bor-legierung - Google Patents
Ods-molybdän-silizium-bor-legierungInfo
- Publication number
- EP1664362A1 EP1664362A1 EP04761036A EP04761036A EP1664362A1 EP 1664362 A1 EP1664362 A1 EP 1664362A1 EP 04761036 A EP04761036 A EP 04761036A EP 04761036 A EP04761036 A EP 04761036A EP 1664362 A1 EP1664362 A1 EP 1664362A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- molybdenum
- oxides
- alloy
- alloy according
- volume
- 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
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
- C22C27/04—Alloys based on tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/18—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on silicides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
- C22C37/04—Cast-iron alloys containing spheroidal graphite
-
- 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 relates to a Mo-Si-B alloy consisting of the intermetallic phases molybdenum silicide and molybdenum borosilicate, optionally additionally molybdenum boride, the total content of intermetallic phase components being 25 to 90% by volume and the proportion of other structural components being ⁇ 5% by volume and the rest consists of molybdenum or mixed molybdenum crystal.
- Molybdenum and molybdenum alloys are widely used in industry because of their good mechanical strength properties at high temperatures. A problem with these alloys is their poor resistance to oxidation at temperatures above about 600 ° C.
- the known measures for improving the oxidation properties are correspondingly diverse. They range from the application of superficial protective layers to alloying measures.
- EP 0 804627 describes an oxidation-resistant molybdenum alloy which consists of a molybdenum matrix and intermetallic phase regions dispersed therein from 10 to 70% by volume Mo-B silicide, optionally up to 20% by volume Mo-boride and optionally up to 20 vol.% Mo silicide exists.
- the alloy comprises the elements C, Ti, Hf, Zr, W, Re, Al, Cr, V, Nb, Ta, B and Si in the form that one or more elements from the group Ti, Zr, Hf and Al must be present in the Mo mixed crystal phase in a proportion of 0.3-10% by weight.
- the alloy can optionally contain up to 2.5 vol.% Carbide.
- the alloy can be manufactured by various methods, preferably by means of powder metallurgical methods or by means of layer deposition methods. Alloys according to EP 0804627 form a borosilicate layer at temperatures above 540 ° C, which prevents further penetration of oxygen into the interior of the body.
- the addition of elements such as Ti, Zr, Hf or Al promotes the wetting of the boron-silicate layer, increases its melting point and leads to the formation of a high-melting oxide layer below the boron-silicate layer, which reduces further oxygen transport into the interior.
- the addition of carbides leads to an increase in mechanical strength. A serious disadvantage of such alloys is their low fracture toughness.
- alloys with an optimum silicon and boron content with regard to their oxidation resistance can no longer be produced using forming technology.
- the material according to the invention consists of the intermetallic phases molybdenum silicide and molybdenum boron silicide, optionally also molybdenum boride and molybdenum or molybdenum mixed crystal.
- Other structural components are also possible, although tests have shown that their volume content must be ⁇ 5%.
- Mo 3 Si and Mo 5 SiB 2 may be mentioned as preferred molybdenum silicide or molybdenum boron silicide phases.
- Oxides or mixed oxides, which have a vapor pressure of ⁇ 5x10 "2 bar at 1500 ° C, are finely distributed in this alloy matrix.
- the preferred mean particle size is ⁇ 5 ⁇ m.
- oxide additives in Mo-Si-B alloys not only increase the strength, as is customary in the case of ODS alloys, but surprisingly also to a high degree the ductility properties.
- Alloys with the structure according to the invention have an elongation at break which is at least 3 times higher at 1200 ° C. than Mo-Si-B alloys according to the prior art with the same silicon and boron content, but without the oxide additives according to the invention.
- a steam pressure at 1500 ° C of ⁇ 5x10 "2 is required to ensure adequate processability guarantee.
- the preferred oxides are: Y 2 O 3) ZrO 2 , Hf0 2 , TiO 2 , Al 2 O 3 , CaO, MgO and SrO.
- the alloy according to the invention can contain elements which form a mixed crystal with molybdenum. These include Re, Ti, Zr, Hf, V, Nb, Ta, Cr and AI. An Nb addition has proven particularly advantageous.
- Nb 5 atomic% Nb to a Mo-Si-B alloy with 8.8 atomic% Si and 7.6 atomic% B and 0.5 vol.% Yttrium oxide, the tensile strength can be changed at a test temperature of 1000 ° C 5% can be increased while increasing the elongation at break by 80%.
- the silicon and boron contents are advantageously chosen so that the composition in the three-substance system molybdenum silicon boron is in the range Mo-Mo 3 Si-T 2 (Mo 5 SiB 2 ) - Mo 2 B. This is the case if the Si content is 0.1-8.9% by weight and the B content is 0.1-5.3% by weight.
- a particularly advantageous concentration range in terms of strength, creep resistance, fracture toughness and oxidation behavior is 2-6% by weight Si, 0.5-2% by weight B and 0.2-1% by volume oxide.
- Powder mixtures consisting of the corresponding components are treated by mechanical alloying, whereby both elementary powders and pre-alloyed powders can be used.
- Usual high-energy mills such as attritors, ball mills or vibrating mills are suitable as units.
- Hot isostatic pressing has proven itself as a compacting process.
- the ground powder is poured into a Mo alloy jug, welded in a vacuum-tight manner and compacted at temperatures in the range of 1300 ° C - 1500 ° C.
- Other pressure-assisted hot compacting processes, such as powder extrusion can also be used.
- melt metallurgy manufacturing processes can also be used. Particularly noteworthy are spray compacting processes where oxide additives are added during the spray phase.
- 0.5% by weight of yttrium oxide powder with a mean grain size according to Fisher of 0.8 ⁇ m was mixed with 96.5% by weight of Mo with a grain size of 4.12 ⁇ m, 3.1% by weight of Si with a grain size of 4.41 ⁇ m and 1, 14 wt.% B with a grain size of 0.92 ⁇ m and mechanically alloyed.
- Mechanical alloying was carried out in an attritor under hydrogen. The attritor volume was 50 l and 100 kg balls made of a Fe-Cr-Ni alloy with a diameter of 9 mm were used. The attraction time was 10 hours. After mechanical alloying, only molybdenum and Y 2 Ü3 could be detected using XRD.
- the powder was placed in a jug made of an Mo-based alloy.
- the jug was evacuated and vacuum-sealed.
- the jug and powder were heated to a temperature of 1500 ° C. in an indirect oven and compacted by extrusion.
- the extrusion ratio was 1: 6.
- Tensile specimens were worked out from the extrusions thus produced by means of erosion and turning processes.
- a material without yttrium oxide was also produced for comparison purposes, the process steps mentioned above being used.
- the samples according to the invention and the comparative samples were characterized by a hot tensile test, the elongation rate being 10 '4 seconds "1.
- the test temperature was increased successively until a temperature could be determined at which the elongation of the tested sample was at least 10%.
- a temperature of 1000 ° C. could be determined in the sample according to the invention. For the material without the addition of oxide, this was 1300 ° C. The corresponding strength values at 1300 ° C were 300 MPa for the sample according to the invention and 200 MPa for the sample without added oxide.
- La (OH) 3 powder with an average grain size of 0.2 ⁇ m was mixed with 93.9% by weight of Mo with a powder grain size of 4.25 ⁇ m, 3.9% by weight of Si with a powder grain size of 4.30 ⁇ m and 1.4% by weight of B with a powder grain size of 1.15 ⁇ m and mechanically alloyed. Mechanical alloying was again carried out in an attritor under hydrogen for 10 hours. The powder was cold isostatically pressed at 2000 bar and then compacted by a sintering treatment at 1350 ° C. for 5 hours under hydrogen. The determination of the density showed that 91% of the theoretical density (8.7 g / cm 3 ) could be achieved.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0064003U AT6955U1 (de) | 2003-09-19 | 2003-09-19 | Ods-molybdän-silizium-bor-legierung |
PCT/AT2004/000314 WO2005028692A1 (de) | 2003-09-19 | 2004-09-15 | Ods-molybdän-silizium-bor-legierung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1664362A1 true EP1664362A1 (de) | 2006-06-07 |
EP1664362B1 EP1664362B1 (de) | 2012-02-01 |
Family
ID=32234844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04761036A Expired - Lifetime EP1664362B1 (de) | 2003-09-19 | 2004-09-15 | Ods-molybdän-silizium-bor-legierung |
Country Status (5)
Country | Link |
---|---|
US (1) | US7806995B2 (de) |
EP (1) | EP1664362B1 (de) |
CN (1) | CN1852999B (de) |
AT (2) | AT6955U1 (de) |
WO (1) | WO2005028692A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102017217082A1 (de) | 2017-09-26 | 2019-03-28 | Siemens Aktiengesellschaft | Pulver aus einer Molybdän, Silizium und Bor enthaltenden Legierung, Verwendung dieses Pulvers und additives Herstellungsverfahren für ein Werkstück aus diesem Pulver |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090011266A1 (en) * | 2007-07-02 | 2009-01-08 | Georgia Tech Research Corporation | Intermetallic Composite Formation and Fabrication from Nitride-Metal Reactions |
CN101397617B (zh) * | 2008-10-28 | 2010-11-24 | 西安交通大学 | 一种纳米稀土氧化物掺杂钼-硅-硼合金的制备方法 |
CN102424928B (zh) * | 2011-12-03 | 2013-07-31 | 西北有色金属研究院 | 一种Mo-Si-B-W多相复合材料及其制备方法 |
US9884367B2 (en) * | 2011-12-28 | 2018-02-06 | A.L.M.T. Corp. | Mo—Si—B-based alloy powder, metal-material raw material powder, and method of manufacturing a Mo—Si—B-based alloy powder |
WO2013177028A1 (en) * | 2012-05-21 | 2013-11-28 | Dow Corning Corporation | Silicothermic reduction of metal oxides to form eutectic composites |
JP5394582B1 (ja) | 2012-06-07 | 2014-01-22 | 株式会社アライドマテリアル | モリブデン耐熱合金 |
WO2014164859A2 (en) | 2013-03-11 | 2014-10-09 | Rolls-Royce Corporation | Compliant layer for ceramic components and methods of forming the same |
US9358613B2 (en) * | 2013-04-08 | 2016-06-07 | Baker Hughes Incorporated | Hydrophobic porous hard coating with lubricant, method for making and use of same |
US9992917B2 (en) | 2014-03-10 | 2018-06-05 | Vulcan GMS | 3-D printing method for producing tungsten-based shielding parts |
US9994937B1 (en) | 2014-05-20 | 2018-06-12 | Imaging Systems Technology, Inc. | Mo-Si-B manufacture |
DE102015214730A1 (de) * | 2014-08-28 | 2016-03-03 | MTU Aero Engines AG | Kriech- und oxidationsbeständige Molybdän - Superlegierung |
DE102015209583A1 (de) * | 2015-05-26 | 2016-12-01 | Siemens Aktiengesellschaft | Molybdän-Silizium-Borlegierung und Verfahren zur Herstellung sowie Bauteil |
CN105220051B (zh) * | 2015-10-28 | 2017-04-12 | 西北有色金属研究院 | 一种Mo‑Si‑B金属间化合物棒材及其制备方法 |
CN105506331B (zh) * | 2016-01-19 | 2017-10-03 | 西安航天新宇机电设备厂 | 一种Mo‑Si‑B‑Ti‑Zr‑Al‑Nb复合材料及其制备方法 |
CN105821272B (zh) * | 2016-05-18 | 2017-07-28 | 金堆城钼业股份有限公司 | 一种抗磨削的钼合金材料及其制备方法 |
CN108034875B (zh) * | 2017-11-21 | 2020-03-31 | 西安理工大学 | 一种掺杂稀土氧化物的Mo-Si-B合金及其制备方法 |
CN108015445B (zh) * | 2017-12-06 | 2024-05-10 | 中广核研究院有限公司 | 微合金化连接方法及微合金化连接结构 |
CN108193115B (zh) * | 2017-12-14 | 2019-09-24 | 昆山胜典机电科技进出口有限公司 | 一种钼合金的制备方法、钼合金及其应用 |
CN108060338B (zh) * | 2017-12-21 | 2019-11-08 | 陕西理工大学 | 一种铈锌共强化钼硅硼合金及其制备方法 |
DE102018113340B4 (de) | 2018-06-05 | 2020-10-01 | Otto-Von-Guericke-Universität Magdeburg | Dichteoptimierte Molybdänlegierung |
AT16308U3 (de) * | 2018-11-19 | 2019-12-15 | Plansee Se | Additiv gefertigtes Refraktärmetallbauteil, additives Fertigungsverfahren und Pulver |
CN109518053B (zh) * | 2018-11-30 | 2019-09-24 | 江苏东浦钨钼制品有限责任公司 | 一种高纯钼铼镧三元合金导杆及其生产工艺 |
CN111041319B (zh) * | 2019-12-31 | 2020-12-08 | 中国人民解放军空军工程大学 | 一种强韧抗高温氧化钼合金及其制备的方法 |
CN112176235A (zh) * | 2020-09-14 | 2021-01-05 | 自贡硬质合金有限责任公司 | 一种钼合金及其制备方法 |
US11761064B2 (en) * | 2020-12-18 | 2023-09-19 | Rtx Corporation | Refractory metal alloy |
CN112941407B (zh) * | 2021-01-27 | 2022-07-01 | 中国核动力研究设计院 | 反应堆用纳米氧化物强化铁素体钢、管材及其制备方法 |
CN114540814A (zh) * | 2022-03-08 | 2022-05-27 | 南京理工大学 | 一种高温耐磨抗氧化涂层 |
CN114406284A (zh) * | 2022-03-09 | 2022-04-29 | 南京理工大学 | 一种低密度高强度抗高温氧化的Mo-Si-B-Ti合金 |
Family Cites Families (11)
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US4195247A (en) * | 1978-07-24 | 1980-03-25 | General Electric Company | X-ray target with substrate of molybdenum alloy |
JPS6075545A (ja) * | 1983-09-29 | 1985-04-27 | Toshiba Corp | ダイス及びその製造方法 |
JPS60197839A (ja) * | 1984-03-22 | 1985-10-07 | Toshiba Corp | セラミツクス焼結用治具及びその製造方法 |
US4755712A (en) | 1986-12-09 | 1988-07-05 | North American Philips Corp. | Molybdenum base alloy and lead-in wire made therefrom |
AT395493B (de) * | 1991-05-06 | 1993-01-25 | Plansee Metallwerk | Stromzufuehrung |
US5693156A (en) | 1993-12-21 | 1997-12-02 | United Technologies Corporation | Oxidation resistant molybdenum alloy |
NO180361C (no) * | 1995-01-20 | 1997-04-09 | Modulvegger Marketing As | Anordning ved en knekt, såsom en hylleknekt, og et profil tilknyttet en lettvegg |
US5865909A (en) * | 1995-07-28 | 1999-02-02 | Iowa State University Research Foundation, Inc. | Boron modified molybdenum silicide and products |
US5868876A (en) * | 1996-05-17 | 1999-02-09 | The United States Of America As Represented By The United States Department Of Energy | High-strength, creep-resistant molybdenum alloy and process for producing the same |
AT2017U1 (de) * | 1997-05-09 | 1998-03-25 | Plansee Ag | Verwendung einer molybdän-/wolfram-legierung in bauteilen für glasschmelzen |
CN1083900C (zh) * | 1999-04-06 | 2002-05-01 | 株洲硬质合金厂 | 一种掺杂钼合金的制备方法 |
-
2003
- 2003-09-19 AT AT0064003U patent/AT6955U1/de not_active IP Right Cessation
-
2004
- 2004-09-15 CN CN2004800270857A patent/CN1852999B/zh not_active Expired - Fee Related
- 2004-09-15 EP EP04761036A patent/EP1664362B1/de not_active Expired - Lifetime
- 2004-09-15 AT AT04761036T patent/ATE543921T1/de active
- 2004-09-15 WO PCT/AT2004/000314 patent/WO2005028692A1/de active Application Filing
-
2006
- 2006-03-20 US US11/384,631 patent/US7806995B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO2005028692A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102017217082A1 (de) | 2017-09-26 | 2019-03-28 | Siemens Aktiengesellschaft | Pulver aus einer Molybdän, Silizium und Bor enthaltenden Legierung, Verwendung dieses Pulvers und additives Herstellungsverfahren für ein Werkstück aus diesem Pulver |
Also Published As
Publication number | Publication date |
---|---|
US7806995B2 (en) | 2010-10-05 |
ATE543921T1 (de) | 2012-02-15 |
US20060169369A1 (en) | 2006-08-03 |
AT6955U1 (de) | 2004-06-25 |
CN1852999B (zh) | 2012-05-30 |
EP1664362B1 (de) | 2012-02-01 |
WO2005028692A1 (de) | 2005-03-31 |
CN1852999A (zh) | 2006-10-25 |
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