EP1664362B1 - Ods-alloy of molybdenum, silicon and boron - Google Patents
Ods-alloy of molybdenum, silicon and boron Download PDFInfo
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- EP1664362B1 EP1664362B1 EP04761036A EP04761036A EP1664362B1 EP 1664362 B1 EP1664362 B1 EP 1664362B1 EP 04761036 A EP04761036 A EP 04761036A EP 04761036 A EP04761036 A EP 04761036A EP 1664362 B1 EP1664362 B1 EP 1664362B1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- 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
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- 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
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- 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
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- 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 Molybdänborsilizid, optionally additionally molybdenum boride, wherein the Summengehalt intermetallic phase constituents 25 to 90 vol.% And the proportion of other microstructural constituents according to claim 1 and the balance of molybdenum or molybdenum mixed crystal.
- Molybdenum and molybdenum alloys are widely used in engineering because of their good mechanical strength properties at high temperatures. A problem of these alloys is their low oxidation resistance at temperatures above about 600 ° C. Accordingly diverse are the known measures for improving the oxidation properties. They range from applying superficial protective coatings to alloying measures.
- the EP 0 804 627 describes an oxidation resistant molybdenum alloy consisting of a molybdenum matrix and intermetallic phase domains dispersed therein of 10-70 vol.% Mo-B silicide, optionally up to 20 vol.% Mo boride and optionally up to 20 vol.% Mo-silicide exists.
- the alloy comprises, in addition to molybdenum, the elements C, Ti, Hf, Zr, W, Re, Al, Cr, V, Nb, Ta, B and Si in the form that, in addition to the abovementioned phases, one or more elements of the group Ti, Zr, Hf and Al must be present in a proportion of 0.3 to 10 wt.% In the Mo mixed crystal phase.
- the alloy may contain up to 2.5 vol.% Carbide.
- the alloy can be produced by various processes, preferably by powder metallurgy or by Schichtabscheideclar. Alloys according to the EP 0 804 627 Form at temperatures above 540 ° C a borosilicate layer, which prevents further penetration of oxygen into 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 refractory oxide layer below the boron silicate layer, which reduces further oxygen transport into the interior.
- the object of the present invention is then to provide an oxidation-resistant Mo-Si-B alloy with high strength, which compared to known alloys has improved fracture toughness and improved formability at temperatures of about 1000 ° C.
- 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.
- Mo 3 Si and Mo 5 SiB 2 are to be mentioned as preferred molybdenum silicide or Molybdänborsilizid phases.
- oxides or mixed oxides which have a vapor pressure at 1500 ° C of ⁇ 5x10 -2 bar, finely dispersed.
- the preferred mean particle size is ⁇ 5 ⁇ m.
- alloys with the structure according to the invention have an elongation at break which is at least a factor of 3 at 1200 ° C., compared to state-of-the-art Mo-Si-B alloys having the same silicon and boron content, but without the oxide additives according to the invention.
- a vapor pressure at 1500 ° C of ⁇ 5x10 -2 is required to provide sufficient processability guarantee.
- Preferred oxides are: Y 2 O 3 , ZrO 2 , HfO 2 , TiO 2 , Al 2 O 3 , CaO, MgO and SrO.
- the alloy according to the invention may contain elements which form a mixed crystal with molybdenum. These include Re, Ti, Zr, Hf, V, Nb, Ta, Cr and Al. A Nb addition has proved to be particularly advantageous.
- Nb 5 at% of Nb to a Mo-Si-B alloy containing 8.8 at% Si and 7.6 at% B and 0.5 vol.% Of yttria, the tensile strength can be measured at a test temperature of 1000 ° C 5%, while increasing the elongation at break by 80%.
- the silicon and boron contents are advantageously to be selected such that the composition in the three-component system molybdenum-silicon-boron in the range Mo-Mo 3 Si-T 2 (Mo 5 SiB 2 ) - Mo 2 B is. This is the case when the Si content is 0.1-8.9 wt.% And the B content is 0.1-5.3 wt.%.
- a particularly advantageous concentration range both in terms of strength, creep resistance, fracture toughness and oxidation behavior is 2-6 wt.% Si, 0.5-2 wt.% B and 0.2-1 vol.% Oxide content.
- suitable powder metallurgical process techniques ensures that the oxide additives are present in sufficient fineness and homogeneity in the alloy matrix.
- powder mixtures consisting of the corresponding components are treated by mechanical alloying, wherein both elemental powders, as well as pre-alloyed powders can be used.
- aggregates are customary high energy mills such as attritors, ball drop mills or vibrating mills suitable.
- compaction process the hot isostatic pressing has been proven. The milled powder is filled into a jar made of a Mo alloy, welded vacuum-tight and compressed at temperatures in the range of 1300 ° C - 1500 ° C.
- Other pressure-assisted hot-compacting processes such as powder extrusion presses, can also be used.
- melt metallurgical production processes can be used.
- spray compacting processes where oxide additives are added during the spraying phase.
- 0.5% by weight of yttrium oxide powder having a mean grain size of Fisher of 0.8 microns was 96.5 wt.% Mo with a grain size of 4.12 .mu.m, 3.1 wt.% Si with a grain size of 4.41 microns and 1.14 wt.% B with a particle size of 0.92 microns mixed and mechanically alloyed.
- the mechanical alloying took place in an attritor under hydrogen.
- the attritor volume was 50 l and 100 kg balls of Fe-Cr-Ni alloy with a diameter of 9 mm were used.
- the attrition time was 10 hours. After mechanical alloying, only molybdenum and Y 2 O 3 could be detected by XRD.
- the powder was filled in a pot of Mo base alloy.
- the pot was evacuated and vacuum-sealed. Jug and powder were heated in an indirect oven to a temperature of 1500 ° C and compacted by extrusion. In this case, the extrusion ratio was 1: 6.
- Tensile samples were worked out by means of erosion and turning processes from the extrudates produced in this way.
- a material without yttrium oxide was prepared using the above-mentioned process steps.
- the characterization of the samples according to the invention and of the comparative samples was carried out by a hot tensile test, the strain rate being 10 -4 sec -1 . The test temperature was successively increased until a temperature could be determined at which the elongation of the tested sample was at least 10%.
- La (OH) 3 powder having an average particle size of 0.2 ⁇ m was coated with 93.9% by weight of Mo with a powder particle size of 4.25 ⁇ m, 3.9% by weight of Si with a powder particle size of 4.30 .mu.m and 1.4 wt.% B mixed with a powder grain size of 1.15 .mu.m and mechanically alloyed.
- the mechanical alloying again took place in an attritor under hydrogen for 10 hours.
- the powder was cold isostatically pressed at 2000 bar and then compacted by sintering at 1350 ° C / 5 hours under hydrogen.
- the determination of the density showed that 91% of the theoretical density (8.7 g / cm 3 ) could be achieved.
Abstract
Description
Die Erfindung betrifft eine Mo-Si-B-Legierung, bestehend aus den intermetallischen Phasen Molybdänsilizid und Molybdänborsilizid, wahlweise zusätzlich Molybdänborid, wobei der Summengehalt intermetallischer Phasenbestandteile 25 bis 90 Vol.% und der Anteil weiterer Gefügebestandteile gemäß Anspruch 1 beträgt und der Rest aus Molybdän oder Molybdänmischkristall besteht.The invention relates to a Mo-Si-B alloy consisting of the intermetallic phases molybdenum silicide and Molybdänborsilizid, optionally additionally molybdenum boride, wherein the Summengehalt intermetallic phase constituents 25 to 90 vol.% And the proportion of other microstructural constituents according to claim 1 and the balance of molybdenum or molybdenum mixed crystal.
Molybdän und Molybdän-Legierungen finden wegen ihrer guten mechanischen Festigkeitseigenschaften bei hohen Temperaturen verbreitet technische Verwendung. Ein Problem dieser Legierungen ist deren geringe Oxidationsbeständigkeit bei Temperaturen oberhalb etwa 600°C. Entsprechend vielfältig sind die bekannten Maßnahmen zur Verbesserung der Oxidationseigenschaften. Sie reichen vom Aufbringen oberflächlicher Schutzschichten bis zu legierungstechnischen Maßnahmen.Molybdenum and molybdenum alloys are widely used in engineering because of their good mechanical strength properties at high temperatures. A problem of these alloys is their low oxidation resistance at temperatures above about 600 ° C. Accordingly diverse are the known measures for improving the oxidation properties. They range from applying superficial protective coatings to alloying measures.
Die
Die Zugabe von Karbiden führt zu einer Steigerung der mechanischen Festigkeit. Ein schwerwiegender Nachteil derartiger Legierungen ist deren niedrige Bruchzähigkeit. Es schränkt nicht nur die technische Anwendung ein, sondern erschwert und beschränkt die Formgebung von daraus gefertigten Bauteilen. So lassen sich Legierungen mit einem in Hinblick auf deren Oxidationsbeständigkeit optimalen Silizium- und Bor-Gehalt (ca. 4 Gew.% Si, ca. 1,5 Gew.% B) umformtechnisch nicht mehr herstellten.The addition of carbides leads to an increase in mechanical strength. A serious disadvantage of such alloys is their low fracture toughness. It not only restricts the technical application, but complicates and restricts the shape of components made from it. Thus, alloys with an optimum in terms of their oxidation resistance silicon and boron content (about 4 wt.% Si, about 1.5 wt.% B) forming technology no longer produced.
Aufgabe der vorliegenden Erfindung ist danach die Bereitstellung einer oxidationsbeständigen Mo-Si-B-Legierung mit hoher Festigkeit, welche gegenüber bekannten Legierungen eine verbesserte Bruchzähigkeit und ein verbessertes Umformvermögen bei Temperaturen von ca. 1000°C besitzt.The object of the present invention is then to provide an oxidation-resistant Mo-Si-B alloy with high strength, which compared to known alloys has improved fracture toughness and improved formability at temperatures of about 1000 ° C.
Gelöst wird diese Aufgabe durch eine Mo-Si-B-Legierung, die 0,1 - 5 Vol.% eines oder mehrerer Oxide oder Mischoxide mit einem Dampfdruck bei 1500 °C von < 5x10-2 bar enthält wie gemäß Anspruch 1.This object is achieved by a Mo-Si-B alloy containing 0.1-5 vol.% Of one or more oxides or mixed oxides having a vapor pressure at 1500 ° C of <5x10 -2 bar as in claim 1.
Der erfindungsgemäße Werkstoff besteht aus den intermetallischen Phasen Molybdänsilizid und Molybdänborsilizid, wahlweise auch Molybdänborid und Molybdän bzw. Molybdänmischkristall. Als bevorzugte Molybdänsilizid bzw. Molybdänborsilizid Phasen sind dabei Mo3Si und Mo5SiB2 zu nennen. In dieser Legierungsmatrix sind Oxide oder Mischoxide, die einen Dampfdruck bei 1500°C von < 5x10-2 bar aufweisen, feinst verteilt. Die bevorzugte, mittlere Teilchengröße liegt dabei bei < 5 µm.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. Mo 3 Si and Mo 5 SiB 2 are to be mentioned as preferred molybdenum silicide or Molybdänborsilizid phases. In this alloy matrix are oxides or mixed oxides, which have a vapor pressure at 1500 ° C of <5x10 -2 bar, finely dispersed. The preferred mean particle size is <5 μm.
Es hat sich gezeigt, dass Oxidzusätze bei Mo-Si-B-Legierungen nicht nur, wie bei ODS-Legierungen üblich, die Festigkeit erhöhen, sondern überraschenderweise auch in hohem Maße die Duktilitätseigenschaften. So weisen Legierungen mit dem erfindungsgemäßen Aufbau eine bei 1200°C um zumindest den Faktor 3 höhere Bruchdehnung auf, als Mo-Si-B-Legierungen nach dem Stand der Technik mit gleichem Silizium- und Bor-Gehalt, jedoch ohne den erfindungsgemäßen Oxidzusätzen. Ein Dampfdruck bei 1500°C von < 5x10-2 ist erforderlich, um eine ausreichende Verarbeitbarkeit zu gewährleisten. Als bevorzugte Oxide sind dabei zu nennen: Y2O3, ZrO2, HfO2, TiO2, Al2O3, CaO, MgO und SrO. Ein erfindungsgemäßer Effekt kann auch dann erzielt werden, wenn Mischoxide zum Einsatz kommen.It has been shown that additions of oxides in the case of Mo-Si-B alloys not only increase the strength, as usual with ODS alloys, but also, to a large extent, the ductility properties to a great extent. Thus, alloys with the structure according to the invention have an elongation at break which is at least a factor of 3 at 1200 ° C., compared to state-of-the-art Mo-Si-B alloys having the same silicon and boron content, but without the oxide additives according to the invention. A vapor pressure at 1500 ° C of <5x10 -2 is required to provide sufficient processability guarantee. Preferred oxides are: Y 2 O 3 , ZrO 2 , HfO 2 , TiO 2 , Al 2 O 3 , CaO, MgO and SrO. An inventive effect can also be achieved when mixed oxides are used.
Weiters kann die erfindungsgemäße Legierung Elemente enthalten, die mit Molybdän einen Mischkristall bilden. Zu nennen sind dabei Re, Ti, Zr, Hf, V, Nb, Ta, Cr und Al. Besonders vorteilhaft hat sich dabei ein Nb-Zusatz erwiesen. Durch die Zugabe von 5 Atom% Nb zu einer Mo-Si-B-Legierung mit 8,8 Atom% Si und 7,6 Atom% B und 0,5 Vol.% Yttriumoxid kann die Zugfestigkeit bei einer Prüftemperatur von 1000°C um 5 % gesteigert werden, bei gleichzeitiger Erhöhung der Bruchdehnung um 80 %.Furthermore, the alloy according to the invention may contain elements which form a mixed crystal with molybdenum. These include Re, Ti, Zr, Hf, V, Nb, Ta, Cr and Al. A Nb addition has proved to be particularly advantageous. By adding 5 at% of Nb to a Mo-Si-B alloy containing 8.8 at% Si and 7.6 at% B and 0.5 vol.% Of yttria, the tensile strength can be measured at a test temperature of 1000 ° C 5%, while increasing the elongation at break by 80%.
Die Silizium- und Bor-Gehalte sind vorteilhafterweise so zu wählen, dass sich die Zusammensetzung im Dreistoffsystem Molybdän-Silizium-Bor im Bereich Mo-Mo3Si-T2 (Mo5SiB2) - Mo2B befindet. Dies ist dann der Fall, wenn der Si-Gehalt bei 0,1 - 8,9 Gew.% und der B-Gehalt bei 0,1 - 5,3 Gew.% liegt. Ein besonders vorteilhafter Konzentrationsbereich sowohl im Hinblick auf Festigkeit, Kriechbeständigkeit, Bruchzähigkeit und Oxidationsverhalten liegt bei 2 - 6 Gew.% Si, 0,5 - 2 Gew.% B und 0,2 - 1 Vol.% Oxidanteil. Bei Anwendung geeigneter pulvermetallurgischer Verfahrenstechniken ist gewährleistet, dass die Oxidzusätze in ausreichender Feinheit und Homogenität in der Legierungsmatrix vorliegen. Dabei werden Pulvermischungen, die aus den entsprechenden Komponenten bestehen durch mechanisches Legieren behandelt, wobei sowohl elementare Pulver, als auch vorlegierte Pulver zum Einsatz kommen können. Als Aggregate sind dabei übliche Hochenergiemühlen wie beispielsweise Attritoren, Kugelfallmühlen oder Schwingmühlen geeignet. Um eine Oxidation der Legierungskomponenten zu vermeiden, ist es vorteilhaft, den Mahlprozess unter Wasserstoff durchzuführen. Als Kompaktierverfahren hat sich das heißisostatische Pressen bewährt. Dabei wird das gemahlene Pulver in eine Kanne aus einer Mo-Legierung gefüllt, vakuumdicht verschweißt und bei Temperaturen im Bereich von 1300°C - 1500°C verdichtet. Auch andere druckunterstützte Warmkompaktierverfahren, wie beispielsweise Pulverstrangpressen, können zum Einsatz kommen. Um eine Gefügefeinung und Homogenisierung zu erreichen, ist es vorteilhaft, den kompaktierten Körper einem Umformprozess zu unterziehen. Dies erweist sich besonders dann als günstig, wenn die Warmkompaktierung durch druckloses Sintern erfolgt. Dabei werden die nach dem Sintern grob vorliegenden intermetallischen Phasenanteile zerkleinert. Eine nennenswerte Vergröberung der intermetallischen Phasenanteile während der thermomechanischen Behandlung wird durch die Oxidzusätze verhindert. Zudem wird eine Rekristallisation, speziell auch der molybdänreichen Phasenanteile, vermieden.The silicon and boron contents are advantageously to be selected such that the composition in the three-component system molybdenum-silicon-boron in the range Mo-Mo 3 Si-T 2 (Mo 5 SiB 2 ) - Mo 2 B is. This is the case when the Si content is 0.1-8.9 wt.% And the B content is 0.1-5.3 wt.%. A particularly advantageous concentration range both in terms of strength, creep resistance, fracture toughness and oxidation behavior is 2-6 wt.% Si, 0.5-2 wt.% B and 0.2-1 vol.% Oxide content. Using suitable powder metallurgical process techniques ensures that the oxide additives are present in sufficient fineness and homogeneity in the alloy matrix. In this case, powder mixtures consisting of the corresponding components are treated by mechanical alloying, wherein both elemental powders, as well as pre-alloyed powders can be used. As aggregates are customary high energy mills such as attritors, ball drop mills or vibrating mills suitable. In order to avoid oxidation of the alloy components, it is advantageous to carry out the milling process under hydrogen. As compaction process, the hot isostatic pressing has been proven. The milled powder is filled into a jar made of a Mo alloy, welded vacuum-tight and compressed at temperatures in the range of 1300 ° C - 1500 ° C. Other pressure-assisted hot-compacting processes, such as powder extrusion presses, can also be used. In order to achieve texture refinement and homogenization, it is advantageous to have the compacted body undergo a forming process. This proves to be particularly favorable when the hot compaction is carried out by pressureless sintering. In this case, the coarsely present after sintering intermetallic phase fractions are crushed. A significant coarsening of the intermetallic phase components during the thermomechanical treatment is prevented by the oxide additives. In addition, a recrystallization, especially the molybdenum-rich phase components avoided.
Neben pulvermetallurgischen Verfahrenstechniken können grundsätzlich auch schmelzmetallurgische Herstellprozesse zum Einsatz kommen. Zu nennen sind dabei besonders Sprühkompaktierverfahren, wo Oxidzusätze während der Sprühphase beigemengt werden.In addition to powder metallurgical process techniques, in principle also melt metallurgical production processes can be used. Particularly noteworthy are spray compacting processes, where oxide additives are added during the spraying phase.
Im Folgenden wird die Erfindung durch Beispiele näher beschrieben.In the following the invention will be described by examples.
0,5 Gew.% Yttriumoxidpulver mit einer mittleren Korngröße nach Fisher von 0,8 µm wurde mit 96,5 Gew.% Mo mit einer Korngröße von 4,12 µm, 3,1 Gew.% Si mit einer Korngröße von 4,41 µm und 1,14 Gew.% B mit einer Korngröße von 0,92 µm vermengt und mechanisch legiert. Das mechanische Legieren erfolgte in einem Attritor unter Wasserstoff. Das Attritorvolumen betrug 50 l und es kamen 100 kg Kugeln aus einer Fe-Cr-Ni-Legierung mit einem Durchmesser von 9 mm zum Einsatz. Die Attritierzeit betrug 10 Stunden. Nach dem mechanischen Legieren konnten mittels XRD nur Molybdän und Y2O3 detektiert werden. Das Pulver wurde in ein Kanne aus einer Mo-Basislegierung gefüllt. Die Kanne wurde evakuiert und vakuumdicht verschweißt. Kanne und Pulver wurden in einem Indirektofen auf eine Temperatur von 1500°C erhitzt und durch Strangpressen verdichtet. Das Strangpressverhältnis betrug dabei 1 : 6. Aus den so hergestellten Strangpresslingen wurden Zugproben mittels Erosion und Drehverfahren herausgearbeitet. Zu Vergleichszwecken wurde auch ein Werkstoff ohne Yttriumoxid hergestellt, wobei die oben erwähnten Verfahrensschritte zum Einsatz kamen. Die Charakterisierung der erfindungsgemäßen Proben und der Vergleichsproben erfolgte durch einen Warmzugversuch, wobei die Dehnrate 10-4Sek-1 betrug. Die Prüftemperatur wurde dabei sukzessive erhöht, bis eine Temperatur ermittelt werden konnte, bei der die Dehnung der geprüften Probe zumindest 10 % betrug. Bei der erfindungsgemäßen Probe konnte dabei eine Temperatur von 1000°C bestimmt werden. Beim Werkstoff ohne Oxidzusatz betrug diese 1300°C. Die korrespondierenden Festigkeitswerte bei 1300 °C betrugen dabei 300 MPa für die erfindungsgemäße Probe und 200 MPa für die Probe ohne Oxidzusatz.0.5% by weight of yttrium oxide powder having a mean grain size of Fisher of 0.8 microns was 96.5 wt.% Mo with a grain size of 4.12 .mu.m, 3.1 wt.% Si with a grain size of 4.41 microns and 1.14 wt.% B with a particle size of 0.92 microns mixed and mechanically alloyed. The mechanical alloying took place in an attritor under hydrogen. The attritor volume was 50 l and 100 kg balls of Fe-Cr-Ni alloy with a diameter of 9 mm were used. The attrition time was 10 hours. After mechanical alloying, only molybdenum and Y 2 O 3 could be detected by XRD. The powder was filled in a pot of Mo base alloy. The pot was evacuated and vacuum-sealed. Jug and powder were heated in an indirect oven to a temperature of 1500 ° C and compacted by extrusion. In this case, the extrusion ratio was 1: 6. Tensile samples were worked out by means of erosion and turning processes from the extrudates produced in this way. For comparison purposes, a material without yttrium oxide was prepared using the above-mentioned process steps. The characterization of the samples according to the invention and of the comparative samples was carried out by a hot tensile test, the strain rate being 10 -4 sec -1 . The test temperature was successively increased until a temperature could be determined at which the elongation of the tested sample was at least 10%. In the case of the sample according to the invention, it was possible to determine a temperature of 1000 ° C. For the material without added 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.
0,7 Gew.% La(OH)3-Pulver mit einer mittleren Korngröße von 0,2 µm wurde mit 93,9 Gew.% Mo mit einer Pulverkorngröße von 4,25 µm, 3,9 Gew.% Si mit einer Pulverkorngröße von 4,30 µm und 1,4 Gew.% B mit einer Pulverkorngröße von 1,15 µm vermengt und mechanisch legiert. Das mechanische Legieren erfolgte wiederum in einem Attritor unter Wasserstoff während 10 Stunden. Das Pulver wurde kaltisostatisch bei 2000 bar verpresst und anschließend durch eine Sinterbehandlung bei 1350°C / 5 Stunden unter Wasserstoff verdichtet. Die Bestimmung der Dichte zeigte, dass 91 % der theoretischen Dichte (8,7 g/cm3) erreicht werden konnte. Da der Anteil an offener Porosität vernachlässigbar gering war, konnte eine weitere Verdichtung durch heißisostatisches Pressen ohne die Verwendung einer Kanne erfolgen. Die Temperatur betrug dabei 1500°C, der Druck 1980 bar und die HIP-Zeit 4 Stunden. Die Dichte nach dem heißisostatischen Pressen betrug 9,5 g/cm3, was 99 % der theoretischen Dichte entspricht. Aus dieser Legierung gefertigte Proben wurden eine Oxidationsbehandlung bei 1200°C unterzogen. Die Gewichtsmessung erfolgte nach 1, 3, 10 und 30 Stunden. Diese Werte und Werte eines Werkstoffes ohne Oxidzusatz, ansonsten jedoch gleicher Zusammensetzung und Herstellung, sind in nachstehender Tabelle wiedergegeben.
Claims (11)
- Mo-Si-B alloy with 0.1 - 8.9 wt.% of Si and 0.1 - 5.3 wt.% of B, comprising the intermetallic phases of molybdenum silicide and molybdenum borosilicide, optionally additionally molybdenum boride, wherein the total content of intermetallic phase constituents is 25 to 90 vol.% and the remainder comprises molybdenum or a molybdenum mixed crystal,
characterized in that
the alloy contains 0.1 - 5 vol.% of at least one oxide or mixed oxide from the group of oxides of the metals Y, lanthanides, Zr, Hf, Ti, Al, Ca, Mg and Sr with a vapour pressure at 1,500 °C of < 5 x 10-2 bar. - Mo-Si-B alloy according to claim 1, characterized in that the oxides or mixed oxides have an average particle size of < 5 µm.
- Mo-Si-B alloy according to one of the preceding claims, characterized in that the oxides or mixed oxides have a vapour pressure of < 5 x 10-4 bar.
- Mo-Si-B alloy according to one of the preceding claims, characterized in that the total content of molybdenum silicide and molybdenum borosilicide is 40 - 80 vol.%.
- Mo-Si-B alloy according to one of the preceding claims, characterized in that the Mo mixed crystal contains one or more metals from the group of Re, Ti, Zr, Hf, V, Nb, Ta, Cr and Al.
- Mo-Si-B alloy according to one of the preceding claims, characterized in that this comprises 2 - 6 wt.% of Si, 0.5 - 2 wt.% of B, 0.2 - 1 vol.% of Y2O3 and Mo as the remainder.
- Mo-Si-B alloy according to one of the preceding claims, characterized in that this comprises 0.1 - 8.9 wt.% of Si, 0.1 - 5.3 wt.% of B, 1 - 25 wt.% of Nb, 0.1 - 5 vol.% of one or more oxides or mixed oxides of the metals of the group Y, lanthanides, Zr, Hf, Ti, Al, Ca, Mg and Sr and molybdenum as the remainder.
- Mo-Si-B alloy according to one of the preceding claims, characterized in that this comprises 2 - 6 wt.% of Si, 0.5 - 2 wt.% of B, 0.2 - 1 vol.% of Y2O3, 5 - 10 wt.% of Nb and molybdenum as the remainder.
- Process for the preparation of an Mo-Si-B alloy according to one of the preceding claims, characterized in that powder metallurgy process techniques are employed.
- Process for the preparation of an Mo-Si-B alloy according to claim 9, characterized in that the oxides or mixed oxides are ground by mechanical alloying into the alloy powder, which can be in elemental or prealloyed form.
- Process for the preparation of an Mo-Si-B alloy according to claim 9 and 10, characterized in that the mechanically alloyed powder is compacted by thermal compacting.
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AT0064003U AT6955U1 (en) | 2003-09-19 | 2003-09-19 | ODS MOLYBDENUM-SILICON ALLOY BOR |
PCT/AT2004/000314 WO2005028692A1 (en) | 2003-09-19 | 2004-09-15 | Ods-alloy of molybdenum, silicon and boron |
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EP1664362B1 true EP1664362B1 (en) | 2012-02-01 |
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US (1) | US7806995B2 (en) |
EP (1) | EP1664362B1 (en) |
CN (1) | CN1852999B (en) |
AT (2) | AT6955U1 (en) |
WO (1) | WO2005028692A1 (en) |
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AT2017U1 (en) * | 1997-05-09 | 1998-03-25 | Plansee Ag | USE OF A MOLYBDENUM / TUNGSTEN ALLOY IN COMPONENTS FOR GLASS MELTING |
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-
2003
- 2003-09-19 AT AT0064003U patent/AT6955U1/en not_active IP Right Cessation
-
2004
- 2004-09-15 WO PCT/AT2004/000314 patent/WO2005028692A1/en active Application Filing
- 2004-09-15 CN CN2004800270857A patent/CN1852999B/en not_active Expired - Fee Related
- 2004-09-15 EP EP04761036A patent/EP1664362B1/en not_active Not-in-force
- 2004-09-15 AT AT04761036T patent/ATE543921T1/en active
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2006
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Cited By (4)
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DE102015209583A1 (en) * | 2015-05-26 | 2016-12-01 | Siemens Aktiengesellschaft | Molybdenum-silicon-boron alloy and process for the production and component |
US10865467B2 (en) | 2015-05-26 | 2020-12-15 | Siemens Aktiengesellschaft | Molybdenum-silicon-boron alloy and method for producing same, and component |
DE102017217082A1 (en) * | 2017-09-26 | 2019-03-28 | Siemens Aktiengesellschaft | Powder of a molybdenum, silicon and boron-containing alloy, use of this powder and additive manufacturing process for a workpiece from this powder |
WO2019063498A1 (en) | 2017-09-26 | 2019-04-04 | Siemens Aktiengesellschaft | Powder made of an alloy containing molybdenum, silicon and boron, use of said powder and additive production method for a workpiece made of said powder |
Also Published As
Publication number | Publication date |
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CN1852999B (en) | 2012-05-30 |
WO2005028692A1 (en) | 2005-03-31 |
US20060169369A1 (en) | 2006-08-03 |
ATE543921T1 (en) | 2012-02-15 |
CN1852999A (en) | 2006-10-25 |
US7806995B2 (en) | 2010-10-05 |
EP1664362A1 (en) | 2006-06-07 |
AT6955U1 (en) | 2004-06-25 |
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