EP1844172B1 - Iron-based powder combination - Google Patents

Iron-based powder combination Download PDF

Info

Publication number
EP1844172B1
EP1844172B1 EP06701553.7A EP06701553A EP1844172B1 EP 1844172 B1 EP1844172 B1 EP 1844172B1 EP 06701553 A EP06701553 A EP 06701553A EP 1844172 B1 EP1844172 B1 EP 1844172B1
Authority
EP
European Patent Office
Prior art keywords
powder
iron
molybdenum
weight
alloyed
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.)
Active
Application number
EP06701553.7A
Other languages
German (de)
French (fr)
Other versions
EP1844172A1 (en
EP1844172A4 (en
Inventor
Mats Larsson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoganas AB
Original Assignee
Hoganas AB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoganas AB filed Critical Hoganas AB
Publication of EP1844172A1 publication Critical patent/EP1844172A1/en
Publication of EP1844172A4 publication Critical patent/EP1844172A4/en
Application granted granted Critical
Publication of EP1844172B1 publication Critical patent/EP1844172B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C22C33/0207Using a mixture of prealloyed powders or a master alloy
    • 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
    • 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
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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
    • C22C38/16Ferrous alloys, e.g. steel alloys containing copper

Definitions

  • the present invention refers to iron-based powder metallurgical combinations and to methods for preparing sintered powder metallurgical components therefrom. More specifically the invention refers to the production of sintered components including copper, nickel and molybdenum by using these combinations.
  • Sintered iron-based components can be produced by mixing alloying elements with the pure iron powders. However, this may cause problems with dust and segregation which may lead to variations in size and mechanical properties of the sintered component.
  • the alloying elements may be pre-alloyed or diffusion alloyed with the iron powder. In one method molybdenum is pre-alloyed with iron powder and this pre-alloyed iron powder is subsequently diffusion alloyed with copper and nickel for production of sintered components from iron-based powder compositions containing molybdenum, nickel and copper.
  • US 5082433 disclose moulded articles, particularly cams for camshafts of internal combustion engines, subjected to high wear conditions. In order to make them resistant to wear, they are produced from a sintered alloy which has been fabricated by powder metallurgical means.
  • the alloy has a hardened matrix with interstitial copper and consists of 0.5 to 16% by weight of molybdenum, 1 to 20% by weight of copper, 0.1 to 1.5% by weight of carbon and, optionally, of admixtures of chromium, manganese, silicon and nickel totalling, at most, 5% by weight, the remainder being iron.
  • US 5567890 disclose an iron-based powder for producing highly resistant components having a small local variation in dimensional change by powder compacting and sintering.
  • the powder contains - in addition to Fe - 0.5-4.5% by weight Ni, 0.65-2.25% by weight Mo and 0.35-0.65% by weight C, and optionally a lubricant and impurities.
  • the maximum variation in dimensional change is 0.07% for a minimum density of 6.7 g/cm 3 .
  • WO 2004/038054 disclose a method of controlling the dimensional change to a predetermined value including the steps of providing a first powder (A) consisting of an iron based powder (1) and copper in the form of elemental copper (2), or copper diffusion bonded to said iron-based powder (3). Providing a second powder (B) consisting of said iron-based powder (1) and a pre-alloyed iron-copper powder (4); mixing said first and second powder mixtures (A) and (B) in proportions resulting in the desired dimensional change adding graphite and lubricant and optionally hard phase materials and other alloying elements to the obtained mixture. At last compacting the obtained mixture and sintering the compacted body.
  • the present invention provides a method of eliminating the need of producing a specific powder for each desired chemical composition of the sintered iron-based component having alloying elements from molybdenum, copper and nickel.
  • the invention also offers the advantage of providing a method for controlling the dimensional change and the tensile strength to predetermined values.
  • the dimensional change is independent of the carbon content and the density.
  • the invention concerns a powder metallurgical combination of three different iron-based powders as defined in claim 1.
  • the first of these iron-based powders consisting of core particles of iron, pre-alloyed with molybdenum, which is additionally diffusion alloyed with copper and the second iron-based powder consisting of core particles of iron, pre-alloyed with molybdenum, which is diffusion alloyed with nickel.
  • the third iron-based powder essentially consists of particles of iron pre-alloyed with molybdenum.
  • a method according to the invention is defined in claim 6 and comprises the steps of combining these three iron-based powders in predetermined amounts, mixing the combination with graphite, compacting the obtained mixture and sintering the obtained green body to provide a sintered component having a predetermined strength and a predetermined dimensional change during sintering.
  • Figs 1-4 illustrate diagrams for determining the copper and nickel content in the powder metallurgical combination for a predetermined strength and dimensional change.
  • iron-based powder metallurgical combination according to the invention comprises:
  • the amount of copper and nickel which is diffusion alloyed to the core particles is limited in the upper range to 15% copper and 12% nickel.
  • the lower limit of copper and nickel which is diffusion alloyed to the core particles should be substantially higher than the amount required in the sintered component to achieve the advantages of the invention.
  • an iron-based powder essentially consisting of core particles pre-alloyed with molybdenum and comprising at least 6% copper diffusion alloyed to the core particles and an iron-based powder having core particles pre-alloyed with molybdenum and comprising at least 4.5% nickel diffusion alloyed to the core particles are of special interest.
  • the powders A, B and C essentially consist of particles of iron pre-alloyed with molybdenum, but other elements, except unavoidable impurities, may be pre-alloyed to the particles.
  • Such elements may be nickel, copper, chromium and manganese.
  • the respective amounts of powder A, B and C are determined and mixed with graphite in the amount required for the predetermined strength.
  • the obtained mixture may be mixed with other additives before compaction and sintering.
  • the amount of graphite which is mixed in the powder combination is 0.3-0.7%.
  • additives are selected from the group consisting of lubricants, binders, other alloying elements, hard phase materials, machinability enhancing agents.
  • powder C is essentially free from Cu and Ni.
  • the relation between powder A, B and C is chosen so that the copper content will be 0.2-2% by weight, the nickel content will be 0.1-4% by weight and the molybdenum content is preferably 0.5-1.5% by weight of the sintered component.
  • the copper content is 0.2-2%, preferably 0.4-0.8% and the nickel content is 0.1-4%, it has been unexpectedly been found that the dimensional change during sintering is independent of the carbon content and sintered density.
  • the amounts of copper, nickel and carbon, respectively, in the sintered component is determined by means of diagrams, e.g. from fig 1-4 .
  • the required amounts of powder A, B and C, respectively, may then be determined by a person skilled in the art.
  • the powders are mixed with graphite to obtain the final desired carbon content.
  • the powder combination is compacted at a compaction pressure between 400-1000 MPa and the obtained green body is sintered at 1100-1300°C for 10-60 minutes in a protective atmosphere.
  • the sintered body may be subjected to further post treatments, such as heat treatment, surface densification, machining etc.
  • the exemplifying diagrams in fig 1-4 are valid at a compaction pressure of 600 MPa, sintered at 1120°C for 30 minutes in an atmosphere of 90% nitrogen and 10% of hydrogen.
  • sintered components containing various amounts of molybdenum, copper and nickel may be produced. This is achieved by using a combination of three different powders, which are mixed in different proportions to achieve a powder having the required chemical composition for the actual sintered component.
  • a particular advantage of the invention is that the dimensional change during sintering as well as the strength of the sintered component can be controlled.
  • the advantage of being able to control the dimensional change will facilitate the use of existing pressing tools.
  • a certain scatter in carbon content and density may be unavoidable.
  • the scatter in dimensions after sintering will be reduced hence subsequent machining and machining costs can be decreased.
  • This example demonstrates how to choose an alloying composition having a desired strength of about 600 MPa and three levels of dimensional change (-0.1%, 0.0% and +0.1%). This was done for two carbon levels, 0.5% C and 0.3% C, respectively, in the powder combinations according to table 1, where the lower carbon content yields better ductility as can be seen in table 2.
  • the powder combinations according to the present invention were prepared from a powder A with 10% of copper diffusion alloyed to the surface of an iron-based powder pre-alloyed with 0.85% of molybdenum, a powder B with 5% of nickel diffusion alloyed to the surface of an iron-based powder pre-alloyed with 0.85% of molybdenum and a powder C of an iron-based powder pre-alloyed with 0.85% of molybdenum.
  • the powder combinations were mixed with 0.8% amide wax as a lubricant and graphite, to yield a sintered carbon content of 0.3 % and 0.5 %, respectively.
  • the obtained mixtures were compacted to tensile test specimen according to ISO 2740.
  • the compaction pressure was 600 MPa and the sintering conditions were: 1120°C, 30 min, 90% N 2 /10% H 2 .
  • table 2 other mechanical properties from the powder combinations according to the invention are presented. It can be clearly seen that the powder combinations according to the invention have the predetermined dimensional change according to fig 3 .
  • Powder combination (1) 0.6 1.3 0.83 0.5 7.08 -0.104 Powder combination (2) 1.15 0.8 0.83 0.5 7.06 0.004 Powder combination (3) 1.55 0.4 0.83 0.5 7.04 0.096 Powder combination (4) 0.9 2.3 0.83 0.3 7.11 -0.096 Powder combination (5) 1.3 2 0.83 0.3 7.09 0.007 Powder combination (6) 1.6 1.7 0.83 0.3 7.07 0.095 Table 2 Hardness HV10 Tensile strength (MPa) Yield strength (MPa) Young's modulus (GPa) Elongation (%) Powder combination (1) 219 599 413 139 2.0 Powder combination (2) 223 601 429 139 1.8 Powder combination (3) 219 602 447 139 1.6 Powder combination (4) 207 601 397 138 2.4 Powder combination (5) 209 604 408 137 2.2 Powder combination (6) 206 602 417 137 2.1
  • This example illustrates powder combinations according to the invention, comprising 0.6% Cu and 2% Ni and a specific embodiment having dimensional change independent of carbon content and sintered density as shown in table 3.
  • the results obtained with these combinations are compared with the results obtained with Distaloy AB (available from Höganäs AB, Sweden) as well as with a powder having the same chemical composition as the powder combination according to the invention but wherein iron-based powder pre-alloyed with molybdenum has both copper and nickel diffusion alloyed to the surface, in table 3 designated as "fixed composition".
  • the powder combinations according to the present invention were prepared from a powder A with 10% of copper diffusion alloyed to the surface of an iron-based powder pre-alloyed with 0.85% of molybdenum, a powder B with 5% of nickel diffusion alloyed to the surface of an iron-based powder pre-alloyed with 0.85% of molybdenum and a powder C consisting of an iron-based powder pre-alloyed with 0.85% of molybdenum.
  • Table 3 shows a specific example where a mixture of powder A, powder B and powder C having a total content of 0.6% copper, 2% of nickel and 0.83% of molybdenum is compared with a known powder, Distaloy AB, and an iron-based powder having 0.83% of pre-alloyed molybdenum, 0.6% of copper and 2% of nickel diffusion alloyed to the surface of the iron-based powder.
  • the dimensional change of sintered samples, produced from the powder combination according to the invention is essentially independent of the carbon content and density compared with the known powder Distaloy AB or the iron-based powder diffusion alloyed with both copper and nickel.
  • the powder combinations were mixed with 0.8% amide wax as a lubricant and graphite, to yield a sintered carbon content according to table 3.
  • the obtained mixtures were compacted to tensile test specimen according to ISO 2740 at different compaction pressures according to table 3.
  • the tensile test specimens were sintered at 1120°C for 30 minutes in an atmosphere of 90 % nitrogen and 10 % of hydrogen.
  • table 4 further mechanical properties are presented.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Description

    FIELD OF THE INVENTION
  • The present invention refers to iron-based powder metallurgical combinations and to methods for preparing sintered powder metallurgical components therefrom. More specifically the invention refers to the production of sintered components including copper, nickel and molybdenum by using these combinations.
  • BACKGROUND OF THE INVENTION
  • Within the powder metallurgical field, copper, nickel and molybdenum has since long been used as alloying elements in the production of high strength sintered components.
  • Sintered iron-based components can be produced by mixing alloying elements with the pure iron powders. However, this may cause problems with dust and segregation which may lead to variations in size and mechanical properties of the sintered component. In order to avoid segregation the alloying elements may be pre-alloyed or diffusion alloyed with the iron powder. In one method molybdenum is pre-alloyed with iron powder and this pre-alloyed iron powder is subsequently diffusion alloyed with copper and nickel for production of sintered components from iron-based powder compositions containing molybdenum, nickel and copper.
  • It is however obvious that, when producing a sintered iron-based component, from a powder wherein molybdenum is pre-alloyed and wherein copper and nickel are diffusion alloyed, the content of the alloying elements in the sintered iron-based component will be substantially identical with the content of alloying elements in the used diffusion alloyed powder. In order to reach different contents of the alloying elements in the sintered component, yielding different properties, iron-based powders having different contents of the alloying elements have to be used.
  • US 5082433 disclose moulded articles, particularly cams for camshafts of internal combustion engines, subjected to high wear conditions. In order to make them resistant to wear, they are produced from a sintered alloy which has been fabricated by powder metallurgical means. The alloy has a hardened matrix with interstitial copper and consists of 0.5 to 16% by weight of molybdenum, 1 to 20% by weight of copper, 0.1 to 1.5% by weight of carbon and, optionally, of admixtures of chromium, manganese, silicon and nickel totalling, at most, 5% by weight, the remainder being iron.
  • US 5567890 disclose an iron-based powder for producing highly resistant components having a small local variation in dimensional change by powder compacting and sintering. The powder contains - in addition to Fe - 0.5-4.5% by weight Ni, 0.65-2.25% by weight Mo and 0.35-0.65% by weight C, and optionally a lubricant and impurities. The maximum variation in dimensional change is 0.07% for a minimum density of 6.7 g/cm3.
  • WO 2004/038054 disclose a method of controlling the dimensional change to a predetermined value including the steps of providing a first powder (A) consisting of an iron based powder (1) and copper in the form of elemental copper (2), or copper diffusion bonded to said iron-based powder (3). Providing a second powder (B) consisting of said iron-based powder (1) and a pre-alloyed iron-copper powder (4); mixing said first and second powder mixtures (A) and (B) in proportions resulting in the desired dimensional change adding graphite and lubricant and optionally hard phase materials and other alloying elements to the obtained mixture. At last compacting the obtained mixture and sintering the compacted body.
  • The article "New high performance ferrous P/M material for demanding automotive applications" by James, W.B,, Baran, M.C., Semel, F.J., Causton, R.J., Narasimhan, K.S., Murphy, T.F., presented at Euro2000, Munich, 18th-20th October 2000, discloses that engineered binder-treated premixes have been developed as alternatives to diffusion-alloyed powders including those based on a pre-alloyed powder (1.5 w/o molybdenum). The engineered binder-treated materials are compacted with their diffusion-alloyed counterparts.
  • The present invention provides a method of eliminating the need of producing a specific powder for each desired chemical composition of the sintered iron-based component having alloying elements from molybdenum, copper and nickel. The invention also offers the advantage of providing a method for controlling the dimensional change and the tensile strength to predetermined values. In a specific embodiment the dimensional change is independent of the carbon content and the density.
  • SUMMARY OF THE INVENTION
  • In brief the invention concerns a powder metallurgical combination of three different iron-based powders as defined in claim 1. The first of these iron-based powders consisting of core particles of iron, pre-alloyed with molybdenum, which is additionally diffusion alloyed with copper and the second iron-based powder consisting of core particles of iron, pre-alloyed with molybdenum, which is diffusion alloyed with nickel. The third iron-based powder essentially consists of particles of iron pre-alloyed with molybdenum.
  • A method according to the invention is defined in claim 6 and comprises the steps of combining these three iron-based powders in predetermined amounts, mixing the combination with graphite, compacting the obtained mixture and sintering the obtained green body to provide a sintered component having a predetermined strength and a predetermined dimensional change during sintering.
  • DESCRIPTION OF THE DRAWINGS
  • Figs 1-4 illustrate diagrams for determining the copper and nickel content in the powder metallurgical combination for a predetermined strength and dimensional change.
  • DETAILED DESCRIPTION OF THE INVENTION
  • Specifically the iron-based powder metallurgical combination according to the invention comprises:
    • an iron-based powder A essentially consisting of core particles of iron pre-alloyed with molybdenum, whereby 6-15%, preferably 8-12% by weight of copper, is diffusion alloyed to the core particles.
    • an iron-based powder B essentially consisting of core particles of iron pre-alloyed with molybdenum, whereby 4.5-8%, preferably 5-7% by weight of nickel, is diffusion alloyed to the core particles, and
    • an iron-based powder C, essentially consisting of particles of iron pre-alloyed with molybdenum and the relation between powders A, B and C is chosen so that the copper content of the powder metallurgical combination is 0.2 - 2 % by weight, the nickel content of the powder metallurgical combination is 0.1 - 4 % by weight and the molybdenum content of the powder metallurgical combination is 0.3 - 2 % by weight, and the graphite content of the powder metallurgical combination is 0.3-0.7% by weight,
    • wherein the amount of molybdenum in each of powder A, B or C is 0.3-2%, preferably 0.5-1.5%, by weight, and the amount of molybdenum is essentially the same in each of powder A, B or C. Amounts above 2% of Mo do not give an increase of the strength justifying the increase of the costs. Amounts of Mo below 0.3% do not give a significant effect of the strength.
  • The amount of copper and nickel which is diffusion alloyed to the core particles is limited in the upper range to 15% copper and 12% nickel. The lower limit of copper and nickel which is diffusion alloyed to the core particles should be substantially higher than the amount required in the sintered component to achieve the advantages of the invention. Thus, for practical reasons an iron-based powder essentially consisting of core particles pre-alloyed with molybdenum and comprising at least 6% copper diffusion alloyed to the core particles and an iron-based powder having core particles pre-alloyed with molybdenum and comprising at least 4.5% nickel diffusion alloyed to the core particles are of special interest.
  • The powders A, B and C, respectively, essentially consist of particles of iron pre-alloyed with molybdenum, but other elements, except unavoidable impurities, may be pre-alloyed to the particles. Such elements may be nickel, copper, chromium and manganese.
  • In order to produce a sintered component from the powder combination according to the present invention, the respective amounts of powder A, B and C are determined and mixed with graphite in the amount required for the predetermined strength. The obtained mixture may be mixed with other additives before compaction and sintering. The amount of graphite which is mixed in the powder combination is 0.3-0.7%.
  • Other additives are selected from the group consisting of lubricants, binders, other alloying elements, hard phase materials, machinability enhancing agents.
  • In accordance with one embodiment of the powder metallurgical combination, powder C is essentially free from Cu and Ni.
  • The relation between powder A, B and C is chosen so that the copper content will be 0.2-2% by weight, the nickel content will be 0.1-4% by weight and the molybdenum content is preferably 0.5-1.5% by weight of the sintered component.
  • When the copper content is 0.2-2%, preferably 0.4-0.8% and the nickel content is 0.1-4%, it has been unexpectedly been found that the dimensional change during sintering is independent of the carbon content and sintered density.
  • In order to produce a sintered component with a predetermined dimensional change and strength, the amounts of copper, nickel and carbon, respectively, in the sintered component is determined by means of diagrams, e.g. from fig 1-4. The required amounts of powder A, B and C, respectively, may then be determined by a person skilled in the art.
  • The powders are mixed with graphite to obtain the final desired carbon content. The powder combination is compacted at a compaction pressure between 400-1000 MPa and the obtained green body is sintered at 1100-1300°C for 10-60 minutes in a protective atmosphere. The sintered body may be subjected to further post treatments, such as heat treatment, surface densification, machining etc.
  • The exemplifying diagrams in fig 1-4 are valid at a compaction pressure of 600 MPa, sintered at 1120°C for 30 minutes in an atmosphere of 90% nitrogen and 10% of hydrogen.
  • According to the present invention sintered components containing various amounts of molybdenum, copper and nickel may be produced. This is achieved by using a combination of three different powders, which are mixed in different proportions to achieve a powder having the required chemical composition for the actual sintered component.
  • To summarize a particular advantage of the invention is that the dimensional change during sintering as well as the strength of the sintered component can be controlled. The advantage of being able to control the dimensional change will facilitate the use of existing pressing tools. When producing sintered parts a certain scatter in carbon content and density may be unavoidable. By utilising the combinations having a dimensional change independent of the density and carbon content the scatter in dimensions after sintering will be reduced hence subsequent machining and machining costs can be decreased.
  • The invention is illustrated by the following nonlimiting examples:
  • Example 1
  • This example demonstrates how to choose an alloying composition having a desired strength of about 600 MPa and three levels of dimensional change (-0.1%, 0.0% and +0.1%). This was done for two carbon levels, 0.5% C and 0.3% C, respectively, in the powder combinations according to table 1, where the lower carbon content yields better ductility as can be seen in table 2.
  • The powder combinations according to the present invention were prepared from a powder A with 10% of copper diffusion alloyed to the surface of an iron-based powder pre-alloyed with 0.85% of molybdenum, a powder B with 5% of nickel diffusion alloyed to the surface of an iron-based powder pre-alloyed with 0.85% of molybdenum and a powder C of an iron-based powder pre-alloyed with 0.85% of molybdenum.
  • The powder combinations were mixed with 0.8% amide wax as a lubricant and graphite, to yield a sintered carbon content of 0.3 % and 0.5 %, respectively. The obtained mixtures were compacted to tensile test specimen according to ISO 2740.
  • The compaction pressure was 600 MPa and the sintering conditions were: 1120°C, 30 min, 90% N2/10% H2. In table 2 other mechanical properties from the powder combinations according to the invention are presented. It can be clearly seen that the powder combinations according to the invention have the predetermined dimensional change according to fig 3. Table 1
    Cu (%) Ni (%) Mo (%) C (%) Sintered density (g/cm3) Dimensional change (%)
    Powder combination (1) 0.6 1.3 0.83 0.5 7.08 -0.104
    Powder combination (2) 1.15 0.8 0.83 0.5 7.06 0.004
    Powder combination (3) 1.55 0.4 0.83 0.5 7.04 0.096
    Powder combination (4) 0.9 2.3 0.83 0.3 7.11 -0.096
    Powder combination (5) 1.3 2 0.83 0.3 7.09 0.007
    Powder combination (6) 1.6 1.7 0.83 0.3 7.07 0.095
    Table 2
    Hardness HV10 Tensile strength (MPa) Yield strength (MPa) Young's modulus (GPa) Elongation (%)
    Powder combination (1) 219 599 413 139 2.0
    Powder combination (2) 223 601 429 139 1.8
    Powder combination (3) 219 602 447 139 1.6
    Powder combination (4) 207 601 397 138 2.4
    Powder combination (5) 209 604 408 137 2.2
    Powder combination (6) 206 602 417 137 2.1
  • Example 2
  • This example illustrates powder combinations according to the invention, comprising 0.6% Cu and 2% Ni and a specific embodiment having dimensional change independent of carbon content and sintered density as shown in table 3. The results obtained with these combinations are compared with the results obtained with Distaloy AB (available from Höganäs AB, Sweden) as well as with a powder having the same chemical composition as the powder combination according to the invention but wherein iron-based powder pre-alloyed with molybdenum has both copper and nickel diffusion alloyed to the surface, in table 3 designated as "fixed composition".
  • The powder combinations according to the present invention were prepared from a powder A with 10% of copper diffusion alloyed to the surface of an iron-based powder pre-alloyed with 0.85% of molybdenum, a powder B with 5% of nickel diffusion alloyed to the surface of an iron-based powder pre-alloyed with 0.85% of molybdenum and a powder C consisting of an iron-based powder pre-alloyed with 0.85% of molybdenum.
  • Table 3 shows a specific example where a mixture of powder A, powder B and powder C having a total content of 0.6% copper, 2% of nickel and 0.83% of molybdenum is compared with a known powder, Distaloy AB, and an iron-based powder having 0.83% of pre-alloyed molybdenum, 0.6% of copper and 2% of nickel diffusion alloyed to the surface of the iron-based powder. As disclosed in table 3 the dimensional change of sintered samples, produced from the powder combination according to the invention, is essentially independent of the carbon content and density compared with the known powder Distaloy AB or the iron-based powder diffusion alloyed with both copper and nickel.
  • The powder combinations were mixed with 0.8% amide wax as a lubricant and graphite, to yield a sintered carbon content according to table 3. The obtained mixtures were compacted to tensile test specimen according to ISO 2740 at different compaction pressures according to table 3. The tensile test specimens were sintered at 1120°C for 30 minutes in an atmosphere of 90 % nitrogen and 10 % of hydrogen. In table 4 further mechanical properties are presented. Table 3
    Cu (%) Ni (% ) Mo (%) C (%) Compacting pressure (MPa) Sintered density (g/cm3) Dimensional change (%)
    Powder combination (7)* 0.6 % 0.38 600 7.11 -0.117
    Powder combination (8)* 0.6 2 0.54 600 7.09 -0.118
    Powder combination (9)* 0.6 2 0.74 600 7.06 -0.117
    Powder combination (10)* 0.6 2 0.55 400 6.77 -0.114
    Powder combination (11)* 0.6 2 0.53 800 7.22 -0.129
    Fixed composition (1) 0.6 2 0.21 600 7.16 -0.155
    Fixed composition (2) 0.6 2 0.50 600 7.12 -0.147
    Fixed composition (3) 0.6 2 0.78 600 7.08 -0.118
    Fixed composition (4) 0.6 2 0.21 400 6.79 -0.134
    Fixed composition (5) 0.6 2 0.49 800 7.26 -0.163
    Distaloy AB (2) 1.5 1.75 0.5 0.35 0.35 600 7.06 -0.012
    Distaloy AB (3) 1.5 1.75 0.5 0.54 600 7.05 -0.034
    Distaloy AB (4) 1.5 1.75 0.5 0.73 600 7.04 -0.056
    Distaloy AB (5) 1.5 1.75 0.5 0.54 400 6.73 -0.048
    Distaloy AB (6) 1.5 1.75 0.5 0.53 800 7.19 -0.027
    (*) Powder combination according to the invention
    Table 4
    Hardness HV10 Tensile strength (MPa) Yield strength (MPa) Young's modulus (GPa) Elongation (%)
    Powder combination (7)* 183 570 391 137 2.6
    Powder combination (8)* 206 632 433 135 1.8
    Powder combination (9)* 244 669 485 138 1.1
    Powder combination (10)* 171 507 363 114 1.3
    Powder combination (11)* 234 672 450 143 2.1
    Fixed composition (1) - - - - -
    Fixed composition (2) 213 649 437 133 2.2
    Fixed composition (3) - - - - -
    Fixed composition (4) - - - - -
    Fixed composition (5) - - - - -
    Distaloy AB (2) 160 562 333 133 3.8
    Distaloy AB (3) 189 618 392 136 2.2
    Distaloy AB (4) 218 626 437 139 1.1
    Distaloy AB (5) 160 523 344 115 1.0
    Distaloy AB (6) 200 658 411 145 2.8
    (*) Powder combination according to the invention

Claims (6)

  1. A powder metallurgical combination comprising:
    - an iron-based powder A, consisting of core particles of iron pre-alloyed with molybdenum, whereby 6-15% by weight of powder A is copper being diffusion alloyed to the core particles,
    - an iron-based powder B, consisting of core particles of iron pre-alloyed with molybdenum, whereby 4.5-8% by weight of powder B is nickel being diffusion alloyed to the core particles, and
    - an iron-based powder C, consisting of particles of iron pre-alloyed with molybdenum
    - the relation between powder A, B and C is chosen so that the copper content of the powder metallurgical combination is 0.2 - 2 % by weight, the nickel content of the powder metallurgical combination is 0.1 - 4 % by weight, the molybdenum content of the powder metallurgical combination is 0.3 - 2 % by weight, and the graphite content of the powder metallurgical combination is 0.3-0.7% by weight,
    - wherein the amount of molybdenum in each of powder A, B or C is 0.3-2%, preferably 0.5-1.5%, by weight, and the amount of molybdenum is essentially the same in each of powder A, B or C.
  2. The powder metallurgical combination according to claim 1, wherein the amount of copper in powder A is 8-12% by weight.
  3. The powder metallurgical combination according to claim 1 or 2, wherein the amount of nickel in powder B is 5-7% by weight.
  4. The powder metallurgical combination according to any one of claims 1 to 3, comprising other additives selected from the group consisting of lubricants, binders, other alloying elements, hard phase materials, machinability enhancing agents.
  5. The powder metallurgical combination according to any one of claims 1 to 4, wherein powder C is essentially free from Cu and Ni.
  6. A method to obtain a sintered component, having a predetermined strength and a predetermined dimensional change during sintering, including the steps of :
    - determining the required amounts of copper, nickel, molybdenum and carbon in the sintered component needed for obtaining the predetermined strength and dimensional change,
    - determining the respective amounts of powder A, B and C as defined in any one of claims 1-5,
    - mixing the determined amounts of powders A, B and C with graphite and optional other additives ,
    - compacting the mixture to form a powder compact; and
    - sintering the powder compact,
    wherein the mixture is compacted at a compaction pressure between 400-1000 MPa and the sintering is done at 1100-1300°C for 10-60 minutes.
EP06701553.7A 2005-02-04 2006-01-20 Iron-based powder combination Active EP1844172B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0500261 2005-02-04
PCT/SE2006/000080 WO2006083206A1 (en) 2005-02-04 2006-01-20 Iron-based powder combination

Publications (3)

Publication Number Publication Date
EP1844172A1 EP1844172A1 (en) 2007-10-17
EP1844172A4 EP1844172A4 (en) 2010-07-21
EP1844172B1 true EP1844172B1 (en) 2019-07-03

Family

ID=36777515

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06701553.7A Active EP1844172B1 (en) 2005-02-04 2006-01-20 Iron-based powder combination

Country Status (12)

Country Link
US (1) US20080089801A1 (en)
EP (1) EP1844172B1 (en)
JP (1) JP5108531B2 (en)
KR (1) KR100970796B1 (en)
CN (1) CN100532606C (en)
BR (1) BRPI0607356A2 (en)
CA (1) CA2595905A1 (en)
MX (1) MX2007009531A (en)
RU (1) RU2366537C2 (en)
TW (1) TWI325896B (en)
WO (1) WO2006083206A1 (en)
ZA (1) ZA200705662B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8858675B2 (en) 2007-07-17 2014-10-14 Hoganas Ab (Publ) Iron-based powder combination
KR100992713B1 (en) 2007-10-04 2010-11-05 기아자동차주식회사 dead lock device for electric steering column lock system
US20110252922A1 (en) * 2008-12-23 2011-10-20 Hoganas Ab (Publ) method of producing a diffusion alloyed iron or iron-based powder, a diffusion alloyed powder, a composition including the diffusion alloyed powder, and a compacted and sintered part produced from the composition
BR112013025725B1 (en) * 2011-04-06 2019-09-03 Hoeganaes Corp metallurgical powder composition, compacted part and additive to prepare metallurgical powder composition
CN105344992A (en) * 2015-11-19 2016-02-24 苏州紫光伟业激光科技有限公司 Metallurgy powder composition
DE102018209682A1 (en) * 2018-06-15 2019-12-19 Mahle International Gmbh Process for the manufacture of a powder metallurgical product
US11939646B2 (en) 2018-10-26 2024-03-26 Oerlikon Metco (Us) Inc. Corrosion and wear resistant nickel based alloys
RU2701232C1 (en) * 2018-12-12 2019-09-25 Публичное акционерное общество "Северсталь" Method of producing alloyed powder mixture for production of critical structural powder parts
KR20210029582A (en) 2019-09-06 2021-03-16 현대자동차주식회사 Iron-based prealloy powder, iron-based diffusion-bonded powder, and iron-based alloy powder for powder metallurgy using the same
KR20210104418A (en) * 2020-02-17 2021-08-25 현대자동차주식회사 A outer ring for variable oil pump and manufacturing method thereof
CN116024483B (en) * 2022-12-30 2023-09-15 江苏群达机械科技有限公司 Low-alloy high-strength Cr-Mo steel material and preparation method thereof

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1305608A (en) * 1970-03-18 1973-02-07
US4069044A (en) 1976-08-06 1978-01-17 Stanislaw Mocarski Method of producing a forged article from prealloyed-premixed water atomized ferrous alloy powder
JPS54104406A (en) * 1978-02-06 1979-08-16 Toyo Kohan Co Ltd Production of high temperature abrasion resistant sintered alloy steel
JPS5594401A (en) * 1979-01-09 1980-07-17 Daido Steel Co Ltd Stainless steel powder
JPS59215401A (en) * 1983-05-19 1984-12-05 Kawasaki Steel Corp Alloy steel powder for powder metallurgy and its production
JPS61130401A (en) * 1984-11-28 1986-06-18 Kawasaki Steel Corp Alloy steel powder for powder metallurgy and its production
JPS61183444A (en) * 1985-02-08 1986-08-16 Toyota Motor Corp High strength sintered alloy and its manufacture
JPS61253342A (en) * 1985-04-30 1986-11-11 Fuji Electric Co Ltd Manufacture of sintered stainless steel
JPH0745683B2 (en) * 1987-09-30 1995-05-17 川崎製鉄株式会社 Composite steel powder with excellent compressibility and homogeneity
JPH01165702A (en) * 1987-12-23 1989-06-29 Kawasaki Steel Corp Manufacture of alloy steel sintered compact having high density and high strength
JPH01312056A (en) * 1988-06-09 1989-12-15 Kawasaki Steel Corp Manufacture of sintered compact of alloy steel having high density and high strength
DE3942091C1 (en) * 1989-12-20 1991-08-14 Etablissement Supervis, Vaduz, Li
JPH04297502A (en) * 1991-03-25 1992-10-21 Kawasaki Steel Corp Manufacture of ni-containing ferrous sintered material
SE9101819D0 (en) * 1991-06-12 1991-06-12 Hoeganaes Ab ANNUAL BASED POWDER COMPOSITION WHICH SINCERATES GOOD FORM STABILITY AFTER SINTERING
JPH0681001A (en) * 1992-09-02 1994-03-22 Kawasaki Steel Corp Alloy steel powder
JP3351844B2 (en) * 1993-03-01 2002-12-03 川崎製鉄株式会社 Alloy steel powder for iron-based sintered material and method for producing the same
JPH07233402A (en) * 1993-12-28 1995-09-05 Kawasaki Steel Corp Atomized steel powder excellent in machinability and wear resistance and sintered steel produced therefrom
JP3446322B2 (en) * 1994-08-03 2003-09-16 Jfeスチール株式会社 Alloy steel powder for powder metallurgy
JP3475545B2 (en) * 1995-02-08 2003-12-08 Jfeスチール株式会社 Mixed steel powder for powder metallurgy and sintering material containing it
FR2784691B1 (en) * 1998-10-16 2000-12-29 Eurotungstene Poudres MICRONIC PREALLY METALLIC POWDER BASED ON 3D TRANSITIONAL METALS
SE0201824D0 (en) * 2002-06-14 2002-06-14 Hoeganaes Ab Pre-alloyed iron based powder
SE0203135D0 (en) 2002-10-23 2002-10-23 Hoeganaes Ab Dimensional control
JP2004292861A (en) * 2003-03-26 2004-10-21 Jfe Steel Kk Iron-based powdery mixture for powder metallurgy, and its production method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
RU2007133101A (en) 2009-03-10
JP5108531B2 (en) 2012-12-26
EP1844172A1 (en) 2007-10-17
RU2366537C2 (en) 2009-09-10
JP2008528811A (en) 2008-07-31
KR100970796B1 (en) 2010-07-16
TWI325896B (en) 2010-06-11
TW200632111A (en) 2006-09-16
WO2006083206A1 (en) 2006-08-10
US20080089801A1 (en) 2008-04-17
MX2007009531A (en) 2008-02-12
CA2595905A1 (en) 2006-08-10
ZA200705662B (en) 2009-01-28
KR20070099690A (en) 2007-10-09
CN101111617A (en) 2008-01-23
BRPI0607356A2 (en) 2009-09-01
CN100532606C (en) 2009-08-26
EP1844172A4 (en) 2010-07-21

Similar Documents

Publication Publication Date Title
EP1844172B1 (en) Iron-based powder combination
JP2741199B2 (en) High density sintered iron alloy
EP2176019B1 (en) Iron-based powder combination and process for producing it
EP1184107B1 (en) Alloyed steel powder for powder metallurgy
CN1116944C (en) Steel powder for the prepn. of sintered products
US20050274222A1 (en) Method for making sintered body with metal powder and sintered body prepared therefrom
KR20110099336A (en) A method of producing a diffusion alloyed iron or iron-based powder, a diffusional alloyed powder, a composition including the diffusion alloyed powder, and a compacted and sintered part produced from the composition
KR20140010026A (en) Iron based powders for powder injection molding
EP1513640A1 (en) Prealloyed iron-based powder, a method of producing sintered components and a component
JP2010090470A (en) Iron-based sintered alloy and method for producing the same
JP4201830B2 (en) Iron-based powder containing chromium, molybdenum and manganese and method for producing sintered body
US6261514B1 (en) Method of preparing sintered products having high tensile strength and high impact strength
JP6528899B2 (en) Method of manufacturing mixed powder and sintered body for powder metallurgy
US7329380B2 (en) Method of controlling the dimensional change when sintering an iron-based powder mixture
JP4121383B2 (en) Iron-base metal bond excellent in dimensional accuracy, strength and sliding characteristics and method for manufacturing the same
KR100978901B1 (en) MANUFACTURING METHOD OF Fe-BASED SINTERED BODY WITH HIGH TENSILE STRENGTH AND HIGH HARDNESS
JP4839271B2 (en) Mixed powder for powder metallurgy and sintered iron powder
EP1323840B1 (en) Iron base mixed powder for high strength sintered parts
JPH09195006A (en) Raw material powder for sintering wear resistant material
JPH0751721B2 (en) Low alloy iron powder for sintering
JP5923023B2 (en) Mixed powder for powder metallurgy and method for producing sintered material
JP3303026B2 (en) High strength iron-based sintered alloy and method for producing the same
KR102250915B1 (en) Powder metallurgy mixed powder, sintered body, and manufacturing method of sintered body
JP5119006B2 (en) Mixed powder for powder metallurgy and sintered iron powder
JPH1072648A (en) High strength ferrous sintered alloy excellent in wear resistance and its production

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070615

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LARSSON, MATS

A4 Supplementary search report drawn up and despatched

Effective date: 20100623

17Q First examination report despatched

Effective date: 20160714

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/12 20060101ALI20190114BHEP

Ipc: C22C 38/08 20060101ALI20190114BHEP

Ipc: C22C 33/02 20060101AFI20190114BHEP

Ipc: B22F 1/00 20060101ALI20190114BHEP

Ipc: C22C 38/16 20060101ALI20190114BHEP

INTG Intention to grant announced

Effective date: 20190130

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LARSSON, MATS

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1151070

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190715

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006058242

Country of ref document: DE

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190703

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1151070

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191104

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191004

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200224

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006058242

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG2D Information on lapse in contracting state deleted

Ref country code: IS

26N No opposition filed

Effective date: 20200603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200120

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200120

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200131

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200131

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20221212

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20221207

Year of fee payment: 18