EP1812187A1 - Powder metal composition comprising secondary amides as lubricant and/or binder - Google Patents

Powder metal composition comprising secondary amides as lubricant and/or binder

Info

Publication number
EP1812187A1
EP1812187A1 EP05783351A EP05783351A EP1812187A1 EP 1812187 A1 EP1812187 A1 EP 1812187A1 EP 05783351 A EP05783351 A EP 05783351A EP 05783351 A EP05783351 A EP 05783351A EP 1812187 A1 EP1812187 A1 EP 1812187A1
Authority
EP
European Patent Office
Prior art keywords
composition according
lubricant
amide
powder
iron
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
Application number
EP05783351A
Other languages
German (de)
French (fr)
Other versions
EP1812187B1 (en
Inventor
Åsa AHLIN
Maria Ramstedt
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
Priority claimed from SE0402239A external-priority patent/SE0402239D0/en
Application filed by Hoganas AB filed Critical Hoganas AB
Priority to PL05783351T priority Critical patent/PL1812187T3/en
Publication of EP1812187A1 publication Critical patent/EP1812187A1/en
Application granted granted Critical
Publication of EP1812187B1 publication Critical patent/EP1812187B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02Compacting only
    • B22F2003/023Lubricant mixed with the metal powder
    • 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
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • Powder metal composition comprising secondary amides as lubricant and/or binder.
  • the present invention concerns a powder metal composition. Specifically the invention concerns a powder metal composition including a lubricant and/or binder comprising at least one secondary amide. The invention further concerns a method of producing a green body, a method of producing a bonded iron-based powder composition and use of the lubricant and/or binder.
  • Metal powders are used in industry for the manufacture of metal products by compacting the metal powder in a die under high pressures, ejecting the compact from the die and optionally sintering the product.
  • a lubricant is comprised in the powder in order to provide the necessary lubrication action between powder particles during compaction and between the die and the compact during ejection from the die.
  • Lubrication achieved by a lubricant included in the metal powder is referred to as internal lubrication in contrast to external lubrication, which is achieved by applying a lubricant to the walls of the die, wherein the powder is compacted.
  • Insufficient lubrication during ejection results in excessive friction between the compact and the die resulting in high ejection energies and damage of die surfaces and product surfaces .
  • lubrication is achieved by using special lubricants. Normally these lubricants are admixed with the iron or iron-based powder in the form of a powder. Some lubricants may also be used for binding additives, such as e.g. alloying elements, to the iron or iron-based particles. In these cases the lubricants thus work as binding agents and reduce or eliminate segregation of the additives during shipping and handling. Commonly used lubricants for PM applications are metal soaps, such as lithium and zinc stearate.
  • a disadvantage with this type of lubricant is that oxides of the metals in the lubricant contaminate the inside of the sintering furnace as a result of release of metals from the lubricant during sintering, another problem is that stains may be formed on the component after sintering.
  • Another commonly used lubricant is ethylene bis stearamide (EBS) . Stains may also be formed on the component after sintering when using this lubricant, but to a lesser extent compared with using e.g. zinc stearate.
  • EBS ethylene bis stearamide
  • Stains may also be formed on the component after sintering when using this lubricant, but to a lesser extent compared with using e.g. zinc stearate.
  • a powder metal composition comprising an iron based powder and a lubricant and/or binder comprising at least one secondary amide.
  • the invention further concerns a method of producing a green body by subjecting the above mentioned composition to compaction.
  • the method of producing a bonded powder metal composition comprises: mixing an iron-based powder with at least one secondary amide and heating the mixture to a temperature above the melting point of the at least one secondary amide.
  • the invention concerns the use of the at least one secondary amide as a lubricating and/or binding agent for iron-based powders, and its use for die wall lubrication.
  • the lubricant and/or binder in the powder metal composition according to the invention is at least one secondary amide that may be defined by the general formula:
  • Ri- and R 2 ⁇ groups which may be the same or different, are straight or branched, saturated or unsaturated aliphatic hydrocarbon groups.
  • Ri and R 2 independently include 10 to 24 carbon atoms .
  • Ri and R 2 are selected from the group con ⁇ sisting of alkyl and alkenyl.
  • the alkyl groups may be chosen from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl.
  • the alkenyl groups may be chosen from decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl.
  • the amount of secondary amides may constitute 0.05- 2.0 % by weight of the powder metal composition, preferably 0.05-1.0% by weight.
  • One embodiment of the invention concerns a powder metal composition
  • a powder metal composition comprising a lubricant and/or binder further comprising at least one primary amide in addition to the at least one secondary amide.
  • the at least one primary amide is preferably a saturated or unsaturated fatty acid amide having 12-24, preferably 14-22 C-atoms and most preferably 16-22 C-atoms.
  • Especially preferred primary amides are stearic acid amide (stearamide) , behenic acid amide (behenamide) , eurcic acid amide (erucamide) , palmitic acid amide (palmitamide) and arachidic acid amide (arachidamide) .
  • the primary and secondary amides according to the invention are either commercially obtainable or may be produced from commercially obtainable material by the use of processes well known in the art.
  • the amount of primary and secondary amides may constitute a total of 0.05-2.0 % by weight of the powder metal composition, preferably 0.05-1.0% by weight.
  • the amount of the at least one primary amide may be 0.05-1.0% by weight and the amount of the at least one secondary amide may be 0.05-1.0% by weight for the embodiment of the invention comprising both types of amides .
  • the lubricant and/or binder may be added to the powder metal composition in the form of solid particles of each amide.
  • the average particle size may vary, but is preferably less than 150 ⁇ m.
  • the lubricant and/or binder may be added to the powder metal composition as a molten and subsequently solidified particulate mixture of the amides. This may be accomplished by mixing the amides in a predetermined ratio, the mixture is then melted, cooled and subsequently milled to a lubricant powder.
  • the at least one secondary amide according to the invention may be used as a binder for obtaining a bonded mixture, wherein optional alloying elements and the at least one secondary amide are bonded to the iron-based powder. This may be achieved by mixing an iron-based powder with at least one secondary amide according to the invention, and heating the mixture to a temperature above the melting point of the at least one secondary amide. At least one primary amide may further be mixed into the above mentioned mixture and the heating temperature may then be lower than the melting point of the primary amide.
  • the powder metal composition according to the invention may, if so desired, contain other lubricants, such as zinc stearate, lithium stearate, EBS etc.
  • bonding systems such as alkydes, cellulose ester resins, hydroxyalkyl cellulose resins having 1-4 carbon atoms in the alkyl group, or thermoplastic phenolic resins.
  • iron-based powder encompasses powder essentially made up of pure iron, iron powder that has been pre-alloyed with other elements improving the strength, the hardening properties, the electromagnetic properties or other desirable properties of the end products and particles of iron mixed with particles of such alloying elements (diffusion annealed mixture or purely mechanical mixture) .
  • alloying elements are copper, molybdenum, chromium, manganese, phosphorous, carbon in the form of graphite, nickel, silicon, boron, vanadium, titanium, aluminium, cobalt and tungsten, which are used either separately or in combination, e.g. in the form of compounds (Fe 3 P and FeMo) .
  • the iron based powders may be used for the preparation of soft magnetic parts and may, for this application, be electrically insulated. Electrical insulation of the powder particles may be made of an inorganic material. Especially suitable are the type of insulation disclosed in the US 6348265, which concerns particles of a base powder consisting of essentially pure iron having an insulating oxygen- and phosphorus-contai ⁇ ning barrier. Insulated powder particles are available as SomaloyTM 500 and 550 from Hoganas AB, Sweden.
  • the powder metal composition according to the invention may contain one or more additives selected from the group consisting of processing aids and hard phases.
  • the processing aids used in the powder metal composition may consist of talc, forsterite, manganese sulphide, sulphur, molybdenum disulphide, boron nitride, tellurium, selenium, barium difluoride and calcium difluoride, which are used either separately or in combination.
  • the hard phases used in the powder metal composition may consist of carbides of tungsten, vanadium, molyb ⁇ denum, chromium, AI 2 O 3 , B 4 C and various ceramic materials.
  • the invention further concerns a method of producing a green body comprising: compacting the powder metal composition according to the invention to a compacted body, wherein the composition comprises an iron based powder and a lubricant and/or binder comprising at least one secondary amide having the general formula:
  • Ri-NH-CO-R2 wherein Ri and R 2 are the same or different, straight or branched, saturated or unsaturated aliphatic hydrocarbon groups.
  • the compacted body may be sintered or heat-treated. With the aid of conventional techniques, the iron- based powder, the lubricant and/or binder and optional additives may be mixed to a substantially homogeneous powder composition before the compaction step.
  • the powder metal composition and/or the die may be preheated before the compaction.
  • the invention further concerns the use of at least one secondary amide, defined as above, as a lubricating and/or binding agent for iron or iron based powders .
  • a further embodiment of the invention concerns the use of at least one secondary amide, defined as above, as a die wall lubricant.
  • FIG. 1 shows stain formation of components after sintering due to the use of different lubricants.
  • EBS Ethylene bisstearamide
  • This example demonstrates the lubrication properties of different secondary amides and different combinations of secondary and primary amides, which are added as a powder in iron-based powder mixes .
  • Base powder ASC 100.29 (available from Hoganas AB, Sweden) was mixed with 0.5% by weight of graphite (uf-4 from Kropfmuhl) and 0.8% by weight of lubricants, according to Table 3 and 4, in a L ⁇ dige mixer for 2 minutes.
  • Ethylene bisstearamide (EBS, available as Licowax TM from Clariant, Germany) was used as a reference.
  • the lubricants had a particle size less than 150 ⁇ m.
  • Compositions comprising both a secondary and a primary amide contained 50% of each amide (0.8% by weight of the total composition) .
  • the base powder ASC 100.29 was mixed with 2% by weight of Copper (-lOO ⁇ m) , 0.8% by weight graphite and 0.8% by weight of lubricants (a) EBS or b) oleyl palmitamide) in a L ⁇ dige mixer for 2 minutes .
  • the lubricants had a particle size less than 150 ⁇ m.
  • cylindrical components with a diameter of 64 mm and a height of 32 mm were compacted to a green density of 7.1 g/cm 3 at ambient temperature.
  • the weight of one cylinder was 700 g.
  • the components were sintered in an atmosphere containing 90/10 N 2 /H 2 at 1120 0 C for 15 minutes.
  • This example demonstrates the lubrication properties of different combinations of secondary and primary amides, which have been melted together, cooled and milled before being mixed with iron-based powder mixes .
  • the lubricant combinations were made according to following method: The mixed lubricants, 50% primary and
  • the base powder ASClOO.29 was mixed with 0.5 % by weight of graphite and 0.8 % by weight of lubricant combination (see Table 5), in a L ⁇ dige mixer for 2 minutes.
  • rings with inner diameter of 45 mm, outer diameter 55 mm and a height 10 mm were compacted at three different compaction pressures, 400, 600 and 800 MPa at ambient temperature.
  • the resulting ejection energies and densities are shown in Table 5.
  • Table 5 Densities and ejection energies (secondary + primary amides and reference) .
  • This example demonstrates the lubricating and binding properties of different combinations of amides in powder metal compositions.
  • the lubricants had a particle size less than 150 ⁇ m.
  • the base powder ASClOO.29 was mixed with 2% by weight Cu-100, 0.8 % by weight of graphite and 0,8 % by weight of lubricant/binder combination according to Table 6, in a Lodige mixer for 2 minutes.
  • the mixture with EBS was kept as reference while the mixtures comprising amides were heated to a temperature above the melting point of the secondary amide but below the melting point of the primary amide during mixing in another mixer followed by cooling to accomplish bonding of the additives to the iron powder.
  • the secondary amide will thus act as a binder and the primary amide will act as a lubricant.
  • the melting temperatures of the amides are disclosed in Table 7.
  • the ejection energy was measured on rings having an outer diameter of 55 mm and an inner diameter of 45 mm and a height of 10 mm compacted at three different compaction pressures, 400, 600 and 800 MPa at ambient temperature.
  • the resulting ejection energies and green densities are shown in Table 8.
  • Samples produced with the aid of the lubricant/binder according to the invention show lower ejection energies compared to samples produced with the lubricant used as reference, i.e. EBS.
  • Use of the powder composition comprising the lubricant/binder according to the invention resulted in compacted sintered parts (sintered in 90/10 N 2 /H 2 at 112O 0 C for 30 minutes) with excellent surface finishes, i.e. essentially without scratches and no stain formation.
  • Example 5 A coarse soft magnetic iron-based powder, wherein the particles are surrounded by an inorganic insulation was mixed with secondary amide lubricant according to Table 9.
  • secondary amide lubricant As reference lubricants the known substances Zinc- stearate and EBS were used.
  • the particle size distribution of the used iron-based powder is disclosed in Table 10.
  • the obtained mixes were transferred to a die and compacted into cylindrical test samples (50 g) having a diameter of 25 mm, in an uniaxial press movement at a compaction pressure of 1100 MPa.
  • the die material used was conventional tool steel. During ejection of the com ⁇ pacted samples the ejection force was recorded. The total ejection energy/enveloping area needed in order to eject the samples from the die was calculated.

Abstract

The invention concerns a powder metal composition comprising an iron based powder and a lubricant and/or binder comprising at least one secondary amide of the general formula: R<sub

Description

Powder metal composition comprising secondary amides as lubricant and/or binder.
Field of the invention
The present invention concerns a powder metal composition. Specifically the invention concerns a powder metal composition including a lubricant and/or binder comprising at least one secondary amide. The invention further concerns a method of producing a green body, a method of producing a bonded iron-based powder composition and use of the lubricant and/or binder.
Background of the invention
Metal powders are used in industry for the manufacture of metal products by compacting the metal powder in a die under high pressures, ejecting the compact from the die and optionally sintering the product. In the majority of powder metallurgical (PM) applications a lubricant is comprised in the powder in order to provide the necessary lubrication action between powder particles during compaction and between the die and the compact during ejection from the die. Lubrication achieved by a lubricant included in the metal powder is referred to as internal lubrication in contrast to external lubrication, which is achieved by applying a lubricant to the walls of the die, wherein the powder is compacted. Insufficient lubrication during ejection results in excessive friction between the compact and the die resulting in high ejection energies and damage of die surfaces and product surfaces .
Internal lubrication is achieved by using special lubricants. Normally these lubricants are admixed with the iron or iron-based powder in the form of a powder. Some lubricants may also be used for binding additives, such as e.g. alloying elements, to the iron or iron-based particles. In these cases the lubricants thus work as binding agents and reduce or eliminate segregation of the additives during shipping and handling. Commonly used lubricants for PM applications are metal soaps, such as lithium and zinc stearate. A disadvantage with this type of lubricant is that oxides of the metals in the lubricant contaminate the inside of the sintering furnace as a result of release of metals from the lubricant during sintering, another problem is that stains may be formed on the component after sintering. Another commonly used lubricant is ethylene bis stearamide (EBS) . Stains may also be formed on the component after sintering when using this lubricant, but to a lesser extent compared with using e.g. zinc stearate. As lubricants strongly affect compacting and sintering properties of metal powders optimization of amount, composition and structure of the used lubricant is of vital importance to obtain high and consistent densities and good surface finishes of the produced parts .
Objects of the invention An object of the present invention is to provide a new powder metal composition comprising a lubricant and/or binder that reduces or eliminates the problems with high ejection forces and stained surfaces of the sintered parts. Further objects of the invention are to provide a method of producing compacted products and sintered or heat treated parts, a method of producing a bonded powder metal composition and use of the lubricant and/or binder.
Summary of the invention
These objects are accomplished by a powder metal composition comprising an iron based powder and a lubricant and/or binder comprising at least one secondary amide. The invention further concerns a method of producing a green body by subjecting the above mentioned composition to compaction. The method of producing a bonded powder metal composition comprises: mixing an iron-based powder with at least one secondary amide and heating the mixture to a temperature above the melting point of the at least one secondary amide.
Additionally, the invention concerns the use of the at least one secondary amide as a lubricating and/or binding agent for iron-based powders, and its use for die wall lubrication.
Detailed description of the invention
The lubricant and/or binder in the powder metal composition according to the invention is at least one secondary amide that may be defined by the general formula:
Ri-NH-CO-R2,
wherein the Ri- and R2~groups, which may be the same or different, are straight or branched, saturated or unsaturated aliphatic hydrocarbon groups.
Preferably, Ri and R2 independently include 10 to 24 carbon atoms .
Preferably Ri and R2 are selected from the group con¬ sisting of alkyl and alkenyl. The alkyl groups may be chosen from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl.
The alkenyl groups may be chosen from decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl.
Examples of preferred secondary amides are shown in Table 1. Table1
General formula: Ri-NH-CO-R2
The amount of secondary amides may constitute 0.05- 2.0 % by weight of the powder metal composition, preferably 0.05-1.0% by weight.
One embodiment of the invention concerns a powder metal composition comprising a lubricant and/or binder further comprising at least one primary amide in addition to the at least one secondary amide. The at least one primary amide is preferably a saturated or unsaturated fatty acid amide having 12-24, preferably 14-22 C-atoms and most preferably 16-22 C-atoms.
Especially preferred primary amides are stearic acid amide (stearamide) , behenic acid amide (behenamide) , eurcic acid amide (erucamide) , palmitic acid amide (palmitamide) and arachidic acid amide (arachidamide) . The primary and secondary amides according to the invention are either commercially obtainable or may be produced from commercially obtainable material by the use of processes well known in the art.
The amount of primary and secondary amides may constitute a total of 0.05-2.0 % by weight of the powder metal composition, preferably 0.05-1.0% by weight.
The amount of the at least one primary amide may be 0.05-1.0% by weight and the amount of the at least one secondary amide may be 0.05-1.0% by weight for the embodiment of the invention comprising both types of amides .
The lubricant and/or binder may be added to the powder metal composition in the form of solid particles of each amide. The average particle size may vary, but is preferably less than 150 μm.
Alternatively, the lubricant and/or binder may be added to the powder metal composition as a molten and subsequently solidified particulate mixture of the amides. This may be accomplished by mixing the amides in a predetermined ratio, the mixture is then melted, cooled and subsequently milled to a lubricant powder. The at least one secondary amide according to the invention may be used as a binder for obtaining a bonded mixture, wherein optional alloying elements and the at least one secondary amide are bonded to the iron-based powder. This may be achieved by mixing an iron-based powder with at least one secondary amide according to the invention, and heating the mixture to a temperature above the melting point of the at least one secondary amide. At least one primary amide may further be mixed into the above mentioned mixture and the heating temperature may then be lower than the melting point of the primary amide.
Apart from the lubricant and/or binder disclosed above, the powder metal composition according to the invention may, if so desired, contain other lubricants, such as zinc stearate, lithium stearate, EBS etc.
To accomplish a bonding of the powder metal composition according to the invention other types of bonding systems may be used such as alkydes, cellulose ester resins, hydroxyalkyl cellulose resins having 1-4 carbon atoms in the alkyl group, or thermoplastic phenolic resins.
As used in the description and the appended claims, the expression "iron-based" powder encompasses powder essentially made up of pure iron, iron powder that has been pre-alloyed with other elements improving the strength, the hardening properties, the electromagnetic properties or other desirable properties of the end products and particles of iron mixed with particles of such alloying elements (diffusion annealed mixture or purely mechanical mixture) . Examples of alloying elements are copper, molybdenum, chromium, manganese, phosphorous, carbon in the form of graphite, nickel, silicon, boron, vanadium, titanium, aluminium, cobalt and tungsten, which are used either separately or in combination, e.g. in the form of compounds (Fe3P and FeMo) . The iron based powders may be used for the preparation of soft magnetic parts and may, for this application, be electrically insulated. Electrical insulation of the powder particles may be made of an inorganic material. Especially suitable are the type of insulation disclosed in the US 6348265, which concerns particles of a base powder consisting of essentially pure iron having an insulating oxygen- and phosphorus-contai¬ ning barrier. Insulated powder particles are available as Somaloy™ 500 and 550 from Hoganas AB, Sweden.
Apart from the iron-based powder and the lubricant and/or binder, the powder metal composition according to the invention may contain one or more additives selected from the group consisting of processing aids and hard phases.
The processing aids used in the powder metal composition may consist of talc, forsterite, manganese sulphide, sulphur, molybdenum disulphide, boron nitride, tellurium, selenium, barium difluoride and calcium difluoride, which are used either separately or in combination.
The hard phases used in the powder metal composition may consist of carbides of tungsten, vanadium, molyb¬ denum, chromium, AI2O3, B4C and various ceramic materials. The invention further concerns a method of producing a green body comprising: compacting the powder metal composition according to the invention to a compacted body, wherein the composition comprises an iron based powder and a lubricant and/or binder comprising at least one secondary amide having the general formula:
Ri-NH-CO-R2, wherein Ri and R2 are the same or different, straight or branched, saturated or unsaturated aliphatic hydrocarbon groups. The compacted body may be sintered or heat-treated. With the aid of conventional techniques, the iron- based powder, the lubricant and/or binder and optional additives may be mixed to a substantially homogeneous powder composition before the compaction step.
The powder metal composition and/or the die may be preheated before the compaction. The invention further concerns the use of at least one secondary amide, defined as above, as a lubricating and/or binding agent for iron or iron based powders .
A further embodiment of the invention concerns the use of at least one secondary amide, defined as above, as a die wall lubricant.
Detailed description of the figure
Figure 1 shows stain formation of components after sintering due to the use of different lubricants. Ia) Ethylene bisstearamide (EBS) ;
Ib) Oleyl palmitamide (a secondary amide according to the invention) .
The invention will now be further described with the following unlimiting examples.
Examples
In the following examples lubricants having the formulas disclosed in Table 2 below have been used.
Table 2.
* The structural formulas for the secondary amides are referring to Ri-NH-CO-R2 as previously described. Example 1
This example demonstrates the lubrication properties of different secondary amides and different combinations of secondary and primary amides, which are added as a powder in iron-based powder mixes .
Base powder ASC 100.29 (available from Hoganas AB, Sweden) was mixed with 0.5% by weight of graphite (uf-4 from Kropfmuhl) and 0.8% by weight of lubricants, according to Table 3 and 4, in a Lδdige mixer for 2 minutes. Ethylene bisstearamide (EBS, available as Licowax TM from Clariant, Germany) was used as a reference. The lubricants had a particle size less than 150 μm. Compositions comprising both a secondary and a primary amide contained 50% of each amide (0.8% by weight of the total composition) .
In order to measure the lubricating properties rings with an inner diameter of 45 mm, an outer diameter of 55 mm and a height of 10 mm were compacted at ambient temperature at three different compaction pressures (400, 600 and 800 MPa) . During ejection of the compacted parts the ejection force was recorded. The green density of the parts was measured after ejection and the total ejection energy/enveloping area needed in order to eject the samples from the die was calculated.
The resulting ejection energies and densities are shown in Table 3 and 4. Lower ejection energies where achieved when using the powder metal composition according to the invention compared with the use of the reference composition comprising EBS. Table 3. Densities and ejection energies (secondary amides and reference) .
Table 4. Densities and ejection energies (secondary + primary amides 1:1 and reference)
Example 2
The base powder ASC 100.29 was mixed with 2% by weight of Copper (-lOOμm) , 0.8% by weight graphite and 0.8% by weight of lubricants (a) EBS or b) oleyl palmitamide) in a Lδdige mixer for 2 minutes . The lubricants had a particle size less than 150 μm. In order to measure the stain formation after sintering of components, cylindrical components with a diameter of 64 mm and a height of 32 mm were compacted to a green density of 7.1 g/cm3 at ambient temperature. The weight of one cylinder was 700 g. The components were sintered in an atmosphere containing 90/10 N2/H2 at 11200C for 15 minutes. Photos of the components are shown in Figure Ia) Ethylene bisstearamide (EBS) and Ib) oleyl palmitamide, in which figure Ia) show stain formation in contrast to the part produced from the powder composition according to the present invention (Ib) which has no stains.
Example 3
This example demonstrates the lubrication properties of different combinations of secondary and primary amides, which have been melted together, cooled and milled before being mixed with iron-based powder mixes .
The lubricant combinations were made according to following method: The mixed lubricants, 50% primary and
50% secondary amide, were melted together at 80-1100C and then cooled. Then the materials were milled to a mean particle size of below 150μm.
The base powder ASClOO.29 was mixed with 0.5 % by weight of graphite and 0.8 % by weight of lubricant combination (see Table 5), in a Lδdige mixer for 2 minutes. In order to measure the lubricating properties rings with inner diameter of 45 mm, outer diameter 55 mm and a height 10 mm were compacted at three different compaction pressures, 400, 600 and 800 MPa at ambient temperature. The resulting ejection energies and densities are shown in Table 5. Table 5. Densities and ejection energies (secondary + primary amides and reference) .
When comparing the test results in Table 5 it can be seen that samples produced from the powder metal composition according to the invention show lower ejection energies compared to samples produced from the known lubricant EBS.
Example 4
This example demonstrates the lubricating and binding properties of different combinations of amides in powder metal compositions.
The lubricants had a particle size less than 150 μm. The base powder ASClOO.29 was mixed with 2% by weight Cu-100, 0.8 % by weight of graphite and 0,8 % by weight of lubricant/binder combination according to Table 6, in a Lodige mixer for 2 minutes. The mixture with EBS was kept as reference while the mixtures comprising amides were heated to a temperature above the melting point of the secondary amide but below the melting point of the primary amide during mixing in another mixer followed by cooling to accomplish bonding of the additives to the iron powder. In this mixture the secondary amide will thus act as a binder and the primary amide will act as a lubricant. The melting temperatures of the amides are disclosed in Table 7.
Further, the ejection energy was measured on rings having an outer diameter of 55 mm and an inner diameter of 45 mm and a height of 10 mm compacted at three different compaction pressures, 400, 600 and 800 MPa at ambient temperature. The resulting ejection energies and green densities are shown in Table 8.
Table 6. Lubricant/binder combinations for example 4
Table 7. Melting temperatures of the amides.
Table 8. Densities and ejection energies (primary + secondary amides and reference) .
Samples produced with the aid of the lubricant/binder according to the invention show lower ejection energies compared to samples produced with the lubricant used as reference, i.e. EBS. Use of the powder composition comprising the lubricant/binder according to the invention resulted in compacted sintered parts (sintered in 90/10 N2/H2 at 112O0C for 30 minutes) with excellent surface finishes, i.e. essentially without scratches and no stain formation.
Example 5 A coarse soft magnetic iron-based powder, wherein the particles are surrounded by an inorganic insulation was mixed with secondary amide lubricant according to Table 9. As reference lubricants the known substances Zinc- stearate and EBS were used. The particle size distribution of the used iron-based powder is disclosed in Table 10.
The obtained mixes were transferred to a die and compacted into cylindrical test samples (50 g) having a diameter of 25 mm, in an uniaxial press movement at a compaction pressure of 1100 MPa. The die material used was conventional tool steel. During ejection of the com¬ pacted samples the ejection force was recorded. The total ejection energy/enveloping area needed in order to eject the samples from the die was calculated.
The results of the measurements regarding ejection energy, green density and surface appearance in the green state are shown in Table 9. Use of the powder metal compositions according to the invention resulted in that compacted components with excellent surface appearance and lower ejection energies were achieved compared with the reference compositions.
Table 9. Densities, ejection energies and surface appearance
Table 10

Claims

1. Powder metal composition comprising an iron based powder and a lubricant and/or binder comprising at least one secondary amide of the general formula:
Ri-NH-CO-R2
characterised in that Ri and R2 are the same or different, straight or branched, saturated or unsaturated aliphatic hydrocarbon groups .
2. Composition according to claim 1, wherein Ri and R2 independently include 10 to 24 carbon atoms.
3. Composition according to claims 1 or 2, wherein Ri and R2 are selected from the group consisting of alkyl and alkenyl.
4. Composition according to claim 3, wherein the alkyl groups are chosen from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl.
5. Composition according to claim 3, wherein the alkenyl groups are chosen from decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl. β. Composition according to claim 1, wherein the secondary amide is chosen from oleyl palmitamide, stearyl stearamide, oleyl stearamide, stearyl oleamide, oleyl oleamide, stearyl erucamide, oleyl erucamide, erucyl stearamide, erucyl oleamide, erucyl erucamide, lignoceryl lauramide, lignoceryl stearamide.
7. Composition according to claim 1, further comprising at least one primary amide. 8. Composition according to claim 7, wherein the primary amide is an amide of a saturated or unsaturated, straight fatty acid having 12-24 carbon atoms.
9. Composition according to claim 7, wherein the primary amide is selected from the group consisting of palmitamide, stearamide, arachidamide, behenamide and erucamide.
10. Composition according to any one of claims 1-9, wherein the lubricant is particulate. 11. Composition according to any one of claims 7-9, wherein the lubricant comprises a molten and subsequently solidified particulate mixture of the at least one secondary amide and the at least one primary amide.
12. Composition according to any one of claims 1-9, wherein the composition is a bonded mixture.
13. Composition according to claim 12 wherein at least one secondary amide is used as a binding agent.
14. Composition according to any one of claims 1-9, wherein the iron-based particles are surrounded by an insulating inorganic coating.
15. Method of producing a green body comprising: compacting the powder metal composition according to any one of claims 1-9 to a compacted body.
16. Method according to claim 15, further comprising a heat treatment or sintering step.
17. Method of producing a bonded iron-based powder composition comprising:
-mixing an iron-based powder with at least one secondary amide according to any one of claims 1-9; -heating the mixture to a temperature above the melting point of the at least one secondary amide.
18. Method according to claim 17, wherein the mixture further comprise at least one primary amide and wherein the heating temperature is lower than the melting point of the primary amide. 19. Use of a lubricant and/or binder according to any one of claims 1-9 as a lubricating and/or binding agent for iron based powders .
20. Use of a lubricant according to any one of claims 1-9 as a die wall lubricant.
EP05783351A 2004-09-17 2005-09-16 Powder metal composition comprising secondary amides as lubricant and/or binder Active EP1812187B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05783351T PL1812187T3 (en) 2004-09-17 2005-09-16 Powder metal composition comprising secondary amides as lubricant and/or binder

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE0402239A SE0402239D0 (en) 2004-09-17 2004-09-17 Powder metal composition comprising a lubricant, method for making compacted products using the lubricant, and using the same
SE0500072 2005-01-12
PCT/SE2005/001343 WO2006031193A1 (en) 2004-09-17 2005-09-16 Powder metal composition comprising secondary amides as lubricant and/or binder

Publications (2)

Publication Number Publication Date
EP1812187A1 true EP1812187A1 (en) 2007-08-01
EP1812187B1 EP1812187B1 (en) 2010-11-10

Family

ID=36060316

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05783351A Active EP1812187B1 (en) 2004-09-17 2005-09-16 Powder metal composition comprising secondary amides as lubricant and/or binder

Country Status (12)

Country Link
EP (1) EP1812187B1 (en)
JP (1) JP4887296B2 (en)
KR (1) KR100862785B1 (en)
CN (1) CN101022903B (en)
AT (1) ATE487552T1 (en)
BR (1) BRPI0515368B1 (en)
CA (1) CA2580509C (en)
DE (1) DE602005024708D1 (en)
MX (1) MX2007003194A (en)
PL (1) PL1812187T3 (en)
RU (1) RU2351434C2 (en)
WO (1) WO2006031193A1 (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010285633A (en) * 2009-06-09 2010-12-24 Kobe Steel Ltd Method of producing powder mixture for powder metallurgy, and method of producing sintered body
CN103014502A (en) * 2012-11-22 2013-04-03 宁波市群星粉末冶金有限公司 Powdery metallurgy material for automobile engine piston and preparation method
CA2923775C (en) 2013-09-12 2021-09-28 National Research Council Of Canada Lubricant for powder metallurgy and metal powder compositions containing said lubricant
CN105176636A (en) * 2014-01-14 2015-12-23 莱芜市冠隆纳米科技有限公司 Super lubricant and preparation method thereof
GB201409250D0 (en) * 2014-05-23 2014-07-09 H Gan S Ab Publ New product
KR101664603B1 (en) * 2014-11-27 2016-10-11 현대자동차주식회사 Powder metallurgical method
EP3321002A1 (en) * 2016-11-15 2018-05-16 Höganäs AB Feedstock for an additive manufacturing method, additive manufacturing method using the same, and article obtained therefrom
WO2018230568A1 (en) 2017-06-16 2018-12-20 Jfeスチール株式会社 Powder mixture for powder metallurgy and method of manufacturing same
JP6648779B2 (en) * 2017-06-16 2020-02-14 Jfeスチール株式会社 Powder mixture for powder metallurgy and method for producing the same
RU2645806C1 (en) * 2017-06-19 2018-02-28 Юлия Алексеевна Щепочкина Sintered iron-based anti-friction material
KR20190128427A (en) 2018-05-08 2019-11-18 현대자동차주식회사 The method of powder metallurgy
WO2022259547A1 (en) * 2021-06-11 2022-12-15 昭和電工マテリアルズ株式会社 Lubricant, combination of lubricants, powder mixture, combination of raw materials for powder mixture and production method for sintered body
EP4105301A1 (en) * 2021-06-15 2022-12-21 Basf Se New gasoline additive packages

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE468121B (en) * 1991-04-18 1992-11-09 Hoeganaes Ab POWDER MIXING CONTAINING BASIC METAL POWDER AND DIAMID WAX BINDING AND MAKING THE MIXTURE
US5256185A (en) * 1992-07-17 1993-10-26 Hoeganaes Corporation Method for preparing binder-treated metallurgical powders containing an organic lubricant
DE69226639T2 (en) * 1992-09-25 1998-12-24 Kawasaki Steel Co Iron-based powder mixture and process for its manufacture
US5627258A (en) * 1994-03-14 1997-05-06 Kabushiki Kaisha Komatsu Seisakusho Binder for use in metal powder injection molding and debinding method by the use of the same
WO1996025261A1 (en) * 1995-02-14 1996-08-22 Komatsu Ltd. Binder for use in metal powder injection molding and debinding method by the use of the same
JP3509408B2 (en) * 1995-08-04 2004-03-22 Jfeスチール株式会社 Iron-based powder mixture for powder metallurgy excellent in fluidity and moldability and method for producing the same
AU723317B2 (en) * 1996-05-13 2000-08-24 Gkn Sinter Metals Inc. Method for preparing high performance ferrous materials
JPH10219303A (en) * 1997-02-07 1998-08-18 Sumitomo Metal Mining Co Ltd Composition for injection molding inorganic powder and sintered compact
JP3445112B2 (en) * 1997-09-25 2003-09-08 日立粉末冶金株式会社 Powder metallurgy in powder metallurgy, lubrication of molding dies and stamping dies
JP2000114018A (en) * 1998-09-30 2000-04-21 Nichia Chem Ind Ltd Composition for bond magnet
JP3882490B2 (en) * 2000-10-13 2007-02-14 住友金属鉱山株式会社 Method for producing highly weather-resistant magnet powder and product obtained
JP4135447B2 (en) * 2002-09-17 2008-08-20 住友金属鉱山株式会社 High weather-resistant magnet powder, resin composition for bonded magnet, and bonded magnet obtained using the same
US7789934B2 (en) * 2004-01-20 2010-09-07 Kabushiki Kaisha Kobe Seiko Sho Lubricant for powder metallurgy, powdery mixture for powder metallurgy, and process for producing sinter

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006031193A1 *

Also Published As

Publication number Publication date
MX2007003194A (en) 2007-05-16
ATE487552T1 (en) 2010-11-15
CA2580509C (en) 2010-11-16
JP4887296B2 (en) 2012-02-29
RU2007114275A (en) 2008-10-27
CN101022903B (en) 2010-11-10
DE602005024708D1 (en) 2010-12-23
BRPI0515368B1 (en) 2014-07-29
KR100862785B1 (en) 2008-10-13
CA2580509A1 (en) 2006-03-23
EP1812187B1 (en) 2010-11-10
KR20070046958A (en) 2007-05-03
PL1812187T3 (en) 2011-04-29
BRPI0515368A (en) 2008-07-22
CN101022903A (en) 2007-08-22
WO2006031193A1 (en) 2006-03-23
RU2351434C2 (en) 2009-04-10
JP2008513602A (en) 2008-05-01

Similar Documents

Publication Publication Date Title
CA2580509C (en) Powder metal composition comprising secondary amides as lubricant and/or binder
EP2370220B1 (en) Lubricant for powder metallurgical compositions
KR20070027758A (en) Powder metallurgical composition comprising carbon black as flow enhancing agent
EP1976652A1 (en) Lubricant for powder metallurgical compositions
EP1737593A1 (en) Method for making compacted products and iron-based powder comprising lubricant
US7416578B2 (en) Powder metal composition
BRPI0620894A2 (en) metallurgical powder composition and method for producing metallurgical powder composition
EP1513638B1 (en) Metal powder composition including a bonding lubricant and a bonding lubricant comprising glyceryl stearate.
TW513484B (en) Lubricant composite and process for the preparation thereof
BRPI0620868A2 (en) metallurgical powder composition
CA2589075C (en) Lubricants for powdered metals and powdered metal compositions containing said lubricants
CA2248447C (en) Boric acid-containing lubricants for powdered metals, and powdered metal compositions containing said lubricants
EP1387730B1 (en) Iron powder composition including an amide type lubricant and a method to prepare it
ES2356177T3 (en) COMPOSITION OF POWDER METAL THAT INCLUDES SECONDARY AMIDAS AS LUBRICANT AND / OR BINDER.
WO2024053141A1 (en) Mixed powder for powder metallurgy
KR20090104140A (en) Powder metallurgical composition comprising carbon black as flow enhancing agent
US20030075017A1 (en) Iron powder composition
KR20050016530A (en) Metal powder composition including a bonding lubricant and a bonding lubricant comprising glyceryl stearate

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: 20070308

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

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20080811

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

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

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602005024708

Country of ref document: DE

Date of ref document: 20101223

Kind code of ref document: P

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

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: VDEP

Effective date: 20101110

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2356177

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20110405

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20101110

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

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: 20101110

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

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: 20110310

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: 20101110

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: 20101110

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: 20101110

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: 20101110

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: 20110210

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: 20101110

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: 20110310

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

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: 20110211

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

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: 20101110

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: 20101110

Ref country code: BE

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: 20101110

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

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: 20101110

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: 20101110

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

26N No opposition filed

Effective date: 20110811

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602005024708

Country of ref document: DE

Effective date: 20110811

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

Ref country code: MC

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

Effective date: 20110930

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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: 20110930

Ref country code: LI

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

Effective date: 20110930

Ref country code: IE

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

Effective date: 20110916

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

Ref country code: LU

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

Effective date: 20110916

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: 20101110

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

Ref country code: HU

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: 20101110

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

Ref country code: GB

Payment date: 20140910

Year of fee payment: 10

Ref country code: SE

Payment date: 20140911

Year of fee payment: 10

Ref country code: ES

Payment date: 20140812

Year of fee payment: 10

Ref country code: PL

Payment date: 20140908

Year of fee payment: 10

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

Ref country code: IT

Payment date: 20140912

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20140906

Year of fee payment: 10

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

Ref country code: IT

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

Effective date: 20150916

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

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

Effective date: 20150916

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

Ref country code: SE

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

Effective date: 20150917

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160531

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: 20150916

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

Ref country code: FR

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

Effective date: 20150930

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20161026

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

Ref country code: PL

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

Effective date: 20150916

Ref country code: ES

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

Effective date: 20150917

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

Ref country code: RO

Payment date: 20190826

Year of fee payment: 15

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

Ref country code: AT

Payment date: 20190827

Year of fee payment: 15

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

Ref country code: RO

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

Effective date: 20200916

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 487552

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200916

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

Ref country code: AT

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

Effective date: 20200916

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

Ref country code: DE

Payment date: 20230808

Year of fee payment: 19