CA2580509C - Powder metal composition comprising secondary amides as lubricant and/or binder - Google Patents
Powder metal composition comprising secondary amides as lubricant and/or binder Download PDFInfo
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- CA2580509C CA2580509C CA2580509A CA2580509A CA2580509C CA 2580509 C CA2580509 C CA 2580509C CA 2580509 A CA2580509 A CA 2580509A CA 2580509 A CA2580509 A CA 2580509A CA 2580509 C CA2580509 C CA 2580509C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F2003/023—Lubricant mixed with the metal powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Powder Metallurgy (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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: R1-NH-CO-R2, wherein R1 and R2 are the same or different, straight or branched, saturated or unsaturated aliphatic hydrocarbon groups . The invention further concerns a method of making green bodies of the powder metal composition according to the invention, a method of producing a bonded iron-based powder composition, as well as the use of the at least one secondary amide as a lubricating and/or binding agent for iron based powders and the use as a die wall lubricant.
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.
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.
2a According to another aspect of the present invention, there is provided powder metal composition comprising an iron based powder selected from pure iron, iron powder pre-alloyed, diffusion annealed, or mixed with one or more alloying elements selected from Cu, Mo, Cr, Mn, P, C, Ni, Si, B, V, Ti, Al, Co, and W, and mixtures thereof, and a lubricant and/or binder comprising 0.05-2% by weight of at least one secondary amide of the general formula:
wherein R1 and R2 are the same or different, straight or branched, saturated or unsaturated aliphatic hydrocarbon groups.
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.
2a According to another aspect of the present invention, there is provided powder metal composition comprising an iron based powder selected from pure iron, iron powder pre-alloyed, diffusion annealed, or mixed with one or more alloying elements selected from Cu, Mo, Cr, Mn, P, C, Ni, Si, B, V, Ti, Al, Co, and W, and mixtures thereof, and a lubricant and/or binder comprising 0.05-2% by weight of at least one secondary amide of the general formula:
wherein R1 and R2 are the same or different, straight or branched, saturated or unsaturated aliphatic hydrocarbon groups.
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:
R1-NH-CO-R2, wherein the R1- and R2-groups, which may be the same or different, are straight or branched, saturated or unsaturated aliphatic hydrocarbon groups.
Preferably, R1 and R2 independently include 10 to 24 carbon atoms.
Preferably R1 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.
a) v a) E a) -a 2 E a) E v E E at i E EE 2 a) E ro E c0 cu E CU cu 0 o m c i o a m E Q O o 0 E ai 2 0 " 0 CI p rn 0) U O U) O c~ O cn O W W W _J _, = U
V N
N N N =
U
co m _ _ = U = U = U U
U U = V = _ F- cli o U U V U U U U U
u U U U M
z =O U O= O= _ I Z Z Z U U
ai ^a0 Zao = . ;: m N _ N
n = N = N = N = = _ = N N
rd U 0 U 0 U 0 U_ U_ U_ U U_ U_ = O = O = O = _ _ = O O
U U U U U U U U U U U U
44 U Z U Z U z U U U U Z Z
= n= = _ _ = co M
n .` n ^ gyn ^ n n n N N
N N N N N N N N N N N N
U = _ _ _ _ _ _ _ _ _ _ _ ~ U U U U U U U U U U U U
M M M M M M M M M M M M
a) a) :a v a) v E a)E v a) a) E a) a) -a (u -a E
(U E ac) E a E v E
E aa) a~i a~i a) c: 0 r- U
a) U a) 0 U 'O .0 U U C U
N a) cv a) a3 O c0 O O U U N
a) X ~a U D O a) -O
E O o U O U -0 !2 0 E O O v O
(6 t0 N a) a) a) a) a ~C0 m 0 0 0 U U U
U O O O O O O O in O O la-~ H
()(c:) U U U U U U U U U U U
O a O a U U -O .O U_ j LC0Q Q 02 c}0 a) a) a) 42 Q Q C C Q Q C a Q
N a) a) a) a) a) a) a) a) a) a) C a) _ _ _ _ C
C C
> > >' >
m a) C aO O
a) a) a) a) a) a) a) U U U U U
N a0 N (U a0 L~0 O O O I`0 N
U U U V U U U o 0 0 0 0 0 0 0 0 0 o a 0 I--O U) C U E Lo N- N- N- ti r I- ti - - I-4- O s- r- r- t- r- N N r- N ~-O N
N cn LC V E 00 co co 00 00 oO co N N N ~1 -t O r- r- ~- r r- N N N N N
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 5 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 pm.
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.
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:
R1-NH-CO-R2, wherein the R1- and R2-groups, which may be the same or different, are straight or branched, saturated or unsaturated aliphatic hydrocarbon groups.
Preferably, R1 and R2 independently include 10 to 24 carbon atoms.
Preferably R1 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.
a) v a) E a) -a 2 E a) E v E E at i E EE 2 a) E ro E c0 cu E CU cu 0 o m c i o a m E Q O o 0 E ai 2 0 " 0 CI p rn 0) U O U) O c~ O cn O W W W _J _, = U
V N
N N N =
U
co m _ _ = U = U = U U
U U = V = _ F- cli o U U V U U U U U
u U U U M
z =O U O= O= _ I Z Z Z U U
ai ^a0 Zao = . ;: m N _ N
n = N = N = N = = _ = N N
rd U 0 U 0 U 0 U_ U_ U_ U U_ U_ = O = O = O = _ _ = O O
U U U U U U U U U U U U
44 U Z U Z U z U U U U Z Z
= n= = _ _ = co M
n .` n ^ gyn ^ n n n N N
N N N N N N N N N N N N
U = _ _ _ _ _ _ _ _ _ _ _ ~ U U U U U U U U U U U U
M M M M M M M M M M M M
a) a) :a v a) v E a)E v a) a) E a) a) -a (u -a E
(U E ac) E a E v E
E aa) a~i a~i a) c: 0 r- U
a) U a) 0 U 'O .0 U U C U
N a) cv a) a3 O c0 O O U U N
a) X ~a U D O a) -O
E O o U O U -0 !2 0 E O O v O
(6 t0 N a) a) a) a) a ~C0 m 0 0 0 U U U
U O O O O O O O in O O la-~ H
()(c:) U U U U U U U U U U U
O a O a U U -O .O U_ j LC0Q Q 02 c}0 a) a) a) 42 Q Q C C Q Q C a Q
N a) a) a) a) a) a) a) a) a) a) C a) _ _ _ _ C
C C
> > >' >
m a) C aO O
a) a) a) a) a) a) a) U U U U U
N a0 N (U a0 L~0 O O O I`0 N
U U U V U U U o 0 0 0 0 0 0 0 0 0 o a 0 I--O U) C U E Lo N- N- N- ti r I- ti - - I-4- O s- r- r- t- r- N N r- N ~-O N
N cn LC V E 00 co co 00 00 oO co N N N ~1 -t O r- r- ~- r r- N N N N N
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 5 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 pm.
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).
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 SomaloyTM 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, A1203, 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:
R1-NH-CO-R2, wherein R1 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.
la) Ethylene bisstearamide (EBS);
lb) Oleyl palmitamide (a secondary amide according to the invention).
The invention will now be further described with the following unlimiting examples.
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, A1203, 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:
R1-NH-CO-R2, wherein R1 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.
la) Ethylene bisstearamide (EBS);
lb) 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.
Chemical name Structural formula* Amide type Ref: Ethylene CH3 (CH2) 16CONH (CH2) 2NHCO (CH2) 16CH3 bis amide bis stearamide (EBS) Stearamide (S) CH3 (CH2) 16CONH2 Primary Arachidamide (A) CH3 (CH2) 18CONH2 Primary Erucamide (E) CH3 (CH2) 7CH=CH (CH2) 11CONH2 Primary Behenamide (B) CH3 (CH2) 20CONH2 Primary Stearyl R1=C18:0 R2=C17:0 Secondary Stearamide (SS) Erucyl R1=C22:1 R2=C17:0 Secondary Stearamide (ES) Oleyl Palmit- R1=C18:1 R2=C15:0 Secondary amide (OP) Stearyl R1=C18:0 R2=C21:1 secondary Erucamide (SE) Oleyl R1=C18:1 R2=C17:0 secondary Stearamide (OS) Stearyl R=C18:0 R2=C17:1 secondary Oleamide (SO) * The structural formulas for the secondary amides are referring to R1-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 5 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, 10 according to Table 3 and 4, in a Lodige'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 pm. 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 2.
Chemical name Structural formula* Amide type Ref: Ethylene CH3 (CH2) 16CONH (CH2) 2NHCO (CH2) 16CH3 bis amide bis stearamide (EBS) Stearamide (S) CH3 (CH2) 16CONH2 Primary Arachidamide (A) CH3 (CH2) 18CONH2 Primary Erucamide (E) CH3 (CH2) 7CH=CH (CH2) 11CONH2 Primary Behenamide (B) CH3 (CH2) 20CONH2 Primary Stearyl R1=C18:0 R2=C17:0 Secondary Stearamide (SS) Erucyl R1=C22:1 R2=C17:0 Secondary Stearamide (ES) Oleyl Palmit- R1=C18:1 R2=C15:0 Secondary amide (OP) Stearyl R1=C18:0 R2=C21:1 secondary Erucamide (SE) Oleyl R1=C18:1 R2=C17:0 secondary Stearamide (OS) Stearyl R=C18:0 R2=C17:1 secondary Oleamide (SO) * The structural formulas for the secondary amides are referring to R1-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 5 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, 10 according to Table 3 and 4, in a Lodige'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 pm. 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).
Lubricant Premixed Green Density Ejection Energy (g/cm3) (J/cm2) 400 MPa 600 MPa 800 MPa 400 MPa 600 MPa 800 MPa EBS (Ref) 6.70 7.04 7.17 19.2 26.1 28.2 SS 6.72 7.06 7.19 17.6 24.7 27.9 ES 6.78 7.12 7.23 16.3 20.3 20.8 OP 6.78 7.14 7.25 16.7 21.3 20.3 SE 6.78 7.13 7.24 16.8 21.9 21.8 OS 6.78 7.13 7.24 17.7 21.3 20.5 SO 6.79 7.13 7.23 15.9 21.4 20.4 Table 4. Densities and ejection energies (secondary +
primary amides 1:1 and reference) Lubricant Premixed Green Density Ejection Energy (g/cm3) (J/cm2) 400 MPa 600 MPa 800 MPa 400 MPa 600 MPa 800 MPa EBS (Ref) 6.70 7.04 7.17 19.2 26.1 28.2 SS+E 6.69 7.06 7.21 19.1 24.2 23.6 OP+S 6.70 7.06 7.19 18.2 22.1 22.3 ES+S 6.71 7.06 7.19 17.9 21.5 21.8 ES+E 6.72 7.11 7.23 17.8 20.7 19.0 Example 2 The base powder ASC 100.29 was mixed with 2% by weight of Copper (-100pm), 0.8% by weight graphite and 0.8% by weight of lubricants (a) EBS or b) oleyl palmitamide) in a Lodige mixer for 2 minutes. The lubricants had a particle size less than 150 pm. 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 1120 C for 15 minutes.
Photos of the components are shown in Figure la) Ethylene bisstearamide (EBS) and 1b) oleyl palmitamide, in which figure la) show stain formation in contrast to the part produced from the powder composition according to the present invention (1b) 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 80-110 C and then cooled. Then the materials were milled to a mean particle size of below 150pm.
The base powder ASC100.29 was mixed with 0.5 % by weight of graphite and 0.8 % by weight of lubricant combination (see Table 5), in a Lodige 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.
Lubricant Premixed Green Density Ejection Energy (g/cm3) (J/cm2) 400 MPa 600 MPa 800 MPa 400 MPa 600 MPa 800 MPa EBS (Ref) 6.70 7.04 7.17 19.2 26.1 28.2 SS 6.72 7.06 7.19 17.6 24.7 27.9 ES 6.78 7.12 7.23 16.3 20.3 20.8 OP 6.78 7.14 7.25 16.7 21.3 20.3 SE 6.78 7.13 7.24 16.8 21.9 21.8 OS 6.78 7.13 7.24 17.7 21.3 20.5 SO 6.79 7.13 7.23 15.9 21.4 20.4 Table 4. Densities and ejection energies (secondary +
primary amides 1:1 and reference) Lubricant Premixed Green Density Ejection Energy (g/cm3) (J/cm2) 400 MPa 600 MPa 800 MPa 400 MPa 600 MPa 800 MPa EBS (Ref) 6.70 7.04 7.17 19.2 26.1 28.2 SS+E 6.69 7.06 7.21 19.1 24.2 23.6 OP+S 6.70 7.06 7.19 18.2 22.1 22.3 ES+S 6.71 7.06 7.19 17.9 21.5 21.8 ES+E 6.72 7.11 7.23 17.8 20.7 19.0 Example 2 The base powder ASC 100.29 was mixed with 2% by weight of Copper (-100pm), 0.8% by weight graphite and 0.8% by weight of lubricants (a) EBS or b) oleyl palmitamide) in a Lodige mixer for 2 minutes. The lubricants had a particle size less than 150 pm. 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 1120 C for 15 minutes.
Photos of the components are shown in Figure la) Ethylene bisstearamide (EBS) and 1b) oleyl palmitamide, in which figure la) show stain formation in contrast to the part produced from the powder composition according to the present invention (1b) 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 80-110 C and then cooled. Then the materials were milled to a mean particle size of below 150pm.
The base powder ASC100.29 was mixed with 0.5 % by weight of graphite and 0.8 % by weight of lubricant combination (see Table 5), in a Lodige 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 S. Densities and ejection energies (secondary +
primary amides and reference).
Lubricant Melted and solidified Green Density Ejection Energy (g/cm3) (J/Cm2) MPa MPa MPa MPa MPa MPa EBS (Ref) 6.70 7.04 7.17 19.2 26.1 28.2 SS+E 6.70 7.06 7.20 18.8 22.4 22.6 OP+S 6.71 7.07 7.20 18.5 23.2 24.4 ES+S 6.71 7.07 7.20 18.9 22.7 23.5 ES+E 6.70 7.07 7.20 17.2 19.8 18.0 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 um. The base powder ASC100.29 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.
Secondary amide Primary amide 0.2% by weight 0.6% by wt ES B
OP S
OP B
EBS (Ref 1) (0.8% by wt) Table 7. Melting temperatures of the amides.
Amide Melting temperature( C) ES 72.9 OP 66.9 B 101.9 S 106.6 Table 8. Densities and ejection energies (primary +
secondary amides and reference).
Binder/Lubricant Melt bonded Green Density Ejection Energy (g/cm3) (J/cm2) MPa MPa MPa MPa MPa MPa ES+B 6.75 7.06 7.19 18.5 24.6 28.1 OP+S 6.73 7.09 7.18 19.3 26.6 28.3 OP+B 6.77 7.08 7.19 19.9 25.3 27.1 EBS (Ref) 6.74 7.06 7.17 21.4 30.8 32.8 Samples produced with the aid of the lubricant/binder 5 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 10 in 90/10 N2/H2 at 1120 C for 30 minutes) with excellent surface finishes, i.e. essentially without scratches and no stain formation.
Example 5 15 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.
Mix no Lubricant Ejection Green Surface (0.2 wt%) energy Density appearance (J/cm2) (g/cm3) 1 ES 76 7.65 Perfect 2 SE 71 7.66 Perfect 3 SS 78 7.63 Perfect 4 OP 76 7.66 Perfect Ref 1 Zinc stearate 117 7.66 Not acceptable Ref 2 EBS 113 7.64 Perfect Table 10 Particle size Coarse powder (um) (wt o ) >425 0.1 425-212 64.2 212-150 34.1 150-106 1.1 106-75 0.3 45-75 0.2 <45 0
primary amides and reference).
Lubricant Melted and solidified Green Density Ejection Energy (g/cm3) (J/Cm2) MPa MPa MPa MPa MPa MPa EBS (Ref) 6.70 7.04 7.17 19.2 26.1 28.2 SS+E 6.70 7.06 7.20 18.8 22.4 22.6 OP+S 6.71 7.07 7.20 18.5 23.2 24.4 ES+S 6.71 7.07 7.20 18.9 22.7 23.5 ES+E 6.70 7.07 7.20 17.2 19.8 18.0 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 um. The base powder ASC100.29 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.
Secondary amide Primary amide 0.2% by weight 0.6% by wt ES B
OP S
OP B
EBS (Ref 1) (0.8% by wt) Table 7. Melting temperatures of the amides.
Amide Melting temperature( C) ES 72.9 OP 66.9 B 101.9 S 106.6 Table 8. Densities and ejection energies (primary +
secondary amides and reference).
Binder/Lubricant Melt bonded Green Density Ejection Energy (g/cm3) (J/cm2) MPa MPa MPa MPa MPa MPa ES+B 6.75 7.06 7.19 18.5 24.6 28.1 OP+S 6.73 7.09 7.18 19.3 26.6 28.3 OP+B 6.77 7.08 7.19 19.9 25.3 27.1 EBS (Ref) 6.74 7.06 7.17 21.4 30.8 32.8 Samples produced with the aid of the lubricant/binder 5 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 10 in 90/10 N2/H2 at 1120 C for 30 minutes) with excellent surface finishes, i.e. essentially without scratches and no stain formation.
Example 5 15 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.
Mix no Lubricant Ejection Green Surface (0.2 wt%) energy Density appearance (J/cm2) (g/cm3) 1 ES 76 7.65 Perfect 2 SE 71 7.66 Perfect 3 SS 78 7.63 Perfect 4 OP 76 7.66 Perfect Ref 1 Zinc stearate 117 7.66 Not acceptable Ref 2 EBS 113 7.64 Perfect Table 10 Particle size Coarse powder (um) (wt o ) >425 0.1 425-212 64.2 212-150 34.1 150-106 1.1 106-75 0.3 45-75 0.2 <45 0
Claims (20)
1. Powder metal composition for compaction when producing powder metal components comprising an iron based powder selected from pure iron, iron powder pre-alloyed, diffusion annealed, or mixed with one or more alloying elements selected from Cu, Mo, Cr, Mn, P, C, Ni, Si, B, V, Ti, Al, Co, and W, and mixtures thereof, and a lubricant and/or binder comprising 0.05-2% by weight of at least one secondary amide of the general formula:
wherein R1 and R2 are the same or different, straight or branched, saturated or unsaturated aliphatic hydrocarbon groups.
wherein R1 and R2 are the same or different, straight or branched, saturated or unsaturated aliphatic hydrocarbon groups.
2. Composition according to claim 1, wherein R1 and R2 independently include 10 to 24 carbon atoms.
3. Composition according to claims 1 or 2, wherein R1 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.
6. 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 the 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.
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 the iron-based powder as defined in claim 1 with the at least one secondary amide as defined in any one of claims 1-9;
- heating the mixture to a temperature above the melting point of the at least one secondary amide.
- mixing the iron-based powder as defined in claim 1 with the at least one secondary amide as defined in 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 comprises 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.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE0402239-8 | 2004-09-17 | ||
| 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 | ||
| SE0500072-4 | 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 |
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| CA2580509A1 CA2580509A1 (en) | 2006-03-23 |
| CA2580509C true CA2580509C (en) | 2010-11-16 |
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| EP (1) | EP1812187B1 (en) |
| JP (1) | JP4887296B2 (en) |
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| 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 |
| ES2724330T3 (en) | 2013-09-12 | 2019-09-10 | Nat Res Council 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 |
| 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 |
| 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 |
| 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 |
| PL4105301T3 (en) * | 2021-06-15 | 2025-03-03 | Basf Se | Gasoline fuel and fuel additive packages comprising an amide compound |
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| SU1547947A1 (en) * | 1988-07-29 | 1990-03-07 | Институт химии высокомолекулярных соединений АН УССР | Method of preparing powder charge of hard alloys for compacting |
| 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 |
| EP0589088B1 (en) * | 1992-09-25 | 1998-08-12 | Kawasaki Steel Corporation | Iron-based powder mixture and method |
| 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 |
| CA2254734A1 (en) * | 1996-05-13 | 1997-11-20 | The Presmet Corporation | Method for preparing high performance ferrous materials |
| JPH10219303A (en) * | 1997-02-07 | 1998-08-18 | Sumitomo Metal Mining Co Ltd | Inorganic powder injection molding composition and sintered body |
| 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 |
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- 2005-09-16 RU RU2007114275/02A patent/RU2351434C2/en not_active IP Right Cessation
- 2005-09-16 MX MX2007003194A patent/MX2007003194A/en active IP Right Grant
- 2005-09-16 CN CN2005800311616A patent/CN101022903B/en not_active Expired - Fee Related
- 2005-09-16 JP JP2007532287A patent/JP4887296B2/en not_active Expired - Fee Related
- 2005-09-16 EP EP05783351A patent/EP1812187B1/en not_active Expired - Lifetime
- 2005-09-16 PL PL05783351T patent/PL1812187T3/en unknown
- 2005-09-16 BR BRPI0515368-9A patent/BRPI0515368B1/en not_active IP Right Cessation
- 2005-09-16 CA CA2580509A patent/CA2580509C/en not_active Expired - Lifetime
- 2005-09-16 KR KR1020077007022A patent/KR100862785B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070046958A (en) | 2007-05-03 |
| ATE487552T1 (en) | 2010-11-15 |
| BRPI0515368A (en) | 2008-07-22 |
| CN101022903B (en) | 2010-11-10 |
| WO2006031193A1 (en) | 2006-03-23 |
| PL1812187T3 (en) | 2011-04-29 |
| CA2580509A1 (en) | 2006-03-23 |
| KR100862785B1 (en) | 2008-10-13 |
| BRPI0515368B1 (en) | 2014-07-29 |
| CN101022903A (en) | 2007-08-22 |
| DE602005024708D1 (en) | 2010-12-23 |
| MX2007003194A (en) | 2007-05-16 |
| EP1812187B1 (en) | 2010-11-10 |
| RU2351434C2 (en) | 2009-04-10 |
| EP1812187A1 (en) | 2007-08-01 |
| JP2008513602A (en) | 2008-05-01 |
| RU2007114275A (en) | 2008-10-27 |
| JP4887296B2 (en) | 2012-02-29 |
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| EEER | Examination request |