CN106660118A

CN106660118A - New product

Info

Publication number: CN106660118A
Application number: CN201580039964.XA
Authority: CN
Inventors: A·阿赫林; P·约翰松
Original assignee: Hoganas AB
Current assignee: Hoganas AB
Priority date: 2014-05-23
Filing date: 2015-05-21
Publication date: 2017-05-10
Anticipated expiration: 2035-05-21
Also published as: KR102357205B1; US20170189959A1; JP6599442B2; WO2015177300A1; JP2017521562A; ES2674801T3; KR20170010825A; TWI659787B; GB201409250D0; CN106660118B; EP3145660B1; PL3145660T3; EP3145660A1; BR112016026840B1; CA2950583A1; CA2950583C; TW201609285A

Abstract

The present invention relates to a metal powder composition for making compacted parts, the metal powder composition comprising (i) sponge iron particles or sponge iron-based particles, and (ii) a lubricant comprising at least two different fatty acid amides.

Description

New product

Technical field

The present invention relates to be used for the new metal-powder compositions of powder metallurgy industry.Especially, the present invention relates to sponge iron Original washing powder powder composition, it includes lubricant, for improving powder properties, compression and processing.

Background technology

In the industry, just become increasingly by compression and the use of the metal product of sintered iron base powder composition production Generally.The prescription of these metal products is continuously risen, and thus needs to develop the new property with improvement Powder composition.

Therefore there are the needs for improving powder properties, compression method and sintering method.The parameter that can improve is such as gold The property of category powder itself or the type or property of various additives.Additive can include alloy element (alloying Element), flow agents (flow agent), lubricant, machinable Contrast agent or hard phase material.As for low The lubricant of density PM application, due to its generally good performance, commonly used zinc stearate or amide waxe.

With regard to the property of metal dust itself, the interest of people is concentrated on atomization (atomised) metal dust and especially Ground is on itself and the use together of certain form of lubricant.Atomized metal pow der can be by by the thread of motlten metal (thin stream) clashes into the high energy jet of fluid (such as water) and prepares.If sought in powder metallurgy structure part High green density (green density), atomized metal pow der is probably favourable.

In US 2012/0187611, it is reported first example that atomized metal pow der and particular lubricants are used together Road atomized metal pow der and three compositions are the lubricating combination use together of substance A, B and C.Tissuemat E is preferred thing Matter A.The option of substance B includes fatty acid amide, fatty acid bis-amides, saturated fatty alcohol and saturated fat acid glycerol.Substance C is Oligoamide, it can have 500 and 30, the molecular weight between 000.Substance C is typically used as the main component of lubricant.Thing Matter A is reported as (ejection) behavior of release has negative effect.Atomization is all based in order to compensate this what is enumerated The negative effect seen in the metal-powder compositions of metal dust, the amount that substance B is used is at least the half of the amount of substance A.

Second example which reports atomized metal pow der and (excellent with the first lubricant in US 2001/0027170 Select ethylenebisstearamide (EBS)) core, the aggregated particle that coated by the second lubricant (preferred zinc stearate) of the surface of core The use of the lubricant combination of (aggregate particle).The example reports this particular aggregates (i.e. with being located at The granule of the second lubricant on the surface of the nuclear particle of the first lubricant) allow to improve obtain based on Atomized metal powder Flowing of the compositionss at end compared with the method for other combinations of the first and second lubricants.

3rd example in 993,429, which reports atomized metal pow der and with lubricating comprising SOLID ORGANIC in US 7 The core of agent, the use together of the compounded lubricant granule of adhesion trickle carbon granule on a surface.For the preferred solid of core Body organic lubricant includes fatty acid, fatty acid mono-amide and fatty acid bis-amides.The example is reported and sticks to SOLID ORGANIC Carbon granule on the surface of core contribute to for the compositionss based on atomized metal pow der for obtaining avoid assemble and improve stream It is dynamic.

Another type of metal dust is so-called sponge iron powder.Compressed the part for preparing by sponge iron powder to have and work as The green strength (green strength) obtained during compression such as atomized powder compares very high green strength.In order to improve pressure The performance contracted during releasing from instrument with compression member, generally adds mixture of powders by lubricant.This has for example may lead The shortcoming for causing the powder flow rate of longer filling time to reduce.

Especially, sponge powder shows relatively low flow rate compared with atomized powder.This is further such that lubricant exists Using in sponge iron-based powder combination complicates.

To the conventional lubricant of metal dust addition, such as metallic stearate remaining lubricant may be caused to be deposited on use In the stove of sintering, and the surface defect of final products is also resulted in, cause higher percent defective (scrap rate) and more high Expensive maintenance.

With regard to lubricant and the example for using of sponge grease powder, such as GB 391,155 is may be referred to, wherein fat Sour such as stearic acid, Palmic acid or Oleic acid can be used for lubricating sponge iron.One example more recently is US2010/0116240, Which describe and be used together synthetic wax such as ethylene bis-stearamide wax and sponge iron powder.

Summary of the invention

Present invention is particularly based on such have now surprisingly been found that, i.e., for sponge iron particle (or sponge iron-based grains), The use of the combination of two or more different fatty acid amides contributes to solving the problems, such as above-mentioned flowable.Especially, this The use of the combination of sample allows to provide metal while suitable apparent density is provided with excellent flowable Powder composition.The use of such combination is also provided further will become bright from the description of this invention given below The advantage for showing.

Thus, the present invention relates to include the metal dust combination of sponge iron particle (or sponge iron-based grains) and lubricant Thing.Especially, the present invention relates to new powder composition, it includes (i) sponge iron powder or sponge iron-based powder, and (ii) spy Fixed lubricant.Thus, optionally, sponge iron powder can include at least at least one alloying agents, in the case its It is referred to as sponge iron-based powder (or granule).Lubricant brings relatively low release power in the method for production compression member, right Flow rate has the negative effect of very little.

The invention further relates to the part prepared by powder composition.

Detailed description of the invention

By iron ore is reduced directly with the reducing gas that can be produced by natural gas or coal, (its form is block, pill to sponge iron Or fine powder) production.Such ferrum can grind or crush to produce granule.These granules generally have irregular shape, height Surface area and internal void.Multiple such granules form powder.Metal dust can grind or crush after annealing.

The invention provides metal-powder compositions, it includes (i) sponge iron particle or sponge iron-based grains, and (ii) bag Lubricant containing at least two different fatty acid amides.

Sponge iron powder particle can be made up of ferrum or can be so-called iron-based and including other alloyings unit substantially Element, such as C, Cu, Ni or Mo (preferred Cu, Ni or Mo；Or, in an especially preferred embodiment, using C and Cu bis- Person).When C is used as alloy element, form of graphite is preferably.

Therefore, at a preferred aspect of the present invention, the composition (i) of metal-powder compositions is comprising sponge iron particle Sponge iron-based grains with one or more of C, Cu, Ni and Mo.Especially, sponge iron-based grains preferably comprise sponge iron particle Granule with one or more of C, Cu, Ni and Mo.In these aspects, both C and Cu are preferably used.

Preferably, in this regard sponge iron-based grains comprising at least 80 weight %, more preferably at least 90 weight %, still more The preferably at least sponge iron particle of 95 weight %.Thus, sponge iron-based grains preferably comprise 20 weight % or it is less, more preferably 10 (it is preferably as mentioned above C, Cu, Ni and Mo for weight % or less, still more preferably 5 weight % or less alloy element One or more, the typically form of granule).

Metal-powder compositions of the invention contain sponge iron or sponge iron-based powder, such as MH80.23, NC100.24 and SC100.26 (can be by SwedenAB is obtained), optionally at least one alloy element, and at least A kind of lubricant.

The alloy element of iron powder can be in powder form added to can include graphite, or the metal dust of non-ferric (such as Cu, Ni or Mo).

At least two different fatty acid amides are included for the lubricant in the present invention.Lubricant can include two kinds, Three kinds, four kinds, five kinds or more kinds of different fatty acid amides.It is, however, preferable that it includes at least three kinds different fatty acids Amide, such as three kinds or four kinds of fatty acid amides.

At least one for the fatty acid amide in the present invention is preferably monoamides, more preferably formula R-C (O)-NH₂'s Monoamides, wherein R are alkyl.Preferably, at least two for the fatty acid amide in the present invention should be monoamides, more preferably It is formula R-C (O)-NH₂Monoamides, wherein R be alkyl.

As described above, lubricant preferably comprises at least three kinds of different fatty acid amides.In this regard, it is preferable that described At least three kinds different fatty acid amides should be monoamides, more preferably formula R-C (O)-NH₂Monoamides, wherein R be alkyl.

For each different formulas R-C (O)-NH₂Monoamides, alkyl (R) certainly should difference.But, alkyl (R) leads to 3 to 27 carbon atoms can often be contained, so that fatty acid amide itself contains altogether 4 to 28 carbon atoms.

Generally it is also preferred that R contain at least 7, preferably at least 9, even more desirably at least 11, even more desirably at least 13 and even more desirably at least 15 carbon atoms.

Generally it is also preferred that R contains 25 or less, more preferably 23 or less, even more preferably 21 or less carbon originals Son.

Alkyl (R) can be straight chain or branched, but preferably straight chain.

Alkyl (R) can be saturation or undersaturated.When unsaturation, its preferably comprise 5 or less, further preferably 4 or less, even preferably comprise 3 or less, even preferably comprise 2 or less, generally only 1 alkenyl group.It is preferred that Alkyl (R) can be saturation.

Preferred option for the fatty acid amide of the present invention includes unsaturated fatty acid amide octanoic acid amide, capric acid acyl Amine, lauric amide, myristic acid amide, palmitamide, stearic amide, arachidamide, behenamide, two Tetradecanoic acid amide and hexacosoic acid amide；Unsaturated fatty acid amide myristicol amide, palmitoleic acid amide, Sapienic acid amide, oleamide, elaidic acid amide, vaccenic acid amide, linoleamide, Linoelaidic acid amide, alpha-linolenic acid amide, arachidonic acid amide, eicosapentaenoic acid amide, erucyl amide With docosahexaenoic acid amide.

Particularly preferably (i.e. wherein alkyl (R) is the chemical combination of alkyl to the fatty acid mono-amide of saturation and non-branching Thing), particularly wherein those of alkyl (R) containing 13 to 23 carbon atoms, more preferably 15 to 21 carbon atoms.Therefore, Petiolus Trachycarpi Sour amide (CH₃(CH₂)₁₄C(O)NH₂), stearic amide (CH₃-(CH₂)₁₆C(O)NH₂), arachidamide (CH₃(CH₂)₁₈C(O) NH₂) and behenamide (CH₃(CH₂)₂₀C(O)NH₂) be fatty acid amide preferred option.Lubricant is preferably comprised At least three kinds of such particularly preferred fatty acid amide.

Preferably, at least one (at least one of i.e. described at least two different fatty acid amide) of fatty acid amide With the alkyl with 15 or less carbon atoms.It is highly preferred that at least one of fatty acid amide is with 15 or more The less but at least alkyl of 13 carbon atoms.Even further preferably, at least one of fatty acid amide is palmitamide.

In a specific preferred aspect of the present invention, lubricant is the mixture of stearmide and palmitamide, and May further include peanutamide and/or Erucamide.It is highly preferred that lubricant is (i) stearic amide, (ii) palm fibre The mixture of palmitic acid acid amide and (iii) arachidamide and/or behenamide.

Lubricant for the present invention preferably comprises described at least two different fatty acid amides as key component.It is special Not, described at least two different fatty acid amides preferably account at least 50 weight % of lubricant, more preferably at least 80 weights Amount %, even more desirably at least 90 weight %.Typically, lubricant is substantially by described at least two different fatty acid amide groups Into.

With regard to the relative quantity of each of described at least two different fatty acid amides, a kind of such fatty acid amide 1 is preferably relative to alternative ratio:1 to 1:4, more preferably 1:1 to 1:3, even more preferably 1:1 to 1:2.This is not excluded for certainly Other fatty acid amides are with the possible presence of minor amount.

When lubricant includes at least three kinds of different fatty acid amides, it preferably comprises at least a kind of fat of 25 weight % Fat acid amide, and each of at least 10% other two kinds of fatty acid amides.More preferably it includes at least 40 weight % A kind of fatty acid amide, and at least 20% other two kinds of fatty acid amides each is (such as particularly preferred at one It includes a kind of fatty acid amide of at least 50 weight % in embodiment, and at least 25% other two kinds of fatty acid amides Each).In this regard, as generally here, unless otherwise noted, % refers to weight %.

In a preferred embodiment, for lubricant (and the metal powder preferably also of the invention of the present invention Powder composition) it is substantially free of the organic lubricant of non-fat sour amide.In particular it is preferred to be substantially free of not preferred such place The organic lubricant of the fatty acid mono-amide for the present invention stated.It is therefore preferable that being substantially free of the double acyls of fatty acid, fatty acid (such as molecular weight is oligomeric for the amide of 500g/mol or higher for amine, fatty acid alcohol, fatty acid glycerine and/or relatively heavy amide Thing).It is also preferred that metallic soap is substantially free of, such as zinc stearate.The such as metallic soap containing metallic lubricant is avoided to be favourable, because its Reduce the amount of undesirable " ash " residual after lubricant has decomposed.

In a concrete preferred aspect of the present invention, lubricant is Erucamide, stearmide and palmitamide Mixture.The stearmide of amount preferably 20 to 50 weight %, the palmitamide of 20 to 50 weight %, and Semen arachidis hypogaeae can be further included Amide, balance of Erucamide.

It is highly preferred that the 22 of stearmide of the amount for 25 weight %, the palmitamide of 25 weight % and 50 weight % Alkane amide.

The present invention relates to include the metal-powder compositions of sponge iron particle and lubricant.Preferably, lubricant is 20 The mixture of dioxane amide, stearmide and palmitamide.

Lubricant is preferably particle form.In this regard, lubricant can include described at least two different fat The separate granule of each of sour amide.Or, lubricant can be the mixing of the different fatty acid amide of particle form Thing (i.e. each single granule generally comprises the mixture of different fatty acid amides).

The amount of lubricant is preferably between 0.2 weight % and 1.4 weight %, preferably 0.4 weight % and 1.0 weight % it Between, or between more 0.6 weight % and 1.0 weight %.Thus, the profit of metal-powder compositions of the invention comprising such amount Lubrication prescription.

The operating temperature of lubricant is from the RT (room temperature) in tool of compression to the standard in longer sequence aborning Operating temperature, for example～60 DEG C and until 80 DEG C.

In the metal-powder compositions of the present invention, sponge iron particle preferably has at least 5 μm of average particle size, preferably At least 10 μm, more preferably at least 20 μm, even more desirably at least 50 μm.Sponge iron particle preferably has 500 μm or lower flat Equal granularity, more preferably 300 μm or lower, even more preferably 200 μm or lower, even more preferably 150 μm or lower.

When deployed, alloy element is preferably particle form.In this regard, alloy element granule preferably has extremely Few 5 μm average particle size, preferably at least 10 μm, more preferably at least 20 μm, even more desirably at least 50 μm.Alloy element Grain preferably have 500 μm or lower average particle size, more preferably 300 μm or lower, even more preferably 200 μm or lower, very To more preferably 150 μm or lower.

As described above, lubricant can be used preferably in granular form.In this regard, lubricant particle preferably has extremely Few 0.5 μm average particle size, preferably at least 1 μm, more preferably at least 2 μm, even more desirably at least 5 μm.Lubricant particle is excellent Select and there is 500 μm or lower average particle size, more preferably 200 μm or lower, even more preferably 100 μm or lower, even more It is preferred that 50 μm or lower.

As employed herein, average particle size preferably refers to the average particle size measured by laser diffraction and scattering method.

Powder composition has preferably flowing, and it increases the productivity ratio and quality of final part.

Powder model system shows low friction during squeeze operation and reduces what is occurred during part is released from tool of compression Release power and release energy.The reduction of these energy causes surface defect less in less tool wear and final products.

Green strength is also improved and it reduces green compact rupture with other " green compact on the forepiece of sintering operation (green) " the risk of related damage.Higher green strength improves production efficiency and reduces the percent defective in production.

By using new mixed-powder system, it is possible to decrease or avoid when the traditional lubrication used in metal powder mixture The surface defect generally occurred within during agent.

Present invention also offers such method, it includes the metal dust combination of (i) compression present invention as above Thing, and (ii) sinter so obtained compressed metal powder composition to produce metal product.Present invention also offers can pass through Or the metal product obtained by such method.

Embodiment 1

Prepare the different ferrous based powder metallurgical mixture according to table 1.As iron-based powder, using sponge iron powder MH80.23, NC100.24 and SC100.26 (can be by SwedenAB is obtained).Also use ABC100.30 (atomized iron powders End), 2%Cu-100 mesh (from the copper powders of Italian Poemton), DACu (can be by SwedenWhat AB was obtained Distaloy ACu) and 0.5%C-UF4 (from GermanyThe graphite of AG).

Table 1

Labelling	Chemical characteristic	Supplier
			X	50% Erucamide/25% stearmide/25% palmitamide	Abril industrial waxes
Znst	Zinc stearate	Faci,UK
			Amide waxe PM	Ethylenebisstearamide	Faci,Italy
PS	50% palmitamide/50% stearmide	Croda,UK
			B	17% Erucamide/46% peanutamide/37% stearmide

Table 2, the ferrous based powder metallurgical mixture for preparing

1 (present invention)	NCx0.4	NC100.24+2%Cu-100+0.5%C-UF4+0.4%X
			2 (present invention)	NCx0.6	NC100.24+2%Cu-100+0.5%C-UF4+0.6%X
3 (present invention)	NCx0.8	NC100.24+2%Cu-100+0.5%C-UF4+0.8%X
			4 (present invention)	NCx1.0	NC100.24+2%Cu-100+0.5%C-UF4+1.0%X
5 (contrasts)	NCZ0.8	NC100.24+2%Cu-100+0.5%C-UF4+0.8%ZnSt
			6 (contrasts)	NCA0.8	NC100.24+2%Cu-100+0.5%C-UF4+0.8% amide waxe PM
7 (present invention)	MHx0.8	MH80.23+2%Cu-100+0.5%C-UF4+0.8%X
			8 (contrasts)	MHZ0.8	MH80.23+2%Cu-100+0.5%C-UF4+0.8%ZnSt
9 (contrasts)	MHA0.8	MH80.23+2%Cu-100+0.5%C-UF4+0.8% amide waxe PM
			10 (present invention)	NCB0.8	NC100.24+2%Cu-100+0.5%C-UF4+0.8%B
11 (contrasts)	ABCx0.8	ABC100.30+1.5%Cu (DACu)+0.5%C-UF4+0.8%X
			12 (contrasts)	ABCA0.8	ABC100.30+1.5%Cu (DACu)+0.5%C-UF4+0.8% amide waxe PM
13 (contrasts)	ABCPS0.8	ABC100.30+1.5%Cu (DACu)+0.5%C-UF4+0.8%PS

Hall flowing (FH) speed is measured and according to ISO13517 according to ISO 4490:2013 measurement Flow Gustavsson (FG) and according to ISO 3923 measure apparent density.

Table 3, the flow velocity (FH and FG) of ferrous based powder metallurgical mixture and apparent density (AD)

Table 3 shows that new sponge iron mixture of powders shows the apparent density being similar to as the mixture with amide waxe Level and for the mixture with zinc stearate obtains highest apparent density.The all of mixture with X shows Go out the mobility of the improvement according to two kinds of different methods for measuring flow.In addition, the mixture (mixture 10) with-B is such as Mobility is improved compared with metal-free bisamide wax (mixture 6).

The flow rate (FH) and apparent AD (AD) of table 4, metal dust, unlubricated dose

For all of mixture, the often encapsulating area that compression sample needs is released from mould by recording The gross energy of (enveloped area) and the often peak value of encapsulating area release power, measurement lubricant properties.Part is diameter The cylindrical shape of 25mm, height 15mm, and the compression pressure for applying is 250,400 and 550MPa.

Table 5, peak value releases power and releases energy

Table 5 shows the amount of the reduction of X for mixture 1 to 6, and wherein NC100.24 gives and zinc stearate and amide waxe The property that mixture is similar in 0.8% Lubricant levels.Similar result is give also using B (in mixture 10).Total For, the result of X is better than comparative example, except releasing power using the static of powder based on SC100.26 under 550MPa.

Measure in 6.45g/cm on the mixture of all preparations³Under green strength.Green compact are tested in TRS test strip Intensity.

Table 6, green strength

50 to 75% are improved as the green strength of NC100.24 mixture compares display when using X, and are improved When using B it can also be seen that.It is more preferable than X for the mixture green strength using MH80.23 improves 30 to 50%.

Claims

1. a kind of metal-powder compositions, it includes (i) sponge iron particle or sponge iron-based grains, and (ii) includes at least two The lubricant of different fatty acid amides.

2. metal-powder compositions of claim 1, wherein lubricant include at least three kinds different fatty acid amides.

3. metal-powder compositions of claim 1 or 2, wherein at least one fatty acid amide is formula R-C (O)-NH₂Single acyl Amine, wherein R are hydrocarbyl groups.

4. metal-powder compositions of claim 3, two kinds of fatty acid amides of wherein at least are formula R-C (O)-NH₂Single acyl Amine, wherein R are hydrocarbyl groups.

5. metal-powder compositions of claim 2, the different fatty acid amide of three kinds of wherein at least is formula R-C (O)-NH₂ Monoamides, wherein R is hydrocarbyl group.

6. metal-powder compositions of any one of claim 3 to 5, wherein R is alkyl and containing 13 to 23 carbon originals Son.

7. metal-powder compositions of any one of claim 1 to 6, wherein at least one fatty acid amide is Palmic acid acyl Amine.

8. metal-powder compositions of any one of aforementioned claim, wherein lubricant is behenamide, stearic acid The mixture of amide and palmitamide.

9. metal-powder compositions of any one of aforementioned claim, the component (i) of wherein metal-powder compositions is to include The sponge iron-based grains of the sponge iron particle together with C, Cu, Ni and Mo one or more.

10. a kind of method, compresses the metal-powder compositions of any one of claim 1 to 9 and (ii) is sintered so including (i) The compressed metal powder composition for obtaining is to produce metal product.

11. the metal product that can be obtained by the method for claim 10.