Vidarsson, Hilmar (Tröskvägen 15 Höganäs, S-263 53, SE)
| 1. | A lubricant for compaction of metallurgical pow der compositions, c h a r a c t e r i s e d in that it contains a polyolefinebased polymer, which has a weight average molecular weight Mw of 50010 000. |
| 2. | A lubricant as claimed in claim 1, c h a r a c t e r i s e d in that the polymer is a polyethylene wax. |
| 3. | A lubricant as claimed in claim 1 or claim 2, c h a r a c t e r i s e d in that it has a weightaver age molecular weight Mw of 100010 000. |
| 4. | A lubricant as claimed in any one of claims 13, c h a r a c t e r i s e d in that it has a polydisper sity Mw/Mn lower than 2.5, preferably lower than 1.5. |
| 5. | A metalpowder composition for compaction con taining metal powder and a lubricant, c h a r a c t e r i s e d in that the lubricant contains a polyolefine based polymer, which has a weightaverage molecular weight Mw of 50010 000, preferably 100010 000. |
| 6. | A metalpowder composition as claimed in claim 5, c h a r a c t e r i s e d in that the polymer is a poly ethylene wax. |
| 7. | A metalpowder composition as claimed in any one of claims 5 to 6, c h ar a c t e r i s e d in that it has a polydispersity Mw/Mn lower than 2.5, preferably lower than 1.5. |
| 8. | A metalpowder composition as claimed in any one of claims 5 to 7, c h a r a c t e r i s e d in that it further contains one or more additives selected from the group consisting of binding agents, processing aids, alloying elements and hard phases. |
| 9. | A metalpowder composition as claimed in any one of claims 5 to 7, c h a r a c t e r i s e d in that it further contains a binding agent and one or more addi tives selected from the group consisting of processing aids, alloying elements and hard phases. |
| 10. | A metalpowder composition as claimed in any one of claims 5 to 9, c h a r a c t e r i s e d in that it comprises a major amount of a metal powder consisting of an ironbased powder, having a weightaverage particle size in the range of about 25350 Fm, and a minor amount of a solid lubricant comprising a polyolefinebased poly mer, which has a weightaverage molecular weight Mw of 50010 000. |
| 11. | A metalpowder composition as claimed in claim 10, c h a r a c t e r i s e d in that the lubricant makes up 0.12.0% by weight of the total composition, preferably 0.20.8% by weight. |
| 12. | A method for making sintered products, compris ing the steps of a) mixing a metal powder and a lubricant to a metal powder composition b) compacting the metalpowder composition to a com pacted body, and c) sintering the compacted body c h a r a c t e r i s e d in that the lubricant contains a polyolefinebased polymer, which has a weight average molecular weight Mw of 50010 000. |
| 13. | A method as claimed in claim 12, c h a r a c t e r i s e d in that the compacted body before step c) is heated to a temperature above the melting point peak of the lubricant during a sufficient period of time for obtaining essentially the same temperature in the entire compacted body. |
| 14. | A method for making sintered products, compris ing the steps of a) mixing a metal powder and a lubricant to a metal powder composition, b) preheating the metalpowder composition to a pre determined temperature, c) compacting the heated metalpowder composition in a heated tool, and d) sintering the compacted metalpowder composition, c h a r a c t e r i s e d in that the lubricant contains a polyolefinebased polymer, which has a weightaverage molecular weight Mw of 100010 000. |
| 15. | A method as claimed in claim 14, c h a r a c t e r i s e d in that the metalpowder composition in step b) is preheated to a temperature below the melting point peak of the polyolefine, preferably to a tempera ture of 550°C below the melting point peak of the lubri cant. |
| 16. | A method as claimed in claim 14 or 15, c h a r a c t e r i s e d in that the tool before step c) is heated to a temperature of the melting point peak of the polyolefine or below, preferably to a temperature of 550°C below the melting point peak of the lubricant. |
| 17. | The use of a lubricant, which contains a poly olefinebased polymer, which has a weightaverage molecu lar weight Mw of 50010 000, in a metallurgical powder composition in cold compaction. |
| 18. | The use of a lubricant, which contains a poly olefinebased polymer, which has a weightaverage molecu lar weight Mw of 100010 000, in a metallurgical powder composition in warm compaction. |
In industry, the use of metal products manufactured by compacting and sintering metal-powder compositions is becoming increasingly widespread. A number of different products of varying shape and thickness are being pro- duced, and the quality requirements placed on these prod- ucts are that the manufactured metal products have high density as well as high strength.
In metal compaction, different standard temperature ranges are used. Thus, cold pressing is predominantly used for compacting metal powder (the powder has room temperature). Both cold pressing and warm pressing re- quire the use of a lubricant.
Compaction at temperatures above room temperature has evident advantages, yielding a product of higher den- sity and higher strength than compaction performed at lower temperatures.
Most of the lubricants used in cold compaction can- not be used in high-temperature compaction, since they seem to be effective within a limited temperature range only. An ineffective lubricant considerably increases the wear of the compacting tool.
How much the tool is worn is influenced by various factors, such as the hardness of the material of the tool, the pressure applied, and the friction between the
compact and the wall of the tool when the compact is com- pacted and ejected. The latter factor is strongly linked to the lubricant used.
The ejection force is the force required for eject- ing the compact from the tool. Since a high ejection force not only increases the wear of the compacting tool but may also damage the compact, this force should pref- erably be reduced.
However, the use of a lubricant may create problems in compaction, and it is therefore important that the lu- bricant is well suited to the type of compaction carried out.
In order to perform satisfactorily, the lubricant should be forced out of the pore structure of the powder composition in the compacting operation, and into the in- terspace between the compact and the tool, thereby lubri- cating the walls of the compaction tool. By such lubrica- tion of the walls of the compaction tool, the ejection force is reduced.
Another reason why the lubricant has to emerge from the compact is that it would otherwise create pores in the compact after sintering. It is well-known that large pores have an adverse effect on the dynamic strength properties of the product.
An object of the new lubricant according to the pre- sent invention is to make it possible to manufacture com- pacted products having high transverse rupture strength, high green density, as well as sintered products having high sintered density and low ejection force from the lubricant in combination with metal powders. As the com- pact is subject to considerable stresses when ejected from the compacting tool and as the product must keep to- gether during the handling between compaction and sinter- ing without cracking or being otherwise damaged, it is important with high transverse rupture strength. This is especially important in the case of thin parts.
The lubricant according to the invention contains a polyolefine-based polymer, which has a weight-average molecular weight Mw of 500-10 000. Polyolefins are a group of thermoplastic polymers with different degrees of crystallinity. Polyolefins are subdivided into simple polyolefins, poly (a-olefins) and copolymers based on ole- fins and/or a-olefins. The copolymers may also include other types of comonomers such as vinylacetates, acry- lates, styrenes, etc. Poly (a-olefins) include polymers such as polypropylene and poly (1-butene). Simple polyole- fines, however, include polymers such as branched chain low-density polyethylene and linear chain high-density polyethylene. Linear chain polyethylenes of relatively low molecular weight are termed polyethylene waxes.
The polymer according to the invention is prefer- ably a polyethylene wax. The lubricant according to the invention can be used in both cold and warm compaction, but in warm compaction the weight-average molecular weight Mw of the lubricant preferably is 1000-10 000.
Preferably, the lubricant of the invention has a polydispersity Mw/Mn lower than 2.5, preferably lower than 1.5.
The invention further concerns a metal-powder compo- sition containing a metal powder and the above-mentioned lubricant, as well as methods for making sintered prod- ucts, both cold and warm compaction. The method for cold compaction according to the invention comprises the steps of a) mixing a metal powder and a lubricant to a metal- powder composition b) compacting the metal-powder composition to a com- pacted body, and c) sintering the compacted body, use being made of a lubricant according to the invention, which has a weight- average molecular weight Mw of 500-10 000.
The method for warm compaction according to the in- vention comprises the steps of a) mixing a metal powder and a lubricant to a metal- powder composition, b) preheating the metal-powder composition to a pre- determined temperature, c) compacting the heated metal-powder composition in a heated tool, and d) sintering the compacted metal-powder composition, use being made of a lubricant according to the invention, which has a weight-average molecular weight Mw of 1000- 10 000.
The present invention further relates to the use of the lubricant according to the invention in a metallurgi- cal powder composition in cold and warm compaction.
The lubricant can make up 0.1-2.0 % by weight of the metal-powder composition according to the invention, preferably 0.2-0.8% by weight, based on the total amount of the metal-powder composition. The possibility of using the lubricant according to the present invention in low amounts is an especially advantageous feature of the in- vention since it permits that compacts and sintered prod- ucts having high densities can be achieved cost-effec- tively.
As used in the description and the appended claims, the expression"metal powder"encompasses iron-based pow- ders essentially made up of iron powders containing not more than about 1.0% by weight, preferably not more than about 0.5% by weight, of normal impurities. Examples of such highly compressible, metallurgical-grade iron pow- ders are the ANCORSTEEL 1000 series of pure iron powders, e. g. 1000,1000B and 1000C, available from Hoeganaes Cor- poration, Riverton, New Jersey and similar powders avail- able from Hoganas AB, Sweden. For example, ANCORSTEEL 1000 iron powder, has a typical screen profile of about 22% by weight of the particles below a No. 325 sieve (U. S. series) and about 10% by weight of the particles
larger than a No. 100 sieve with the remainder between these two sizes (trace amounts larger than No. 60 sieve).
The ANCORSTEEL 1000 powder has an apparent density of about 2.85-3.00 g/cm3, typically 2.94 g/cm3. Other iron powders that can be used in the invention are typical sponge iron powders, such a Hoeganaes'ANCOR MH-100 pow- der.
The iron-based powders can also include iron, pre- ferably substantially pure iron, that has been preal- loyed, diffusion bonded, or admixed with one or more alloying elements. Examples of alloying elements that can be combined with the iron particles include, but are not limited to, molybdenum; manganese; magnesium; chromium ; silicon; copper; nickel; gold; vanadium; columbium (niobium); graphite; phosphorus; aluminium; binary alloys of copper and tin or phosphorus; Ferro-alloys of manga- nese, chromium, boron, phosphorus, or silicon; low mel- ting ternary and quaternary eutectics of carbon and two or three of iron, vanadium, manganese, chromium, and molybdenum; carbides of tungsten or silicon; silicon nitride; aluminium oxide; and sulphides of manganese or molybdenum, and combinations thereof. Typically, the alloying elements are generally combined with the iron powder, preferably the substantially pure iron powder in an amount of up to about 7% by weight, more preferably from about 0.25% to about 5% by weight, more preferably from about 0.25% to about 4% by weight, although in cer- tain specialised uses the alloying elements may be pre- sent in an amount of from about 7% to about 15% by weight, of the iron powder and alloying element.
The iron-based powders can thus include iron parti- cles that are in admixture with the alloying elements that are in the form of alloying powders. The term "alloying powder"as used herein refers to any particu- late element or compound, as previously mentioned, physi- cally blended with the iron particles, whether or not that element or compound ultimately alloys with the iron
powder. The alloying-element particles generally have a weight average particle size below about 100 microns, preferably below about 75 microns, more preferably below about 30 microns. Binding agents are preferably included in admixtures of iron particles and alloying powders to prevent dusting and segregation of the alloying powder from the iron powder. Examples of commonly used binding agents include those set forth in U. S. Patent Nos.
4 483 905 and 4 676 831, both to Engstrom, and in U. S.
Patent No. 4 834 800 to Semel, all of which are incorpo- rated by reference herein in their entireties.
The iron-based powder can further be in the form of iron that has been pre-alloyed with one or more of the alloying elements. The pre-alloyed powders can be pre- pared by making a melt of iron and the desired alloying elements, and then atomising the melt, whereby the ato- mised droplets form the powder upon solidification. The amount of the alloying element or elements incorporated depends upon the properties desired in the final metal part. Pre-alloyed iron powders that incorporate such alloying elements are available from Hoeganaes Corp. as part of its ANCORSTEEL line of powders.
A further example of iron-based powders is diffu- sion-bonded iron-based powder, which contains particles of substantially pure iron that have the alloying ele- ments set forth above diffusion-bonded to their outer surfaces. Such commercially available powders include DISTALOY 4600A diffusion-bonded powder available from Hoeganaes Corporation, which contains about 1.8% nickel, about 0.55% molybdenum, and about 1.6% copper, and DISTA- LOY 4800A diffusion bonded powder available from Hoe- ganaes Corporation, which contains about 4.05% nickel, about 0.55% molybdenum, and about 1.6% copper. Similar grade powders are also available from Hoganas AB, Sweden.
A preferred iron-based powder is made of iron pre- alloyed with molybdenum (Mo). The powder is produced by atomising a melt of substantially pure iron containing
from about 0.5% to about 2.5% by weight of Mo. An example of such a powder is Hoeganaes ANCORSTEEL 85HP steel pow- der, which contains about 0.85% by weight of Mo, less than about 0.4% by weight, in total, of such other mate- rials as manganese, chromium, silicon, copper, nickel, molybdenum or aluminium, and less than about 0.02% by weight of carbon. Another example of such a powder is Hoeganaes ANCORSTEEL 4600V steel powder, which contains about 0.5-0.6% by weight of molybdenum, about 1.5-2.0% by weight of nickel, and about 0.1-0.25% by weight of manga- nese, and less than about 0.02% by weight of carbon.
Another pre-alloyed iron-based powder that can be used in the invention is disclosed in U. S. Patent No.
5 108 93 to Causton, entitled"Steel Powder Admixture Having Distinct Pre-alloyed Powder of Iron Alloys", which is herein incorporated in its entirety. This steel powder composition is an admixture of two different pre-alloyed iron-based powders, one being a pre-alloy of iron with 0.5-2.5% by weight of molybdenum, the other being a pre- alloy of iron with carbon and with at least about 25% by weight of a transition element component, wherein this component comprises at least one element selected from the group consisting of chromium, manganese, vanadium, and columbium. The admixture is in proportions that pro- vide at least about 0.05% by weight of the transition element component to the steel powder composition. An example of such a powder is commercially available as Hoeganaes ANCORSTEEL 41 AB steel powder, which contains about 0.85% by weight of molybdenum, about 1% by weight of nickel, about 0.9% by weight of manganese, about 0.75% by weight of chromium, and about 0.5% by weight of car- bon.
Other iron-based powders that are useful in the practice of the invention are ferromagnetic powders. An example is a composition of substantially pure iron pow- ders in admixture with powder of iron that has been pre- alloyed with small amounts of phosphorus.
Still further iron-based powders that are useful in the practice of the invention are iron particles coated with a thermoplastic material to provide a substantially uniform coating of the thermoplastic material as de- scribed in U. S. Pat. No. 5 198 137 to Rutz et al., which is incorporated herein in its entirety. Preferably, each particle has a substantially uniform circumferential coating about the iron core particle. Sufficient thermo- plastic material issued to provide a coating of about 0.001-15% by weight of the iron particles as coated. Gen- erally the thermoplastic material is present in an amount of at least 0.2% by weight, preferably about 0.4-2% by weight, and more preferably about 0.6-0.9% by weight of the coated particles. Preferred are thermoplastics such as polyethersulfones, polyetherimides, polycarbonates, or polyphenylene ethers, having a weight average molecular weight in the range of about 10 000 to 50 000. Other polymeric coated iron-based powders include those con- taining an inner coating of iron phosphate as set forth in U. S. Patent No. 5 063 011 to Rutz et al., which is incorporated herein in its entirety.
The particles of pure iron, pre-alloyed iron, diffu- sion-bonded iron, or thermoplastic coated iron can have a weight average particle size as small as 1 Fm or below, or up to about 850-1000 Fm, but generally the particles will have a weight average particle size in the range of about 10-500 m. Preferred are those having a maximum number average particle size up to about 350 Fm, prefera- bly 50-150 Fm.
Apart from the metal powder and the lubricant according to the invention, the metal-powder composi- tion may contain one or more additives selected from the group consisting of binders, processing aids and hard phases. The binder may be added to the powder composition in accordance with the method described in US-P-4 834 800 (which is hereby incorporated by reference) and be blended into the metal-powder compositions in amounts of
from about 0.005-3% by weight, preferably about 0.05-1.5% by weight, and more preferably about 0.1-1% by weight, based on the weight of the iron and alloying powders.
The processing aids used in the metal-powder compo- sition may consist of talc, forsterite, manganese sul- phide, sulphur, molybdenum disulphide, boron nitride, tellurium, selenium, barium difluoride and calcium di- fluoride, which are used either separately or in combina- tion.
The hard phases used in the metal-powder composition may consist of carbides of tungsten, vanadium, titanium, niobium, chromium, molybdenum, tantalum and zirconium, nitrides of aluminium, titanium, vanadium, molybdenum and chromium, A1203, B4C, and various ceramic materials.
With the aid of conventional techniques, the metal- powder and the lubricant particles are mixed to a sub- stantially homogeneous powder composition.
Preferably, the lubricant according to the invention is added to the metal-powder composition in the form of solid particles. The average particle size of the lubri- cant may vary, but preferably is in the range of 3-150|A m.
If the particle size is too large, it becomes diffi- cult for the lubricant to leave the pore structure of the metal-powder composition during compaction and the lubri- cant may then give rise to large pores after sintering, resulting in a compact showing impaired strength proper- ties.
In cold compaction according to the invention the steps are the following: a) mixing a metal powder and a lubricant according to the invention, which contains a polyolefine-based polymer, which has a weight-average molecular weight Mw of 500-10 000 to a metal-powder composition, b) compacting the metal-powder composition to a com- pacted body, and c) sintering the compacted body.
In the cold compaction according to the invention it is preferable to heat the compacted body before step c) to a temperature above the melting point peak of the lubricant during a sufficient period of time for obtaining essentially the same temperature in the entire compacted body. With this treatment the compacted body, not yet sintered, is provided with a high transverse rupture strength, which facilitates the handling and processing of the compacted body between compaction and sintering without cracking or being otherwise damaged. As will be apparent from the tests below, these enhanced transverse rupture strengths are not gained with the use of examples of commercially available lubricants for cold compaction, which makes the lubricant according to the invention special.
In warm compaction according to the invention, the metal powder composition is advantageously preheated be- fore being supplied to the preheated compaction tool. In such preheating of the metal powder composition, it is of importance that the lubricant does not begin to soften or melt, which would make the powder composition difficult to handle when filling the compaction tool, which in turn results in a compacted body having a non-uniform density and poor reproducibility of part weights. Moreover, it is important that no partial premelting of the lubricant occurs, i. e. the lubricant should be a uniform product.
Therefore, it is important that the polydispersity Mw/Mn is lower than 2.5, and preferably lower than 1.5.
The steps of the warm compaction process are the following: a) mixing a metal powder and a lubricant according to the invention, which contains a polyolefine-based polymer with a weight-average molecular weight Mw of 1000-10 000; b) preheating the mixture to a predetermined tem- perature, preferably to a temperature below the melting point peak of the lubricant;
c) transferring the heated powder composition to a die, which is heated to a temperature of preferably a temperature of the melting point peak of the lubricant or below; and compacting the composition; and d) sintering the compacted metal-powder composition In step b) of the method, the metal powder composi- tion is preferably preheated to a temperature of 5-50°C below the melting point of the polymer.
A few tests will now be accounted for in order to illustrate that the invention is effective and yields products of high green density as well as high transverse rupture strength.
Test 1 Table 1 below states a number of lubricants by in- dicating melting point peak, weight-average molecular weight Mw, polydispersity (Mw/Mn) measured green density (GD) and ejection force (Ej. F) in cold compaction of ASC 100.29 (marketed by Hoganas AB) mixed with 0.5 % by weight of graphite, 2 % by weight of Cu-200, and 0.6 % by weight of lubricant. The compaction pressure was 600 MPa.
Table 1 Lubricants in cold compaction Lubricant Mw Mw GD Ej. F Melting point (g/mol) Mn (g/cm2) (N/mm2) peak (°C) PEW3700 3700 2. 6 7. 11 22. 0 125 PEW2000 2000 1. 1 7. 12 18. 4 126 EBS-wax*-7. 18 17. 8 144 * outside the scope of the invention PEW 3700 is a polyethylene wax within the scope of the invention.
PEW 2000 is a polyethylene wax within the scope of the invention.
EBS-wax is an ethylene-bis-stearamide-wax.
The green density was measured according to ISO 3927 1985, and the ejection force was measured according to Hoganas Method 404.
The melting point peaks for the lubricants are in- dicated as the peak values of the melting curve, which was measured with the aid of Differential Scanning Calo- rimetry (DSC) technique on a Model 912S DSC instrument available from TA Instruments, New Castle, DE 197 201 USA.
As appears from table 1, similar green densities can be attained, and the same low ejection force remains with the lubricant having the lower Mw/Mn (PEW 2000) according to the invention as with EBS-wax.
Test 2 Table 2 below states a comparison of lubricant PEW 2000 and EBS-wax concerning heating of the compacted body before sintering, whereby the compacted body is heated to a temperature above the melting point peak of the lubricant during a sufficient period of time for ob- taining essentially the same temperature in the entire compacted body.
The metal-powder compositions contained the follow- ing ingredients.
Composition 1 (invention) ASC 100.29, marketed by Hoganas AB 2.0% by weight CU-200 0.5% by weight graphite 0.6% PEW 2000 Composition 2 (EBS-wax) ASC 100.29, marketed by Hoganas AB 2.0% by weight Cu-2000 0.5% by weight graphite 0.8% EBS-wax Table 2 Compacted bodies heat treated before sintering
Composition Comp. Press GD TRS MPa g/cm3 MPa 1 600 7.10 23 2 600 7.06 13 1 *1) 600 7.10 39 2 *2) 600 7. 05 17 *1) Heat treated to a temperature of 150°C for 60 min.
*2) Heat treated to a temperature of 150°C for 60 min.
As appears from table 2, the transverse rupture strength (TRS) is considerably enhanced by the heat treatment of the green compacted body of composition 1, while the transverse rupture strength of the green com- pacted body of composition 2 is not enhanced signifi- cantly by the heat treatment.
The enhanced transverse rupture strength provides a green compacted body, which can be handled and processed before sintering. This possibility is most desirable in many areas.
Test 3 Table 3 below states a number of lubricants by in- dicating melting point peak, weight-average molecular weight Mw, polydispersity (Mw/Mn), compaction pressure (Comp. Press.), measured green density (GD) and ejection energy (Ej. En.) in cold compaction of ASC 100.29 (marketed by Hoganas AB) mixed with 0.45% by weight of lubricant and 0.15% methacrylate binder.
Table 3 Lubricants in bonded metal composition in cold compaction
Lubricant Mw Mw Comp. GD Ej. En. Melting (g/mol) Mn press. (g/cm2) (J/cm2) point peak (MPa) (°C) PEW 655 655 1.08 600 7. 07 32.38 99 8007. 2138. 91 PEW 1000 1000 1.08 600 7. 07 34.99 113 8007. 2141. 88 PEW 2000 2000 1.1 600 7. 06 36.21 126 8007. 2248. 46 PEW 3000 3000 1.1 600 7. 07 37.69 129 8007. 2245. 33 EBS-wax 600 7. 16 47.42 144 If 800 7. 28 59. 20 * outside the scope of the invention PEW 655, PEW 1000, PEW 2000, and PEW 3000 are all lubricants according to the invention and are polyethyl- ene waxes.
As appears from table 3, the ejection energies are lower for the lubricants according to the invention than for the lubricant outside the scope of the invention.
Test 4 Table 4 below states a number of lubricants by indi- cating melting point peak, powder temperature, tool tem- perature and green density (GD) and ejection force (Ej. F).
The metal-powder compositions contained the follow- ing ingredients: Distaloy@AE, marketed by Hoganas AB 0.3% by weight of graphite
0.6% by weight of lubricant according to table 4.
The compaction pressure was 600 MPa.
Table 4 Lubricants in warm compaction Lubricant Melting Powder Tool GD Ej. F point temp temp g/cm2 (N/mm2) peak (C) (°C) (°C) PEW 3000 129 110 110 7.28 20.5 ""110 120 7.29 21.3 *Lubricant X1 176 150 150 7.22 15.0 * Lubricant X1 is a lubricant according to PCT/E95/00636, which essentially consists of an oligomer of amide type with a weight-average molecular weight, Mw, of 18 000.
As appears from table 4, the green density (GD) is slightly higher with the lubricant according to the in- vention. The ejection force is higher with the lubricant according to the invention, but is still low enough to be acceptable.
Compared to the material containing EBS-wax or lubricant Xl, the materials admixed with lubricants according to the invention give comparable green density (GD) and ejection forces (Ej. F).
When a cold compacted body, where the material was admixed with lubricants according to the invention, is heat treated before sintering, it gains an enhanced green strength as compared to a material admixed with EBS-wax.
The enhanced green strength makes it possible to process and handle the compacted body before sintering without cracking or being otherwise damaged.