EP0099015B1 - Verfahren zur Herstellung von Sinterstahl hoher Raumerfüllung durch Einfachsintertechnik - Google Patents
Verfahren zur Herstellung von Sinterstahl hoher Raumerfüllung durch Einfachsintertechnik Download PDFInfo
- Publication number
- EP0099015B1 EP0099015B1 EP83106223A EP83106223A EP0099015B1 EP 0099015 B1 EP0099015 B1 EP 0099015B1 EP 83106223 A EP83106223 A EP 83106223A EP 83106223 A EP83106223 A EP 83106223A EP 0099015 B1 EP0099015 B1 EP 0099015B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder
- layer
- graphite
- iron
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000005245 sintering Methods 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 24
- 229910000831 Steel Inorganic materials 0.000 title claims description 10
- 239000010959 steel Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 230000008569 process Effects 0.000 title description 8
- 239000000843 powder Substances 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229910045601 alloy Inorganic materials 0.000 claims description 26
- 239000000956 alloy Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 238000009792 diffusion process Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910000997 High-speed steel Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910006367 Si—P Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0264—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
- C22C33/0271—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5% with only C, Mn, Si, P, S, As as alloying elements, e.g. carbon steel
-
- 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
- C22C33/0207—Using a mixture of prealloyed powders or a master alloy
Definitions
- the invention relates to a method for producing sintered steel according to the preamble of the main claim.
- the strength properties of sintered steels are essentially determined by the space filling, apart from the composition.
- the pore shape is also important.
- Sintered steels with a space filling> 94% and rounded pores are desirable.
- the most economical way to achieve this goal is the so-called simple sintering technique, in which pressing and sintering is carried out only once.
- the simple sintering technique customary today the sintering of the powder particles takes place essentially by solid phase diffusion, it being possible for it to be supported by the appearance of liquid phases. In the case of two- or three-substance systems, this generally leads to a space filling of around 92%.
- the simple sintering technique with the appearance of liquid phases is used today in the production of components from high-speed steel powders.
- high-speed steels sintered densities of at least 97% are achieved, but the starting powders have very complicated compositions, since they consist of at least five alloy components.
- the particles of the starting powder have a completely homogeneous composition since the alloy is made before pressing and sintering.
- each powder particle is in a solid and in a liquid state of aggregation within a certain temperature range, which leads to the fact that the proportion of pores can be reduced to: g 3%, but the temperature range in which this phenomenon is used for the purpose of Compacting can be exploited by sintering, with 2 to 3 ° C very narrow, which places very high demands on the temperature constancy during the sintering process and is one of the reasons why the sintering process for the high-speed steel powders has to be carried out in a vacuum.
- DE-A-2 625 212 describes a process whose aim is to produce sintered steels with good mechanical properties, the sintering temperature being intended to be as low as possible. For optimal use of the alloying elements, they should be distributed as homogeneously as possible. This goal is achieved by liquid phase sintering with the help of carbon, because diffusion goes much faster over a liquid phase than over a solid phase.
- One difficulty is that a high carbon content of approximately 4% is required because of the desired low sintering temperatures, which would lead to a powder which is difficult to press. Therefore, two different powders are used, which have a different carbon content.
- powder 1 is a atomized, pre-alloyed powder made of iron with other alloy components such as manganese, molybdenum, chromium and nickel and with 4.3 to 4.5% carbon. So this is a hypereutectic alloy.
- the powder 2 which is present in the mixture in at least nine times the amount, is an atomized pre-alloyed powder which contains only 0.1 to 0.8% by weight of carbon and thus largely determines the properties of the powder mixture.
- This powder mixture is then pressed to press densities of, for example, 6.7 g / cm 3 . If this pressed part is now heated for sintering, the carbon-rich phase would lose carbon during the 10 to 20 minute heating, since this readily diffuses away from the surface of the corresponding particles.
- a coating for example made of copper, with a thickness of 0.01 to 200 ⁇ m is placed around the particles of the powder 1 in order to prevent the diffusion of the carbon from the inside of the particle to the outside.
- This also applies just above the melting point of copper, namely 1082 ° C; at the sintering temperature of about 1120 to 1150 ° C, which corresponds approximately to the eutectic temperature of powder 1, the powder 1 is partially liquefied, and the alloying elements including the carbon quickly diffuse out of the powder 1 into the powder 2, since the copper jacket is now destroyed diffusion is no longer slowed down.
- the individual particles of powder 1 are completely homogeneous in themselves, so that above the sintering temperature, ie between the solidus and the liquidus curve, the particles of powder 1 in the copper shell are completely in a two-phase form, namely solid and liquid .
- the copper does not serve as an alloy component here, but only as a diffusion barrier for the carbon of the carbon-rich particles, as long as the copper is still solid.
- the method according to the invention with the characterizing features of the main claim has the advantage over normal sintered steels, which are generally produced by mixing the element powders as a two- or three-material system, that it enables a sintered steel to be used by simple sintering technology to fill a space> 94%. bring to.
- This is done by two-phase sealing sintering, but in the process according to the invention an inhomogeneous starting powder containing several components is used, which, without reactions of the components with one another, only during the entire sintering process is in an aggregate state.
- the two-phase state is achieved during the sintering by reactions of two or more starting components, an initially non-existing new phase being formed, which is then simultaneously present in the solid and liquid physical state.
- the distribution of these components in the compact must be such that the reactions occur at as many locations in the compact as possible during sintering. Furthermore, the two-phase state must be maintained as long as possible so that the pores can largely migrate outwards.
- the composition of the starting powder must be selected so that the component, which occurs simultaneously in the solid and in the liquid state, is available in sufficient quantities.
- the core consists of pure iron
- the alloy components e.g. silicon and phosphorus in the form of ferrosilicon and ferrophosphorus
- the temperature range during the sintering is not so critical, since a range of approximately 30 ° C. is available here.
- the sintering process does not need to be carried out in a vacuum; here, sintering is preferably carried out under hydrogen.
- the sintering temperature for high-speed steel powders is relatively high at more than 1250 ° C.
- the method according to the invention has proven particularly useful, for example, in the production of the technically interesting Fe-Si-P sintered alloy, which basically has the advantage that silicon and phosphorus are inexpensive, readily available elements which cause very little difficulty in the eventual reprocessing of sintered steel parts .
- the two-phase state occurs for alloys up to about 40% Ni above 1450 ° C.
- spherical iron powder was provided with a nickel layer by vapor deposition, the layer thickness of the nickel being chosen so that a gross content of about -5% nickel was reached.
- the powder obtained in this way was shaped at a pressure of about 7 Mp / cm 2 into a compact, which was then first tempered at 1000 ° C., so that an alloy was already formed in the boundary zone between iron and nickel. The temperature was then raised to approximately 1470 ° C.
- Fe-Si-P alloy is a technically interesting alloy.
- Fe-Si-P there are various two-phase areas that can be used for the production of high-density sintered parts.
- Iron, ferrosilicon, ferrophosphorus and graphite powders were used as starting materials. It has been shown that it is also necessary in this case to provide a diffusion brake between the iron and the alloy powders.
- the iron powder first coated with graphite powder by mixing the graphite powder with 5 cm 3 per 1000 g of iron powder of a 35% aqueous dextrin solution as a binder and applying it to the iron powder particles.
- the gross carbon content was between 0.05 and 0.3% by weight.
- this powder was subjected to a heat treatment at 700 ° C. for one hour. Then a mixture of ferrosilicon and ferrophosphorus was applied in the same way and again a heat treatment was carried out as above.
- the powder which is now in the form of a panate, in which each powder grain consists of a core which is encased in a layer of another material, was then pressed in a conventional manner and sintered in hydrogen at 1150-1180 ° C. for one hour.
- iron, ferrosilicon and ferrophosphorus powders were mixed thoroughly in the customary manner, 0.7% by weight of a synthetic wax being added as a pressing aid to some of the samples. These powder mixtures were then processed as above.
- An alloy that is particularly favorable in terms of its properties has the following composition:
- Panat or mixed powder with wax were pressed at 6.5 to 8.5 Mp / cm 2 . After sintering at 1150 ° C. for one hour in hydrogen, the sintered densities were between 7.25 and 7.40 g / c m 3 .
- the main properties of this alloy are:
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823226257 DE3226257A1 (de) | 1982-07-14 | 1982-07-14 | Verfahren zur herstellung von sinterstahl hoher raumerfuellung durch einfachsintertechnik |
| DE3226257 | 1982-07-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0099015A1 EP0099015A1 (de) | 1984-01-25 |
| EP0099015B1 true EP0099015B1 (de) | 1986-10-08 |
Family
ID=6168369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83106223A Expired EP0099015B1 (de) | 1982-07-14 | 1983-06-25 | Verfahren zur Herstellung von Sinterstahl hoher Raumerfüllung durch Einfachsintertechnik |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0099015B1 (enrdf_load_stackoverflow) |
| JP (1) | JPS5923841A (enrdf_load_stackoverflow) |
| DE (2) | DE3226257A1 (enrdf_load_stackoverflow) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839139A (en) * | 1986-02-25 | 1989-06-13 | Crucible Materials Corporation | Powder metallurgy high speed tool steel article and method of manufacture |
| DE4207255C1 (enrdf_load_stackoverflow) * | 1992-03-07 | 1993-06-24 | Ferritslev Jernwarefabrik As | |
| RU2198765C2 (ru) * | 1999-08-31 | 2003-02-20 | Государственное научное учреждение "Научный центр порошкового материаловедения Пермского государственного технического университета" | Способ изготовления деталей из порошковых сталей |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB538227A (en) * | 1939-12-12 | 1941-07-25 | William Arthur Oubridge | Improvements in or relating to the manufacture of metal articles or masses |
| US4011077A (en) * | 1975-06-06 | 1977-03-08 | Ford Motor Company | Copper coated, iron-carbon eutectic alloy powders |
| SE397780B (sv) * | 1976-06-24 | 1977-11-21 | Hoeganaes Ab | Sett for framstellning av sinterstal med hog hallfasthet och god duktivitet |
| DE2708916C2 (de) * | 1977-03-02 | 1985-07-18 | Robert Bosch Gmbh, 7000 Stuttgart | Verwendung einer hochfesten Eisen-Sinterlegierung |
| JPS545516A (en) * | 1977-06-15 | 1979-01-17 | Hitachi Ltd | Induction motor unit |
| JPS5462108A (en) * | 1977-10-27 | 1979-05-18 | Nippon Piston Ring Co Ltd | Abrasion resistant sintered alloy |
| JPS5813603B2 (ja) * | 1978-01-31 | 1983-03-15 | トヨタ自動車株式会社 | 軸部材とその嵌合部材の接合法 |
| DE2913221A1 (de) * | 1979-04-03 | 1980-10-16 | Amsted Ind Inc | Verfahren zur herstellung eines eisenbasismaterials hoher dichte |
| ATE1518T1 (de) * | 1979-06-28 | 1982-09-15 | Bernard Matthews Limited | Nahrungsmittel, seine herstellung und apparat dafuer. |
| DE3004255A1 (de) * | 1980-02-06 | 1981-08-13 | Sintermetallwerk Krebsöge GmbH, 5608 Radevormwald | Verfahren zur herstellung eines metallischen sinterformteils |
-
1982
- 1982-07-14 DE DE19823226257 patent/DE3226257A1/de not_active Withdrawn
-
1983
- 1983-06-25 DE DE8383106223T patent/DE3366712D1/de not_active Expired
- 1983-06-25 EP EP83106223A patent/EP0099015B1/de not_active Expired
- 1983-07-08 JP JP58123559A patent/JPS5923841A/ja active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3226257A1 (de) | 1984-01-19 |
| JPH0478712B2 (enrdf_load_stackoverflow) | 1992-12-11 |
| EP0099015A1 (de) | 1984-01-25 |
| DE3366712D1 (en) | 1986-11-13 |
| JPS5923841A (ja) | 1984-02-07 |
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