EP0175934B1 - Alliage d'inoculation à base de ferrosilicium ou de silicium et procédé de fabrication - Google Patents
Alliage d'inoculation à base de ferrosilicium ou de silicium et procédé de fabrication Download PDFInfo
- Publication number
- EP0175934B1 EP0175934B1 EP85110607A EP85110607A EP0175934B1 EP 0175934 B1 EP0175934 B1 EP 0175934B1 EP 85110607 A EP85110607 A EP 85110607A EP 85110607 A EP85110607 A EP 85110607A EP 0175934 B1 EP0175934 B1 EP 0175934B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- barium
- alloy
- zirconium
- silicon
- seeding
- 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
- 229910045601 alloy Inorganic materials 0.000 title claims description 39
- 239000000956 alloy Substances 0.000 title claims description 39
- 229910000519 Ferrosilicon Inorganic materials 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 12
- 229910052710 silicon Inorganic materials 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000010703 silicon Substances 0.000 title claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 31
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 28
- 239000011575 calcium Substances 0.000 claims description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 17
- 229910052726 zirconium Inorganic materials 0.000 claims description 17
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 229910001018 Cast iron Inorganic materials 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 150000003755 zirconium compounds Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000005997 Calcium carbide Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- -1 oxide Chemical compound 0.000 claims description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims 8
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 239000000523 sample Substances 0.000 description 31
- 238000011081 inoculation Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000006698 induction Effects 0.000 description 6
- 229910005347 FeSi Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000029142 excretion Effects 0.000 description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002054 inoculum Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 101150006573 PAN1 gene Proteins 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 229910014813 CaC2 Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005438 FeTi Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229960005486 vaccine Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
- C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys
Definitions
- the present invention relates to an inoculation alloy based on ferrosilicon or silicon for the production of cast iron with lamellar, compact or spheroidal graphite and a method for the production thereof.
- cast iron contains carbon in an amount of approximately 2 to 4% as the main alloying element.
- certain modification alloy such.
- B. Magnesium succeeds in converting the carbon into compact or spherical graphite. This graphite, which is available in various forms, has a very strong effect on the strength, toughness and thermal conductivity of cast iron. To improve these properties, it is known to additionally use inoculation alloys which act as nucleating agents.
- the freely excreted intermetallic compound Fe 3 C also referred to as carbide or cementite, is preferably formed, which has an increased disadvantageous effect on the properties of the cast iron.
- the actual vaccine-active substances such.
- B. Ca, Al, Mg, Zr or Ba are contained in most known seed alloys in ferrosilicon.
- the calcium content is 1 to 3% and the aluminum content 1 to 2%, since calcium and aluminum have a positive effect on the effect of the other elements.
- ferro-silicon-based inoculant alloys which contain strontium in an amount of 1 to 4% as the vaccine substance.
- US Pat. No. 3,272,623 discloses ferro-silicon-based inoculation alloys which, in addition to barium, zirconium, aluminum and 0.5 to 4% calcium, also contain 2 to 7% manganese.
- the invention has for its object to provide an inoculation alloy based on ferrosilicon or silicon for the production of cast iron with lamellar, compact or spheroidal graphite, which does not have the mentioned disadvantages of the known inoculation alloys or has them to a lesser extent.
- the inoculation alloy according to the invention effectively suppresses carbide excretion, although the aluminum and calcium content is very low. This was unpredictable because it was previously assumed that aluminum and calcium had a positive effect on the elements barium and zirconium.
- the content of barium and / or zirconium is preferably 0.4 to 1.5%. With a content of less than 0.1% of these elements, the effect of the alloy deteriorates very strongly, while above 10% no further improvement is detectable. It is essential for the invention that the contents of aluminum and calcium are as low as possible.
- the aluminum content is preferably below 1.0%, while the calcium content is preferably below 0.1%.
- the alloying constituents barium and / or zirconium do not necessarily have to be present in the alloy in metallic form, but they can also be partially present in non-metallic, for example oxidic, form without negative results being ascertained with regard to the nucleating effect.
- non-metallic barium and / or zirconium compounds introduced into the ferrosilicon or silicon melt are caused by the presence of metallic reducing agents such as e.g. B. calcium and aluminum is reduced, but the majority of these compounds will still be in non-metallic form in the alloy.
- all compounds of these elements are suitable as barium or zirconium compounds.
- Oxygen-containing compounds of barium and zirconium have proven to be particularly advantageous, the carbonate, oxide, hydroxide or sulfate being used in particular.
- the amount of the compounds used depends solely on the desired barium and / or zirconium content in the alloy.
- a reducing agent is preferably used in addition to the barium or zirconium compound.
- Suitable reducing agents are the customary carbon-containing compounds such as calcium carbide or graphite as well as the metallic or metal-containing alkaline earth metal compounds such as calcium, magnesium, calcium silicon or ferrosilicon magnesium.
- the weight ratio of barium and / or zirconium compound to reducing agent depends on the desired metal content of barium or zirconium in the inoculation alloy to be produced. As a rule, the reducing agent is used in a stoichiometric or sub-stoichiometric amount.
- the content of metallic barium and / or zirconium in the alloy can be set relatively high even without a reducing agent by using a master alloy consisting preferably of 5 to 40% metallic barium and / or zirconium, which the ferrosilicon or Silicon melt is added.
- the preparation of the inoculant can be done in a conventional device such as. B. an induction furnace or downhole furnace.
- the advantages of the inoculation alloy according to the invention which is added to the cast iron in amounts of 0.05 to 1% by weight, based on the cast iron, are good nucleating properties and thus good suppression of carbide excretion and its technically simple and inexpensive production.
- the invention therefore also relates to the use of the inoculation alloy according to the invention for the production of cast iron.
- 1 t of cast iron with lamellar graphite is filled into the transport pan from the induction furnace. 250 kg are then poured into the ladle.
- FeSiSr or the FeSiBa alloy according to the invention can then be added to the pouring stream during the filling process. The amount added was 0.3 percent by weight and the iron temperature was 1400 ° C.
- the raw material was broken down to 0.8 - 10 mm and analyzed:
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Ceramic Products (AREA)
- Feed For Specific Animals (AREA)
Claims (15)
1. Alliage d'inoculation à base de ferrosilicium ou de silicium pour la préparation de fonte avec du graphite lamellaire, compact ou sphéroïdal, ayant une teneur en:
a) baryum et/ou zirconium comprise entre 0,1 et 10 %
b) aluminium, inférieure à 2,0 %, et
c) calcium, inférieure à 0,3 %.
2. Alliage d'inoculation suivant la revendication 1, caractérisé en ce que la teneur en baryum et/ou en zirconium est de 0,4 à 1,5 %.
3. Alliage d'inoculation suivant les revendications 1 et 2, caractérisé en ce que la teneur en aluminium est inférieur à 1,0 %.
4. Alliage d'inoculation suivant les revendications 1 à 3, caractérisé en ce que la teneur en calcium est inférieur à 0,1 %.
5. Alliage d'inoculation suivant les revendications 1 à 4, caractérisé en ce que le baryum et/ou le zirconium sont partiellement présents dans l'alliage sous forme non métallique.
6. Alliage d'inoculation suivant les revendications 1 à 5, caractérisé en ce que le baryum et/ou le zirconium sont présents dans l'alliage sous forme d'oxyde.
7. Procédé de préparation de l'alliage d'inoculation suivant l'une des revendications 1 à 6, caractérisé en ce qu'on introduit un composé du baryum et/ou du zirconium dans du ferrosilicium ou du silicium fondu.
8. Procédé suivant la revendication 7, caractérisé en ce qu'on utilise comme composés du baryum et/ou du zirconium, des composés oxygénés de ces éléments.
9. Procédé suivant la revendication 8, caractérisé en ce qu'on utilise comme composés oxygénés le carbonate, l'oxyde, l'hydroxyde ou le sulfate.
10. Procédé suivant la revendication 7, caractérisé en ce qu'on utilise comme composés du baryum et/ou du zirconium, un préalliage qui contient 5 à 40 % de baryum et/ou de zirconium.
11. Procédé suivant l'une des revendications 7 à 9, caractérisé en ce qu'on introduit le composé du baryum et/ou du zirconium en même temps qu'un réducteur dans la masse fondue.
12. Procédé suivant la revendication 11, caractérisé en ce qu'on utilise comme réducteur des composés carbonés tels que le carbure de calcium ou le graphite.
13. Procédé suivant la revendication 11, caractérisé en ce qu'on utilise comme réducteurs des composés alcalino-terreux métalliques ou contenant un métal, tels que le calcium, le magnésium, le calciumsilicium ou le ferrosiliciummagnésium.
14. Procédé suivant les revendications 12 et 13, caractérisé en ce qu'on utilise un réducteur dans une quantité stoechiométrique ou inférieure à la quantité stoechiométrique par rapport aux composés du baryum et/ ou du zirconium.
15. Utilisation de l'alliage d'inoculation suivant les revendications 1 à 6, caractérisée en ce qu'on les ajoute à une masse fondue de fonte dans une quantité de 0,05 à 1 % en poids par rapport à la quantité de fonte.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3433610 | 1984-09-13 | ||
| DE19843433610 DE3433610A1 (de) | 1984-09-13 | 1984-09-13 | Impflegierung auf basis von ferrosilicium oder silicium und verfahren zu ihrer herstellung |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0175934A1 EP0175934A1 (fr) | 1986-04-02 |
| EP0175934B1 true EP0175934B1 (fr) | 1988-06-29 |
Family
ID=6245297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85110607A Expired EP0175934B1 (fr) | 1984-09-13 | 1985-08-23 | Alliage d'inoculation à base de ferrosilicium ou de silicium et procédé de fabrication |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4643768A (fr) |
| EP (1) | EP0175934B1 (fr) |
| JP (1) | JPS6173858A (fr) |
| CA (1) | CA1238787A (fr) |
| DE (2) | DE3433610A1 (fr) |
| NO (1) | NO853547L (fr) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01136920A (ja) * | 1987-11-20 | 1989-05-30 | Hitachi Metals Ltd | 球状黒鉛鋳鉄の製造法 |
| US5002733A (en) * | 1989-07-26 | 1991-03-26 | American Alloys, Inc. | Silicon alloys containing calcium and method of making same |
| US5008074A (en) * | 1990-04-26 | 1991-04-16 | American Alloys, Inc. | Inoculant for gray cast iron |
| DE4124159C2 (de) * | 1991-07-20 | 1996-08-14 | Sueddeutsche Kalkstickstoff | Vorlegierung zur Behandlung von Gußeisenschmelzen |
| GB0614705D0 (en) * | 2006-07-25 | 2006-09-06 | Foseco Int | Improved meethod of producing ductile iron |
| CN107012384B (zh) * | 2016-01-27 | 2018-05-29 | 鞍钢股份有限公司 | 一种硅钢用高纯度低碳硅铁及其冶炼方法 |
| CN113278756A (zh) * | 2021-04-19 | 2021-08-20 | 成都宏源铸造材料有限公司 | 一种铸铁用硅系孕育剂的制备方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490818A (en) * | 1947-08-28 | 1949-12-13 | Kuniansky Max | Cast-iron pipe |
| US2676097A (en) * | 1951-03-08 | 1954-04-20 | Vanadium Corp Of America | Composition for addition to cast iron or steel |
| US2750284A (en) * | 1951-12-22 | 1956-06-12 | Allis Chalmers Mfg Co | Process for producing nodular graphite iron |
| US3151975A (en) * | 1960-05-04 | 1964-10-06 | Julius D Madaras | Process for treating molten ferrous metal |
| US3137570A (en) * | 1962-08-10 | 1964-06-16 | Vanadium Corp Of America | Inoculating alloy |
| GB1002107A (en) * | 1962-08-31 | 1965-08-25 | British Cast Iron Res Ass | Improvements in the manufacture of cast irons |
| US3272623A (en) * | 1963-10-28 | 1966-09-13 | Union Carbide Corp | Inoculating alloys consisting of si-al-ca-ba-mn-zr-fe |
| SU544706A1 (ru) * | 1975-05-11 | 1977-01-30 | Институт Проблем Литья Ан Украинской Сср | Лигатура |
-
1984
- 1984-09-13 DE DE19843433610 patent/DE3433610A1/de not_active Withdrawn
-
1985
- 1985-08-23 EP EP85110607A patent/EP0175934B1/fr not_active Expired
- 1985-08-23 DE DE8585110607T patent/DE3563544D1/de not_active Expired
- 1985-09-10 US US06/774,323 patent/US4643768A/en not_active Expired - Fee Related
- 1985-09-10 CA CA000490287A patent/CA1238787A/fr not_active Expired
- 1985-09-11 JP JP60199651A patent/JPS6173858A/ja active Pending
- 1985-09-11 NO NO853547A patent/NO853547L/no unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0175934A1 (fr) | 1986-04-02 |
| NO853547L (no) | 1986-03-14 |
| CA1238787A (fr) | 1988-07-05 |
| DE3563544D1 (en) | 1988-08-04 |
| JPS6173858A (ja) | 1986-04-16 |
| US4643768A (en) | 1987-02-17 |
| DE3433610A1 (de) | 1986-03-20 |
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