EP2976172B1 - Inoculant with surface particles - Google Patents
Inoculant with surface particles Download PDFInfo
- Publication number
- EP2976172B1 EP2976172B1 EP14716891.8A EP14716891A EP2976172B1 EP 2976172 B1 EP2976172 B1 EP 2976172B1 EP 14716891 A EP14716891 A EP 14716891A EP 2976172 B1 EP2976172 B1 EP 2976172B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- support particles
- mass
- iron
- calcium
- 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.)
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- 239000002245 particle Substances 0.000 title claims description 180
- 239000002054 inoculum Substances 0.000 title claims description 76
- 229910001018 Cast iron Inorganic materials 0.000 claims description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 78
- 239000010439 graphite Substances 0.000 claims description 52
- 229910002804 graphite Inorganic materials 0.000 claims description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000011230 binding agent Substances 0.000 claims description 37
- 239000011575 calcium Substances 0.000 claims description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- 229910045601 alloy Inorganic materials 0.000 claims description 27
- 239000000956 alloy Substances 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- 229910052791 calcium Inorganic materials 0.000 claims description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 229910021332 silicide Inorganic materials 0.000 claims description 10
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 230000001737 promoting effect Effects 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 150000004763 sulfides Chemical class 0.000 claims description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910021346 calcium silicide Inorganic materials 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 5
- 230000035784 germination Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 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 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 3
- AGVJBLHVMNHENQ-UHFFFAOYSA-N Calcium sulfide Chemical class [S-2].[Ca+2] AGVJBLHVMNHENQ-UHFFFAOYSA-N 0.000 claims 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 3
- 235000012255 calcium oxide Nutrition 0.000 claims 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims 2
- 238000007580 dry-mixing Methods 0.000 claims 1
- 238000013038 hand mixing Methods 0.000 claims 1
- 229920005596 polymer binder Polymers 0.000 claims 1
- 239000002491 polymer binding agent Substances 0.000 claims 1
- 238000011282 treatment Methods 0.000 description 28
- 229910005347 FeSi Inorganic materials 0.000 description 25
- 229910000859 α-Fe Inorganic materials 0.000 description 20
- 229910001567 cementite Inorganic materials 0.000 description 18
- 239000010451 perlite Substances 0.000 description 16
- 235000019362 perlite Nutrition 0.000 description 16
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 238000011049 filling Methods 0.000 description 11
- 238000005243 fluidization Methods 0.000 description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 238000005266 casting Methods 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910004709 CaSi Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000011081 inoculation Methods 0.000 description 6
- 229910001141 Ductile iron Inorganic materials 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 229910001562 pearlite Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 235000001508 sulfur Nutrition 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001060 Gray iron Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910001037 White iron Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 iron carbides Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000447437 Gerreidae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241001080024 Telles Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/10—Making spheroidal graphite cast-iron
- C21C1/105—Nodularising additive agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0037—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 by injecting powdered material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D5/00—Heat treatments of cast-iron
- C21D5/02—Heat treatments of cast-iron improving the malleability of grey cast-iron
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
- C22C37/04—Cast-iron alloys containing spheroidal graphite
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
- C22C37/06—Cast-iron alloys containing chromium
- C22C37/08—Cast-iron alloys containing chromium with nickel
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/006—Graphite
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/08—Making cast-iron alloys
Definitions
- the present invention relates to an inoculant product for the treatment of cast iron, as well as to a process for the manufacture of said inoculant.
- Cast iron is a well-known and widely used iron-carbon alloy for the manufacture of mechanical parts. Cast iron is obtained by mixing the constituents of the alloy in the liquid state at a temperature between 1135°C and 1350°C before casting in a mold and cooling the alloy obtained.
- carbon can adopt different physico-chemical structures depending on several parameters.
- White cast iron has the characteristic of being hard and brittle, which is undesirable for some applications.
- Gray cast iron is softer and can be worked.
- the liquid cast iron undergoes an inoculation treatment aimed at introducing into the cast iron graphitizing components which will promote, during the cooling of the cast iron in the mould, the appearance of graphite rather than iron carbide.
- the components of an inoculant are elements which promote the formation of graphite during the solidification of cast iron. Mention may be made, by way of example, of carbon, silicon, calcium, aluminum,
- CN102373361A describes, in the context of a process for manufacturing ductile iron, the use of a graphitizing component, coated over its entire surface with an insulating agent.
- the graphitizing component is made of ferro-silicon, magnesium and a rare earth metal, but does not contain aluminum.
- This inoculant comprises a ferro-silicon core on which titanium carbide particles and optionally nickel particles are distributed.
- DE2157395A1 describes a cast iron treatment agent consisting of a metal core, or support particle, and a coating, or surface particle, covering said core to which it adheres via a binder.
- the support particles are made of a material chosen from silicon, ferrosilicon, magnesium, tin and alloys of silicon with at least one of calcium, strontium, magnesium, iron, rare earth, zirconium, copper, nickel, tin and molybdenum.
- the coating contains the binder material and may be graphite, sulfide, sulfur, iron, pyrite, or an alloy of silicon with iron, calcium, strontium, magnesium, rare earth, copper, tin, nickel or molybdenum.
- an inoculant can also be designed to fulfill other functions and to this end comprise other components having a particular effect.
- the graphite formed may in particular be desired, depending on the desired properties, for the graphite formed to be spheroidal, vermicular or lamellar.
- One or the other graphitic form can be obtained preferentially by a particular treatment of the cast iron using specific components.
- spheroidal graphite can be favored by a so-called nodulizing treatment aimed mainly at providing the cast iron with sufficient quantity of magnesium so that the graphite can grow in such a way as to form round particles (spheroids).
- nodulizing components can be included in the inoculating alloy, for example.
- CN101608280B discloses a cast iron inoculant intended to promote the formation of type D flake graphite.
- it is a material comprising silicon (35-50%, preferably 40%), magnesium (1-4%, preferably 2%), rare earth (4-8%, preferably 6%), titanium (4-9%, preferably 7%), aluminum (1.5-3%, preferably 2 %), antimony (0.5-2%, preferably 1%), calcium (2-5%, preferably 3%), barium (1-4%, preferably 3%), and the balance in iron.
- inoculants are conventionally manufactured from a ferro-silicon alloy of the FeSi 65 or FeSi 75 type with adjustment of the chemistry according to the target composition of the inoculant. Adjustment is possible in the oven or in a ladle, with often mediocre yields depending on the elements to be added. They can also be mixtures of several alloys.
- the inoculation efficiency of the cast iron part also depends on its thickness.
- the cooling will be slower and will favor the formation of graphite.
- the cooling may be too slow and the graphite formed may lose its nodularity near the center of the part.
- the inoculant is also desirable for the inoculant to be insensitive to the basic composition of the cast iron which can vary from one batch to another (initial carbon, silicon, sulfur content, in particular, etc.) .
- the surface particles form a discontinuous coating, the support particle always having areas of contact with the cast iron.
- the surface particles may be placed on the surface of the support particles by any appropriate technique, for example by grafting, gluing, coating, subject to maintaining access for the support particle to the liquid cast iron when the inoculant is incorporated therein.
- the surface particles have a particle size smaller than that of the support particles. It has in fact been found surprisingly that such a configuration, namely a set of support particles partially coated with support particles, of a different nature, such as a different particle size, exhibited a profile of dissolution and inoculation responding to the problems mentioned.
- the difference in nature between carrier particles and support particles can further be expressed in the constituent materials of the particles, respectively.
- the support particles have low inoculant properties.
- the invention it is possible to use products with weak or moderate inoculants which can be doped by this means.
- the support particles have inoculant properties for compositions or conditions different from those for which the set of support particles and surface particles act.
- the support particles are made from silicon, the proportion of which is variable.
- the support particles may be made from carbon associated with silicon, it may be in the form of silicon carbide for example.
- the support particles contain at least 40% by mass of silicon relative to the mass of the support particles.
- the support particles are made from an alloy, more particularly ferrous.
- the support particles comprise, in particular in alloyed form, at least one addition element, in particular between 0.2 and 5% by mass for each addition element, relative to the mass of the support particles.
- the support particles comprise, in particular in alloyed form, at least one treatment element with an anti-shrinkage effect, in particular in an amount of between 0.5 and 6% by mass, relative to the mass of the support particles.
- the proportion of surface particles is between 1 and 8% by mass, preferably from 1 to 5%, relative to the mass of the inoculant.
- the surface particles are distributed in a substantially homogeneous manner on the surface of the support particles, in particular within a batch of particles.
- the surface particles, until their introduction into the cast iron, occupy between 80 and 90% of the surface of the support particles.
- the surface particles are chosen, individually or as a mixture, from aluminum, bismuth and manganese, iron, rare earth and calcium silicides, aluminum, calcium, silicon and barium oxides , sulphides of iron, calcium and rare earths, and barium sulphate.
- the invention also relates to a process for the manufacture of an inoculant of the invention.
- a first step of the method there are support particles as defined above, made of a fusible material in liquid cast iron, having a particle size varying from 0.2 to 7 mm, on the one hand, and surface particles as defined above, having a particle size such that their d50 is less than or equal to one tenth of the d50 of the support particles, on the other hand, then in a second step, the surface particles are deposited on the support particles .
- This step can be implemented by any technique well known to those skilled in the art.
- particle size varying from 0.2 to 7 mm By particle size varying from 0.2 to 7 mm, the conventional particle sizes of the field of cast iron inoculants are included, namely the particle sizes 0.2-0.5 mm, 0.4-2 mm and 2-7 mm.
- the deposition of the surface particles is carried out mechanically, by incrustation.
- the support particles and the surface particles are mixed dry, at high speed, for example from 1000 to 1500 rpm, to obtain a deposit by incrustation of the surface particles on the surface of the support particles, according to a discontinuous distribution.
- the first step there is also a binder in a solvent
- the carrier particles, surface particles and binder can be added at the same time or sequentially, in any order. For example, a preliminary mixing of the surface particles in the binder solution can be carried out, to which the support particles are then added.
- a suitable binder is advantageously chosen from organic and polymeric binders, and in particular from polyvinyl alcohol (PVA), cellulose (CMC), polyvinylpyrrolidone (PVP) and cement.
- PVA polyvinyl alcohol
- CMC cellulose
- PVP polyvinylpyrrolidone
- An inoculant according to the invention may be manufactured in the following way.
- the minimum fluidization speed is determined conventionally, then the air flow is kept substantially constant and greater than this minimum speed.
- the temperature inside the reactor is brought to about 100°C. This temperature will allow the water injected later to be eliminated.
- the particles of this alloy will form the support particles to the surface of which the inoculant particles will be fixed.
- the surface particles will be, in the present example, particles of calcium silicide CaSi and metallic aluminum, both having particle sizes less than 400 micrometers.
- the surface particles to be fixed are mixed beforehand with a binder in aqueous solution, then injected into the reactor in about 30 minutes at a temperature of 100°C.
- the assembly of surface particles, support particles and binder is fluidized and heated until the water introduced has been completely evaporated. It is possible to control the evaporation of the water by any usual method, in particular by measuring the humidity of the air leaving the reactor.
- the inoculant according to the invention is then recovered and characterized in order to evaluate the effectiveness of the coating. This characterization can be made in particular by checking with a scanning electron microscope.
- the binder used may be of the organic or polymer type, such as binders of the polyvinyl alcohol (PVA), cellulose (CMC) and polyvinylpyrrolidone (PVP) type, etc. Obviously, this list is not exhaustive.
- PVA polyvinyl alcohol
- CMC cellulose
- PVP polyvinylpyrrolidone
- the quantity of water used for the dilution of the binder obviously depends on the solubility of the latter in water and must be adapted accordingly.
- mineral binders in particular of the sodium silicate type, as well as hydraulic binders of the cement or lime type.
- binder used may depend on the inoculant materials and supports used.
- the quantity of binder used will be calculated in such a way as to best allow almost total fixation of the surface particles without manifest excess which could then degrade the final performance of the inoculant according to the invention.
- the amount of binder used will obviously depend on its tackiness and will also have to be adapted accordingly. It will be possible in particular to proceed by tests and visual verification with the aid of a scanning electron microscope in particular.
- the amount of binder used may be between 0.001 and 1% by mass of binder relative to the total mass of the particles (support particles and surface particles).
- approximately 500 kg of FeSi 70 containing 1% by mass of Al and 1.5% by mass of Ca, with a particle size of 0.2-0.5 mm are introduced into a fluidized bed reactor.
- the FeSi alloy is fluidized by air injection.
- the temperature inside the reactor is brought to 100°C.
- These particles are the support particles.
- a suspension is made with PVP and water. 8% of surface particles, containing bismuth Bi and ferro-silico-rare earth alloy FeSiTR, both of particle size ⁇ 200 ⁇ m are added to the PVP+water solution, then suspended.
- This suspension is then injected at a rate of 10% by mass into the reactor for about 40 min at a temperature of 100°C. After total injection of the mixture, the inside of the reactor is maintained at 100° C. until the product has completely dried.
- approximately 1000 kg of FeSi 70 containing 1% by mass of Al and 1.5% by mass of Ca, with a particle size of 2-7 mm and approximately 50 kg of Aluminum powder with a particle size ⁇ 300 ⁇ m are introduced into a fluidized bed reactor. All the particles are fluidized by injecting depleted air. The temperature inside the reactor is brought to 100°C. A suspension is made with PVP and water. This suspension is then injected at a rate of 10% by mass into the reactor for about 40 min at a temperature of 100°C. After complete injection of the mixture, the interior of the reactor is maintained at 100° C. until the product has completely dried.
- the implementation of the method is not limited to the use of a fluidized bed reactor and other coating techniques can be used. Mention may in particular be made of the following methods.
- a first method is the use of a high-speed mixer, for example of the order of 1000 to 1500 revolutions per minute.
- the mixing speed allows the mechanical embedding of the fine surface particles in the larger FeSi particles (carrier particles).
- Such mechanical incrustation does not require the use of a binder and we then speak of dry and cold coating.
- Support particles of the FeSi 75 type, containing mainly the FeSi 2,4 and Si phases, can be embedded directly by the surface particles.
- a second method is the use of a high shear mixer.
- the mixing is carried out at more or less high speed (between 50 and 500 revolutions per minute, for example) in a mixer of the mixer-granulator type, in the presence of a binder (examples cited above).
- a drying step is carried out to remove the water from the binder.
- Means of drying can equip the mixer. It may in particular be a burner ramp, for example gas, heating the outside of the mixer by conduction; a heating mat, for example made of silicone, surrounding in particular the walls of the mixer; or even any other system making it possible to bring the powder inside the mixer to a temperature of between 80 and 150° C. in order to eliminate the water.
- a burner ramp for example gas
- a heating mat for example made of silicone
- the mixer systems used, of the drum or granulator type, must allow movement of the powder inside said mixer resulting in effective mixing and a certain regularity of the bonding.
- the mixer can be equipped with stirring fins on its walls or else a mixer-granulator with a central or offset rotation system along one or two axes.
- the method of the invention can be carried out either continuously or discontinuously in batches (batch).
- the support and surface particles can be added either together or separately.
- they When they are added together, they may advantageously be pre-mixed, before adding the binder to ensure bonding.
- the carrier particles When they are added separately, the carrier particles will preferably be introduced first before adding the surface particles, preferably continuously, the binder also being preferably introduced continuously.
- support particles based on FeSi it is of course possible to use other materials conventionally used in foundry, and in particular support particles of the SiC or graphite type. It is appropriate to simply transpose the manufacturing examples to these materials.
- inoculants according to the invention comprising other types of support particles such as silicon carbide or graphite, these materials being however used less frequently in foundries.
- a cast iron bath with spheroidal graphite was treated at a rate of 0.3% by weight with an inoculant alloy of the FeSi 75 type, and containing 0.8% by mass of aluminum and 0.7% by mass of calcium.
- the treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
- the residual magnesium of the cast iron is 400 thousandths.
- the cast iron was then poured into a BCIRA type mould.
- Example 2 inoculant according to the invention
- the treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
- the carbon equivalent amount of cast iron (Ceq) is 4.32%.
- the residual magnesium of the cast iron is 400 thousandths.
- the cast iron was then poured into a BCIRA type mould.
- Example 3 inoculant according to the invention
- the treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
- the amount of carbon equivalent (Ceq) of cast iron is 4.32%. Residual magnesium is 420 thousandths.
- the cast iron is cast in a BCIRA mould.
- a cast iron bath with spheroidal graphite was treated at a rate of 0.3% by mass with an inoculant conventionally prepared of the FeSi 75 type, and containing 1.2% by mass of aluminum, 1.5% by mass of calcium and 1.5% by weight of zirconium.
- the treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
- the carbon equivalent amount of cast iron (Ceq) is 4.32%.
- the residual magnesium of the cast iron is 400 thousandths.
- the cast iron was then poured into a BCIRA type mould.
- the treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
- the carbon equivalent amount of cast iron (Ceq) is 4.3%.
- the cast iron is cast in a BCIRA mould.
- Example 6 inoculant according to the invention
- the treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
- the carbon equivalent amount of cast iron (Ceq) is 4.3%.
- the cast iron is cast in a BCIRA mould.
- the treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
- the carbon equivalent amount of cast iron (Ceq) is 4.3%.
- the cast iron is cast in a BCIRA mould.
- Example 8 Pieces of different thicknesses - inoculant according to the invention
- the treatment is carried out by adding the inoculant to the jet when filling the mould.
- the carbon equivalent amount of cast iron (Ceq) is 4.32%.
- the cast iron is then poured into a mold to make a piece with different thicknesses: 4 mm and 25 mm.
- the treatment is carried out by adding the inoculant to the jet when filling the mould.
- the carbon equivalent amount of cast iron (Ceq) is 4.31%.
- the cast iron is then poured into a mold to make a piece with different thicknesses: 4 mm and 25 mm.
- Example 10 Very thick parts - inoculant according to the invention
- the treatment is carried out by adding the inoculant in the casting basin during the filling of the mould.
- the carbon equivalent amount of cast iron (Ceq) is 4.33%.
- the cast iron is then poured into a mold to make a very thick part (170mm).
- the treatment is carried out by adding the inoculant in the casting basin during the filling of the mould.
- the carbon equivalent amount of cast iron (Ceq) is 4.31%.
- the cast iron is then poured into a mold to make a very thick part: 170 mm.
Description
La présente invention se rapporte à un produit inoculant pour le traitement de la fonte, ainsi qu'à un procédé de fabrication dudit inoculant.The present invention relates to an inoculant product for the treatment of cast iron, as well as to a process for the manufacture of said inoculant.
La fonte est un alliage fer-carbone bien connu et largement utilisé pour la fabrication de pièces mécaniques. La fonte est obtenue par mélange des constituants de l'alliage à l'état liquide à une température comprise entre 1135°C et 1350°C avant coulée dans un moule et refroidissement de l'alliage obtenu.Cast iron is a well-known and widely used iron-carbon alloy for the manufacture of mechanical parts. Cast iron is obtained by mixing the constituents of the alloy in the liquid state at a temperature between 1135°C and 1350°C before casting in a mold and cooling the alloy obtained.
Lors de son refroidissement, le carbone peut adopter différentes structures physico-chimiques dépendant de plusieurs paramètres.During its cooling, carbon can adopt different physico-chemical structures depending on several parameters.
Lorsque le carbone s'associe au fer et forme du carbure de fer FesC (également appelé cémentite), la fonte résultante est appelée fonte blanche. La fonte blanche présente la caractéristique d'être dure et cassante, ce qui n'est pas souhaitable pour certaines applications.When carbon combines with iron and forms iron carbide FesC (also called cementite), the resulting iron is called white iron. White cast iron has the characteristic of being hard and brittle, which is undesirable for some applications.
Si le carbone apparaît sous forme de graphite, la fonte résultante est appelée fonte grise. La fonte grise est plus tendre et peut être travaillée.If the carbon appears as graphite, the resulting iron is called gray iron. Gray cast iron is softer and can be worked.
Pour obtenir des pièces en fonte possédant de bonnes propriétés mécaniques, il faut donc obtenir une structure de la fonte comprenant le maximum de carbone sous forme graphite et limiter le plus possible la formation de ces carbures de fer qui durcissent et fragilisent l'alliage.To obtain cast iron parts having good mechanical properties, it is therefore necessary to obtain a structure of the cast iron comprising the maximum amount of carbon in graphite form and to limit as much as possible the formation of these iron carbides which harden and embrittle the alloy.
En l'absence de tout traitement particulier, le carbone a toutefois tendance à s'associer au fer pour former du carbure de fer.In the absence of any particular treatment, however, carbon tends to combine with iron to form iron carbide.
Il est donc nécessaire de traiter la fonte à l'état liquide de manière à modifier les paramètres d'association du carbone et obtenir la structure souhaitée.It is therefore necessary to treat the cast iron in the liquid state so as to modify the carbon association parameters and obtain the desired structure.
A cette fin, la fonte liquide subit un traitement d'inoculation visant à introduire dans la fonte des composants graphitisants qui vont favoriser, lors du refroidissement de la fonte dans le moule, l'apparition de graphite plutôt que de carbure de fer.To this end, the liquid cast iron undergoes an inoculation treatment aimed at introducing into the cast iron graphitizing components which will promote, during the cooling of the cast iron in the mould, the appearance of graphite rather than iron carbide.
De manière générale, les composants d'un inoculant sont des éléments favorisant la formation de graphite pendant la solidification de la fonte. On peut citer, à titre d'exemple, le carbone, le silicium, le calcium, l'aluminium,In general, the components of an inoculant are elements which promote the formation of graphite during the solidification of cast iron. Mention may be made, by way of example, of carbon, silicon, calcium, aluminum,
Ainsi,
Bien évidemment, un inoculant peut être également conçu pour remplir d'autres fonctions et comprendre à cette fin d'autres composants présentant un effet particulier.Of course, an inoculant can also be designed to fulfill other functions and to this end comprise other components having a particular effect.
On peut notamment souhaiter, selon les propriétés recherchées, que le graphite formé soit sphéroïdal, vermiculaire ou lamellaire. L'une ou l'autre forme graphitique pourra être obtenue de manière préférentielle par un traitement particulier de la fonte à l'aide de composants spécifiques.It may in particular be desired, depending on the desired properties, for the graphite formed to be spheroidal, vermicular or lamellar. One or the other graphitic form can be obtained preferentially by a particular treatment of the cast iron using specific components.
Par exemple, la formation de graphite sphéroïdal peut être favorisée par un traitement dit nodulisant visant principalement à apporter à la fonte du magnésium en quantité suffisante pour que le graphite puisse croître de manière à former des particules rondes (sphéroïdes).For example, the formation of spheroidal graphite can be favored by a so-called nodulizing treatment aimed mainly at providing the cast iron with sufficient quantity of magnesium so that the graphite can grow in such a way as to form round particles (spheroids).
Ces composants nodulisants peuvent être inclus dans l'alliage inoculant, par exemple.These nodulizing components can be included in the inoculating alloy, for example.
Ainsi,
On peut encore citer l'addition de produits désulfurants, ou de produits permettant de traiter spécifiquement certains défauts de la fonte en fonction de la composition initiale du bain de fonte liquide, tels que les micro retassures, susceptibles d'apparaître lors du refroidissement. Il pourra notamment s'agir de lanthane et de terres rares.Mention may also be made of the addition of desulfurizing products, or of products making it possible to specifically treat certain cast iron defects depending on the initial composition of the liquid cast iron bath, such as micro shrinkage, likely to appear during cooling. It may in particular be lanthanum and rare earths.
Ces traitements peuvent s'effectuer en une ou plusieurs fois et à différents moments de la fabrication de la fonte. On connaît notamment des ajouts d'inoculant dans la poche, avant la coulée de la fonte dans le moule (inoculation en poche), pendant la coulée, ou encore dans le jet de coulée (inoculation tardive).These treatments can be carried out once or several times and at different times during the manufacture of the cast iron. In particular, additions of inoculant are known in the ladle, before the cast iron is poured into the mold (ladle inoculation), during casting, or even in the casting jet (late inoculation).
La plupart des inoculants sont classiquement fabriqués à partir d'un alliage ferro-silicium de type FeSi65 ou FeSi75 avec ajustement de la chimie suivant la composition visée de l'inoculant. L'ajustement est possible en four ou en poche, avec des rendements souvent médiocres selon les éléments à ajouter. Il peut également s'agir de mélanges de plusieurs alliages.Most inoculants are conventionally manufactured from a ferro-silicon alloy of the FeSi 65 or FeSi 75 type with adjustment of the chemistry according to the target composition of the inoculant. Adjustment is possible in the oven or in a ladle, with often mediocre yields depending on the elements to be added. They can also be mixtures of several alloys.
Il convient de noter que l'efficacité d'inoculation de la pièce en fonte dépend également de son épaisseur.It should be noted that the inoculation efficiency of the cast iron part also depends on its thickness.
Dans les zones de faibles épaisseurs, refroidissant plus vite, on notera un risque plus élevé de formation de carbures.In areas of low thickness, cooling faster, there is a higher risk of carbide formation.
Inversement, dans les zones de plus fortes épaisseurs, le refroidissement sera plus lent et favorisera la formation de graphite. Toutefois, dans les pièces de fortes épaisseurs, le refroidissement peut être trop lent et le graphite formé peut perdre sa nodularité au voisinage du centre de la pièce.Conversely, in the thicker zones, the cooling will be slower and will favor the formation of graphite. However, in very thick parts, the cooling may be too slow and the graphite formed may lose its nodularity near the center of the part.
Il s'ensuit que les pièces avec des zones d'épaisseur différentes pourront avoir des structures physico-chimiques différentes d'une zone à l'autre, ce qui n'est pas souhaitable.It follows that the parts with zones of different thickness may have different physico-chemical structures from one zone to another, which is not desirable.
Il existe donc un besoin pour un inoculant permettant d'inoculer des pièces en fonte de différentes épaisseurs en limitant le risque de dégénérescence du graphite et la formation de carbures, et d'assurer une bonne uniformité de la structure métallurgique d'une zone de la pièce à l'autre.There is therefore a need for an inoculant making it possible to inoculate cast iron parts of different thicknesses while limiting the risk of degeneration of the graphite and the formation of carbides, and ensuring good uniformity of the metallurgical structure of a zone of the room to another.
Par ailleurs, il est également souhaitable que l'inoculant soit peu sensible à la composition de base de la fonte qui peut varier d'un lot à l'autre (taux de carbone, silicium, soufre initiaux, notamment, etc ...).Furthermore, it is also desirable for the inoculant to be insensitive to the basic composition of the cast iron which can vary from one batch to another (initial carbon, silicon, sulfur content, in particular, etc.) .
De plus, il reste bien évidemment souhaitable qu'un tel inoculant ne nécessite pas un taux d'addition supérieur aux produits connus et qu'il conserve des bonnes propriétés de dissolution dans la fonte, similaires à ces produits et ne génère pas sensiblement plus de crasses et laitiers que ces derniers.In addition, it obviously remains desirable that such an inoculant does not require a higher addition rate than the known products and that it retains good dissolution properties in cast iron, similar to these products and does not generate significantly more dross and slag than the latter.
Pour ce faire, la présente invention vise à proposer un nouveau produit inoculant pour le traitement de la fonte en phase liquide, répondant à tout ou partie de ces contraintes. A cet effet, elle apporte un inoculant particulaire, en poudre, comprenant,
- d'une part, des particules support en un matériau fusible dans la fonte liquide liquide favorisant l'association du carbone au fer sous forme de graphite et comprenant au moins un alliage ferro-silicium, de l'aluminium et du calcium, où le silicium est présent en une teneur d'au moins 40% en masse par rapport à la masse desdites particules support et l'aluminium et le calcium sont présents, sous forme alliée, chacun en une teneur de 0,2 à 5% en masse par rapport à la masse desdites particules support, et
- d'autre part, des particules de surface en un matériau favorisant la germination et la croissance de graphite, choisi, individuellement ou en mélange, parmi des éléments métalliques, des siliciures, des oxydes, des sulfures métalliques, des sulfates et le noir de carbone, le matériau des particules de surface étant différent du matériau des particules support, lesdites particules de surface étant disposées et réparties de manière discontinue à la surface des particules support, les particules de surface présentant une granulométrie inférieure à celle des particules support et telle que leur d50 est inférieur ou égal à un dixième du d50 des particules support.
- on the one hand, support particles in a fusible material in the liquid liquid cast iron favoring the association of carbon with iron in the form of graphite and comprising at least one ferro-silicon alloy, aluminum and calcium, where the silicon is present in a content of at least 40% by mass relative to the mass of said support particles and the aluminum and the calcium are present, in alloyed form, each in a content of 0.2 to 5% by mass relative to the mass of said support particles, and
- on the other hand, surface particles of a material promoting the germination and growth of graphite, chosen, individually or as a mixture, from metallic elements, silicides, oxides, metallic sulphides, sulphates and carbon black , the material of the surface particles being different from the material of the support particles, said surface particles being arranged and distributed in a discontinuous manner on the surface of the support particles, the surface particles having a particle size smaller than that of the support particles and such that their d50 is less than or equal to one tenth of the d50 of the support particles.
Ainsi disposées, les particules de surface forment un enrobage discontinu, la particule support présentant toujours des zones de contact avec la fonte.Arranged in this way, the surface particles form a discontinuous coating, the support particle always having areas of contact with the cast iron.
Les particules de surface pourront être disposées à la surface des particules support par toute technique appropriée, par exemple par greffage, collage, enrobage, sous réserve de conserver pour la particule support des accès à la fonte liquide lorsque l'inoculant y est incorporé.The surface particles may be placed on the surface of the support particles by any appropriate technique, for example by grafting, gluing, coating, subject to maintaining access for the support particle to the liquid cast iron when the inoculant is incorporated therein.
Comme indiqué précédemment, les particules de surface ont une granulométrie inférieure à celle des particules support. Il a en effet été constaté de manière surprenante qu'une telle configuration, à savoir un ensemble de particules support partiellement revêtues de particules de support, d'une nature différente, telle qu'une granulométrie différente, présentait un profil de dissolution et d'inoculation répondant aux problèmes évoqués. La différence de nature entre les particules support et les particules de support peut en outre s'exprimer dans les matériaux constitutifs des particules, respectivement.As indicated previously, the surface particles have a particle size smaller than that of the support particles. It has in fact been found surprisingly that such a configuration, namely a set of support particles partially coated with support particles, of a different nature, such as a different particle size, exhibited a profile of dissolution and inoculation responding to the problems mentioned. The difference in nature between carrier particles and support particles can further be expressed in the constituent materials of the particles, respectively.
Il a notamment été constaté qu'une telle structure physico chimique limitait fortement la dégénération du graphite au centre de pièces de fortes épaisseurs. Une telle structure permet également d'améliorer fortement l'homogénéité de l'inoculation, et plus particulièrement pour les pièces présentant des zones d'épaisseurs variables.It has in particular been observed that such a physico-chemical structure strongly limits the degeneration of the graphite at the center of very thick parts. Such a structure also makes it possible to greatly improve the homogeneity of the inoculation, and more particularly for the parts having zones of variable thickness.
Par ailleurs, par rapport à une technique de fabrication classique en alliage au four, étant donné que l'effet inoculant est apporté par l'ensemble particules support / particules disposées en surface et non par ajustement de la composition chimique d'un alliage, les rendements d'incorporation des éléments additionnés en sont grandement améliorés.Furthermore, compared to a conventional manufacturing technique using a furnace alloy, given that the inoculant effect is provided by the set of support particles/particles arranged on the surface and not by adjusting the chemical composition of an alloy, the incorporation yields of the added elements are greatly improved.
Selon un premier mode de réalisation, les particules support possèdent des propriétés peu inoculantes. Ainsi, grâce à l'invention, on pourra utiliser des produits faiblement ou moyennement inoculants que l'on pourra doper par ce moyen.According to a first embodiment, the support particles have low inoculant properties. Thus, thanks to the invention, it is possible to use products with weak or moderate inoculants which can be doped by this means.
Selon un deuxième mode de réalisation, les particules support possèdent des propriétés inoculantes pour des compositions ou conditions différentes de celles pour lesquelles l'ensemble particules de support et particules de surface agissent.According to a second embodiment, the support particles have inoculant properties for compositions or conditions different from those for which the set of support particles and surface particles act.
Avantageusement, les particules support sont réalisées à partir de silicium, dont la proportion est variable.Advantageously, the support particles are made from silicon, the proportion of which is variable.
De manière complémentaire ou alternative, les particules support pourront être réalisées à partir de carbone associé au silicium, il peut se présenter sous la forme de carbure de silicium par exemple.In a complementary or alternative manner, the support particles may be made from carbon associated with silicon, it may be in the form of silicon carbide for example.
Les particules support contiennent au moins 40 % en masse de silicium par rapport à la masse des particules support.The support particles contain at least 40% by mass of silicon relative to the mass of the support particles.
Les particules support sont réalisées à partir d'un alliage, plus particulièrement ferreux.The support particles are made from an alloy, more particularly ferrous.
De manière avantageuse, les particules support comprennent, notamment sous forme alliée, au moins un élément d'addition, notamment entre 0,2 et 5 % en masse pour chaque élément d'addition, par rapport à la masse des particules support.Advantageously, the support particles comprise, in particular in alloyed form, at least one addition element, in particular between 0.2 and 5% by mass for each addition element, relative to the mass of the support particles.
De manière avantageuse encore, les particules support comprennent, notamment sous forme alliée, au moins un élément de traitement à effet anti-retassure notamment en une quantité comprise entre 0,5 et 6 % en masse, par rapport à la masse des particules support.Also advantageously, the support particles comprise, in particular in alloyed form, at least one treatment element with an anti-shrinkage effect, in particular in an amount of between 0.5 and 6% by mass, relative to the mass of the support particles.
Préférentiellement, la proportion de particules de surface est comprise en 1 et 8 % en masse, de préférence de 1 à 5 %, par rapport à la masse de l'inoculant.Preferably, the proportion of surface particles is between 1 and 8% by mass, preferably from 1 to 5%, relative to the mass of the inoculant.
Avantageusement, les particules de surface sont réparties de manière sensiblement homogène à la surface des particules support, notamment au sein d'un lot de particules.Advantageously, the surface particles are distributed in a substantially homogeneous manner on the surface of the support particles, in particular within a batch of particles.
De manière préférentielle, les particules de surface, jusqu'à l'introduction dans la fonte, occupent entre 80 et 90 % de la surface des particules support.Preferably, the surface particles, until their introduction into the cast iron, occupy between 80 and 90% of the surface of the support particles.
Avantageusement, les particules de surface sont choisies, individuellement ou en mélange, parmil'aluminium, le bismuth et le manganèse, les siliciures de fer, de terres rares et de calcium, les oxydes d'aluminium, de calcium, de silicium et de baryum, les sulfures de fer, de calcium et de terres rares, et le sulfate de baryum.Advantageously, the surface particles are chosen, individually or as a mixture, from aluminum, bismuth and manganese, iron, rare earth and calcium silicides, aluminum, calcium, silicon and barium oxides , sulphides of iron, calcium and rare earths, and barium sulphate.
L'invention concerne aussi un procédé de fabrication d'un inoculant de l'invention. Selon une première étape du procédé, on dispose de particules support telles que définies ci-dessus, en un matériau fusible dans la fonte liquide, présentant une granulométrie variant de 0,2 à 7 mm, d'une part, et de particules de surface telles que définies ci-dessus, présentant une granulométrie telle que leur d50 est inférieur ou égal à un dixième du d50 des particules support, d'autre part, puis dans une seconde étape on procède au dépôt des particules de surface sur les particules de support. Cette étape peut être mise en oeuvre par toute technique bien connue de l'homme du métier.The invention also relates to a process for the manufacture of an inoculant of the invention. According to a first step of the method, there are support particles as defined above, made of a fusible material in liquid cast iron, having a particle size varying from 0.2 to 7 mm, on the one hand, and surface particles as defined above, having a particle size such that their d50 is less than or equal to one tenth of the d50 of the support particles, on the other hand, then in a second step, the surface particles are deposited on the support particles . This step can be implemented by any technique well known to those skilled in the art.
Par granulométrie variant de 0,2 à 7 mm, on inclut les granulométries classiques du domaine des inoculants de la fonte, à savoir les granulométries 0,2-0,5 mm, 0,4-2 mm et 2-7 mm.By particle size varying from 0.2 to 7 mm, the conventional particle sizes of the field of cast iron inoculants are included, namely the particle sizes 0.2-0.5 mm, 0.4-2 mm and 2-7 mm.
Dans une variante de l'invention, le dépôt des particules de surface est réalisé mécaniquement, par incrustation. A cet effet, on mélange les particules support et les particules de surface, à sec, à grande vitesse, par exemple de 1000 à 1500 tours/min, pour obtenir un dépôt par incrustation des particules de surface à la surface des particules support, selon une répartition discontinue.In a variant of the invention, the deposition of the surface particles is carried out mechanically, by incrustation. To this end, the support particles and the surface particles are mixed dry, at high speed, for example from 1000 to 1500 rpm, to obtain a deposit by incrustation of the surface particles on the surface of the support particles, according to a discontinuous distribution.
Dans une autre variante de l'invention, à la première étape, on dispose en outre d'un liant dans un solvant, puis à la seconde étape, on mélange les particules support, les particules de surface et le liant, puis on élimine le solvant du liant, par exemple par évaporation. Comme il sera décrit plus en détail, les particules de support, les particules de surface et le liant peuvent être ajoutés en même temps ou successivement, dans quelque ordre que ce soit. Par exemple, un mélange préalable des particules de surface dans la solution de liant peut être effectué, auquel sont ensuite ajoutées les particules support.In another variant of the invention, in the first step, there is also a binder in a solvent, then in the second step, mixing the support particles, the surface particles and the binder, then the solvent is removed from the binder, for example by evaporation. As will be described in more detail, the carrier particles, surface particles and binder can be added at the same time or sequentially, in any order. For example, a preliminary mixing of the surface particles in the binder solution can be carried out, to which the support particles are then added.
Un liant approprié est avantageusement choisi parmi les liants organiques et polymères, et notamment, parmi l'alcool polyvinylique (APV), la cellulose (CMC), la polyvinylpyrrolidone (PVP) et le ciment.A suitable binder is advantageously chosen from organic and polymeric binders, and in particular from polyvinyl alcohol (PVA), cellulose (CMC), polyvinylpyrrolidone (PVP) and cement.
La présente invention sera mieux comprise à la lumière de la description détaillée et des exemples de mises en oeuvre qui suivent en regard du dessin annexé dans lequel :
- la
figure 1 est une vue d'ensemble au microscope électronique à balayage d'un lot d'inoculant particulaire selon l'invention comprenant des particules support (noires) à la surface desquelles sont fixées des particules de surface (blanches) conférant à l'ensemble un fort pouvoir inoculant. - la
figure 2 est un zoom de lafigure 1 sur une particule inoculante selon l'invention.
- the
figure 1 is an overall view under a scanning electron microscope of a batch of particulate inoculant according to the invention comprising support particles (black) to the surface of which are fixed surface particles (white) giving the whole a strong inoculating power. - the
figure 2 is a zoom of thefigure 1 on an inoculant particle according to the invention.
Un inoculant selon l'invention pourra être fabriqué de la manière suivante.An inoculant according to the invention may be manufactured in the following way.
Environ 500 kilogrammes d'un alliage FeSi contenant 1 % en masse d'aluminium et 1,5 % en masse de calcium et possédant une granulométrie comprise entre 0,4 et 2 mm sont introduits dans un réacteur en lit fluidisé, l'alliage FeSi étant mis en fluidisation par injection d'air.About 500 kilograms of an FeSi alloy containing 1% by mass of aluminum and 1.5% by mass of calcium and having a particle size between 0.4 and 2 mm are introduced into a fluidized bed reactor, the FeSi alloy being fluidized by air injection.
La vitesse minimale de fluidisation est déterminée classiquement, puis le débit d'air est maintenu sensiblement constant et supérieur à cette vitesse minimale.The minimum fluidization speed is determined conventionally, then the air flow is kept substantially constant and greater than this minimum speed.
La température à l'intérieur du réacteur est portée à environ 100°C. Cette température permettra à l'eau injectée ultérieurement d'être éliminée.The temperature inside the reactor is brought to about 100°C. This temperature will allow the water injected later to be eliminated.
Les particules de cet alliage formeront les particules supports à la surface desquelles seront fixées les particules inoculantes.The particles of this alloy will form the support particles to the surface of which the inoculant particles will be fixed.
Les particules de surface seront, dans le présent exemple, des particules de siliciure de calcium CaSi et d'aluminium métallique, présentant toutes deux des granulométries inférieures à 400 micromètres.The surface particles will be, in the present example, particles of calcium silicide CaSi and metallic aluminum, both having particle sizes less than 400 micrometers.
On utilisera 5 % en masse de ces particules de surface, soit environ 25 kilogrammes de ce mélange de particules CaSi et Al.5% by mass of these surface particles will be used, i.e. approximately 25 kilograms of this mixture of CaSi and Al particles.
Afin de permettre la fixation sur les particules supports, les particules de surface à fixer sont préalablement mélangées avec un liant en solution aqueuse, puis injectées dans le réacteur en environ 30 minutes à la température de 100°C.In order to allow the fixing on the support particles, the surface particles to be fixed are mixed beforehand with a binder in aqueous solution, then injected into the reactor in about 30 minutes at a temperature of 100°C.
Après injection totale du mélange de particules et du liant, l'ensemble particules de surface, particules support et liant est fluidisé et chauffé jusqu'à ce que l'eau introduite ait été complètement évaporée. On pourra contrôler l'évaporation de l'eau par toute méthode usuelle, notamment par mesure de l'humidité de l'air sortant du réacteur.After total injection of the mixture of particles and of the binder, the assembly of surface particles, support particles and binder is fluidized and heated until the water introduced has been completely evaporated. It is possible to control the evaporation of the water by any usual method, in particular by measuring the humidity of the air leaving the reactor.
L'inoculant selon l'invention est ensuite récupéré et caractérisé pour évaluer l'efficacité de l'enrobage. Cette caractérisation pourra être faite notamment par contrôle au microscope électronique à balayage.The inoculant according to the invention is then recovered and characterized in order to evaluate the effectiveness of the coating. This characterization can be made in particular by checking with a scanning electron microscope.
Le liant utilisé pourra être de type liant organique ou polymère, comme par exemple, des liants de type alcool polyvinylique (APV), cellulose (CMC) et polyvinylpyrrolidone (PVP) ... Bien évidemment, cette liste n'est pas limitative.The binder used may be of the organic or polymer type, such as binders of the polyvinyl alcohol (PVA), cellulose (CMC) and polyvinylpyrrolidone (PVP) type, etc. Obviously, this list is not exhaustive.
La quantité d'eau utilisée pour la dilution du liant dépend bien évidemment de la solubilité de ce dernier dans l'eau et devra être adaptée en conséquence.The quantity of water used for the dilution of the binder obviously depends on the solubility of the latter in water and must be adapted accordingly.
Il est également possible d'envisager l'utilisation de liants minéraux, notamment de type silicate de sodium, ainsi que des liants hydrauliques de type ciment ou chaux.It is also possible to envisage the use of mineral binders, in particular of the sodium silicate type, as well as hydraulic binders of the cement or lime type.
Bien évidemment, la nature du liant utilisé pourra dépendre des matériaux inoculants et supports utilisés.Obviously, the nature of the binder used may depend on the inoculant materials and supports used.
La quantité de liant utilisée sera calculée de manière à permettre au mieux la fixation quasi-totale des particules de surface sans excès manifeste qui pourrait ensuite dégrader les performances finales de l'inoculant selon l'invention.The quantity of binder used will be calculated in such a way as to best allow almost total fixation of the surface particles without manifest excess which could then degrade the final performance of the inoculant according to the invention.
Cette quantité de liant utilisée dépendra bien évidemment de son pouvoir collant et devra également être adaptée en conséquence. On pourra notamment procéder par tests et vérification visuelle à l'aide d'un microscope électronique à balayage notamment. Typiquement, la quantité de liant utilisée pourra être comprise entre 0,001 et 1 % en masse de liant par rapport à la masse totale des particules (particules support et particules de surface).This amount of binder used will obviously depend on its tackiness and will also have to be adapted accordingly. It will be possible in particular to proceed by tests and visual verification with the aid of a scanning electron microscope in particular. Typically, the amount of binder used may be between 0.001 and 1% by mass of binder relative to the total mass of the particles (support particles and surface particles).
Selon un autre exemple possible de fabrication de l'inoculant selon l'invention, environ 500 kg de FeSi70 contenant 1 % en masse d'AI et 1,5 % en masse de Ca, de granulométrie 0,2-0,5 mm sont introduits dans un réacteur à lit fluidisé. L'alliage FeSi est mis en fluidisation par injection d'air. La température à l'intérieur du réacteur est portée à 100°C. Ces particules sont les particules support. Une suspension est réalisée avec du PVP et de l'eau. 8 % de particules de surface, contenant du bismuth Bi et d'alliage ferro-silico-terres rares FeSiTR, toutes deux de granulométrie <200µm sont ajoutées à la solution PVP + eau, puis mises en suspension. Cette suspension est ensuite injectée à raison de 10 % en masse dans le réacteur pendant environ 40 min à la température de 100°C. Après injection totale du mélange, l'intérieur du réacteur est maintenu à 100°C jusqu'à séchage complet du produit.According to another possible example of manufacture of the inoculant according to the invention, approximately 500 kg of FeSi 70 containing 1% by mass of Al and 1.5% by mass of Ca, with a particle size of 0.2-0.5 mm are introduced into a fluidized bed reactor. The FeSi alloy is fluidized by air injection. The temperature inside the reactor is brought to 100°C. These particles are the support particles. A suspension is made with PVP and water. 8% of surface particles, containing bismuth Bi and ferro-silico-rare earth alloy FeSiTR, both of particle size <200 μm are added to the PVP+water solution, then suspended. This suspension is then injected at a rate of 10% by mass into the reactor for about 40 min at a temperature of 100°C. After total injection of the mixture, the inside of the reactor is maintained at 100° C. until the product has completely dried.
Selon encore un autre exemple possible de fabrication de l'inoculant selon l'invention, environ 1000 kg de FeSi70 contenant 1 % en masse d'AI et 1,5 % en masse de Ca, de granulométrie 2 - 7 mm et environ 50 kg de poudre d'Aluminium de granulométrie <300µm sont introduits dans un réacteur à lit fluidisé. L'ensemble des particules est mis en fluidisation par injection d'air appauvri. La température à l'intérieur du réacteur est portée à 100°C. Une suspension est réalisée avec du PVP et de l'eau. Cette suspension est ensuite injectée à raison de 10 % en masse dans le réacteur pendant environ 40 min à la température de 100°C. Après injection totale du mélange, l'intérieur du réacteur est maintenu à 100°C jusqu'à séchage complet du produit.According to yet another possible example of manufacture of the inoculant according to the invention, approximately 1000 kg of FeSi 70 containing 1% by mass of Al and 1.5% by mass of Ca, with a particle size of 2-7 mm and approximately 50 kg of Aluminum powder with a particle size <300 μm are introduced into a fluidized bed reactor. All the particles are fluidized by injecting depleted air. The temperature inside the reactor is brought to 100°C. A suspension is made with PVP and water. This suspension is then injected at a rate of 10% by mass into the reactor for about 40 min at a temperature of 100°C. After complete injection of the mixture, the interior of the reactor is maintained at 100° C. until the product has completely dried.
Bien évidemment, la mise en oeuvre du procédé n'est pas limitée à l'utilisation d'un réacteur à lit fluidisé et d'autres techniques d'enrobage peuvent être utilisées. On peut notamment citer les méthodes suivantes.Obviously, the implementation of the method is not limited to the use of a fluidized bed reactor and other coating techniques can be used. Mention may in particular be made of the following methods.
Une première méthode est l'utilisation d'un mélangeur à grande vitesse, par exemple de l'ordre de 1000 à 1500 tours par minute.A first method is the use of a high-speed mixer, for example of the order of 1000 to 1500 revolutions per minute.
La vitesse de mélange permet l'incrustation mécanique des fines particules de surface dans les particules plus grosses de FeSi (particules support). Une telle incrustation mécanique ne nécessite pas l'utilisation d'un liant et on parle alors d'enrobage à sec et à froid. Les particules support du type FeSi75 contenant principalement les phases FeSi2,4 et Si, peuvent être incrustées directement par les particules de surface.The mixing speed allows the mechanical embedding of the fine surface particles in the larger FeSi particles (carrier particles). Such mechanical incrustation does not require the use of a binder and we then speak of dry and cold coating. Support particles of the FeSi 75 type, containing mainly the FeSi 2,4 and Si phases, can be embedded directly by the surface particles.
Une deuxième méthode est l'utilisation d'un mélangeur à fort taux de cisaillement.A second method is the use of a high shear mixer.
Dans ce cas, le mélange s'effectue à plus ou moins grande vitesse (entre 50 et 500 tours par minutes, par exemple) dans un mélangeur du type mélangeur granulateur, en présence d'un liant (exemples cités précédemment). Après mélange, on procède à une étape de séchage pour éliminer l'eau du liant.In this case, the mixing is carried out at more or less high speed (between 50 and 500 revolutions per minute, for example) in a mixer of the mixer-granulator type, in the presence of a binder (examples cited above). After mixing, a drying step is carried out to remove the water from the binder.
Des moyens de séchage peuvent équiper le mélangeur. Il peut notamment s'agir d'une rampe de brûleurs, par exemple à gaz, chauffant l'extérieur du mélangeur par conduction ; d'un tapis chauffant, par exemple en silicone, entourant notamment les parois du mélangeur ; ou encore de tout autre système permettant d'amener la poudre à l'intérieur du mélangeur à une température comprise entre 80 et 150°C en vue d'éliminer l'eau.Means of drying can equip the mixer. It may in particular be a burner ramp, for example gas, heating the outside of the mixer by conduction; a heating mat, for example made of silicone, surrounding in particular the walls of the mixer; or even any other system making it possible to bring the powder inside the mixer to a temperature of between 80 and 150° C. in order to eliminate the water.
Les systèmes de mélangeurs utilisés, du type à tambour ou granulateur doivent permettre un mouvement de la poudre à l'intérieur dudit mélangeur entraînant un brassage efficace et une certaine régularité du collage.The mixer systems used, of the drum or granulator type, must allow movement of the powder inside said mixer resulting in effective mixing and a certain regularity of the bonding.
A cette fin, le mélangeur peut être équipé d'ailettes de brassage sur ses parois ou encore un mélangeur granulateur à système de rotation central ou déporté selon un ou deux axes.To this end, the mixer can be equipped with stirring fins on its walls or else a mixer-granulator with a central or offset rotation system along one or two axes.
Le procédé de l'invention peut être conduit indifféremment en continu, ou en discontinu par lots (batch).The method of the invention can be carried out either continuously or discontinuously in batches (batch).
Lors de la mise en œuvre, les particules support et de surface peuvent être ajoutées soit ensemble, soit de manière séparée.During processing, the support and surface particles can be added either together or separately.
Lorsqu'elles sont ajoutées ensemble, elles pourront être avantageusement pré-mélangées, avant ajout du liant pour assurer le collage.When they are added together, they may advantageously be pre-mixed, before adding the binder to ensure bonding.
Lorsqu'elles sont ajoutées séparément, on introduira préférentiellement les particules support en premier avant d'ajouter les particules de surface, préférentiellement en continu, le liant étant également introduit préférentiellement en continu.When they are added separately, the carrier particles will preferably be introduced first before adding the surface particles, preferably continuously, the binder also being preferably introduced continuously.
Il convient également de noter que bien qu'illustré avec des particules support à base de FeSi, il est bien évidemment possible d'utiliser d'autres matériaux classiquement utilisés en fonderie, et notamment des particules support de type SiC ou graphite. Il convient de simplement transposer les exemples de fabrication à ces matériaux.It should also be noted that although illustrated with support particles based on FeSi, it is of course possible to use other materials conventionally used in foundry, and in particular support particles of the SiC or graphite type. It is appropriate to simply transpose the manufacturing examples to these materials.
Les résultats d'un tel inoculant selon l'invention ont été testés sur un bain de fonte.The results of such an inoculant according to the invention were tested on a cast iron bath.
Comme pour le procédé de fabrication, les exemples sont donnés pour des cas d'utilisation les plus courants avec un inoculant selon l'invention dont la particule support est de type FeSi.As for the manufacturing process, the examples are given for the most common cases of use with an inoculant according to the invention whose support particle is of the FeSi type.
Cela n'empêche en aucune manière l'utilisation d'inoculants selon l'invention comprenant d'autres types de particules support tel que le carbure de silicium ou le graphite, ces matériaux étant toutefois utilisés moins fréquemment en fonderie.This in no way prevents the use of inoculants according to the invention comprising other types of support particles such as silicon carbide or graphite, these materials being however used less frequently in foundries.
Un bain de fonte à graphite sphéroïdal a été traité à un taux de 0,3 % en poids avec un alliage inoculant de type FeSi75, et contenant 0,8 % en masse d'aluminium et 0,7 % en masse de calcium.A cast iron bath with spheroidal graphite was treated at a rate of 0.3% by weight with an inoculant alloy of the FeSi 75 type, and containing 0.8% by mass of aluminum and 0.7% by mass of calcium.
Le traitement s'effectue par ajout de l'inoculant dans la poche de fonte, avant remplissage du moule.The treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,32 % (calculé selon la formule simplifiée Ceq = %C + 1/3 (%Si + %P) où %C, %Si et %P sont les teneurs en carbone, silicium et phosphore de la fonte).The quantity of carbon equivalent of cast iron (Ceq) is 4.32% (calculated according to the simplified formula Ceq = %C + 1/3 (%Si + %P) where %C, %Si and %P are the contents carbon, silicon and phosphorus from cast iron).
Le magnésium résiduel de la fonte est à 400 millièmes.The residual magnesium of the cast iron is 400 thousandths.
La fonte a ensuite été coulée dans un moule de type BCIRA.The cast iron was then poured into a BCIRA type mould.
A une épaisseur de 6 mm, la fonte traitée présente les caractéristiques suivantes :
- Structure de la matrice : 55 % perlite, 15 % ferrite, 30 % cémentite
- Nombre de nodules par mm2 : 270
- Graphite de type VI : 57 %
- Nodularité moyenne : 85 %
- Diamètre moyen : 16,2 microns
- Matrix structure: 55% pearlite, 15% ferrite, 30% cementite
- Number of nodules per mm 2 : 270
- Type VI graphite: 57%
- Average nodularity: 85%
- Average diameter: 16.2 microns
Un bain de fonte à graphite sphéroïdal a été traité à un taux de 0,3 % en masse avec un inoculant selon l'invention possédant la composition suivante :
- Alliage de particule support : FeSi75, et contenant 0,8 % en masse d'aluminium et 0,7 % en masse de calcium
- Particules de surface: 1,5% en masse de particules de CaSi possédant une taille inférieure à 50 microns et 1,5% en masse de particules d'aluminium métallique de taille inférieure à 50 microns
- Liant : 10% en masse d'une solution aqueuse de PVP
- Dépôt des particules de surface par collage réalisé par fluidisation à 100°C.
- Support particle alloy: FeSi 75 , and containing 0.8% by mass of aluminum and 0.7% by mass of calcium
- Surface particles: 1.5% by mass of CaSi particles having a size less than 50 microns and 1.5% by mass of metallic aluminum particles having a size less than 50 microns
- Binder: 10% by mass of an aqueous solution of PVP
- Deposition of surface particles by bonding carried out by fluidization at 100°C.
Le traitement s'effectue par ajout de l'inoculant dans la poche de fonte, avant remplissage du moule.The treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,32 %.The carbon equivalent amount of cast iron (Ceq) is 4.32%.
Le magnésium résiduel de la fonte est à 400 millièmes.The residual magnesium of the cast iron is 400 thousandths.
La fonte a ensuite été coulée dans un moule de type BCIRA.The cast iron was then poured into a BCIRA type mould.
A une épaisseur de 6 mm, la fonte traitée présente les caractéristiques suivantes :
- Structure de la matrice : 45 % perlite, 50 % ferrite, 5 % cémentite
- Nombre de nodules par mm2 : 540
- Graphite de type VI : 59 %
- Nodularité moyenne : 92 %
- Diamètre moyen : 18,7 microns
- Matrix structure: 45% pearlite, 50% ferrite, 5% cementite
- Number of nodules per mm 2 : 540
- Type VI graphite: 59%
- Average nodularity: 92%
- Average diameter: 18.7 microns
Traitement d'un bain de fonte à graphite sphéroïdal à 0,3 % en masse avec un produit constitué :
- d'un alliage support: FeSi 75 avec Al = 0,8 % en masse et Ca = 0,7 % en masse
- de particules en surface : 2,5 % de particules de Bismuth Bi de taille <100µm, et 2,5 % en masse de particules de l'alliage ferro-silico-terres rares (FeSiTR) de taille <100µm.
- Liant : 10% en masse d'une solution aqueuse de PVP
- Dépôt des particules de surface par collage réalisé par fluidisation à 100°C.
- of a support alloy: FeSi 75 with Al = 0.8% by mass and Ca = 0.7% by mass
- surface particles: 2.5% of Bismuth Bi particles of size <100 μm, and 2.5% by mass of particles of the ferro-silico-rare earth alloy (FeSiTR) of size <100 μm.
- Binder: 10% by mass of an aqueous solution of PVP
- Deposition of surface particles by bonding carried out by fluidization at 100°C.
Le traitement s'effectue par ajout de l'inoculant dans la poche de fonte, avant remplissage du moule.The treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
La quantité de carbone équivalent (Ceq) de la fonte est à 4,32 %. Le magnésium résiduel est à 420 millièmes.The amount of carbon equivalent (Ceq) of cast iron is 4.32%. Residual magnesium is 420 thousandths.
La fonte est coulée dans un moule BCIRA.The cast iron is cast in a BCIRA mould.
A l'épaisseur de 6 mm, la fonte présente les caractéristiques suivantes :
- Structure de la matrice = 50 % Perlite - 50 % Ferrite - 0 % de cémentite
- Nombre de nodules/mm2 = 570
- Graphite de type VI = 62 %
- Nodularité moyenne = 92 %
- Diamètre moyen = 17,8µm
- Matrix structure = 50% Pearlite - 50% Ferrite - 0% cementite
- Number of nodules/mm 2 = 570
- Type VI graphite = 62%
- Average nodularity = 92%
- Average diameter = 17.8µm
Un bain de fonte à graphite sphéroïdal a été traité à un taux de 0,3 % en masse avec un inoculant élaboré classiquement de type FeSi75, et contenant 1,2 % en masse d'aluminium, 1,5 % en masse de calcium et 1,5 % en masse de zirconium.A cast iron bath with spheroidal graphite was treated at a rate of 0.3% by mass with an inoculant conventionally prepared of the FeSi 75 type, and containing 1.2% by mass of aluminum, 1.5% by mass of calcium and 1.5% by weight of zirconium.
Le traitement s'effectue par ajout de l'inoculant dans la poche de fonte, avant remplissage du moule.The treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,32 %.The carbon equivalent amount of cast iron (Ceq) is 4.32%.
Le magnésium résiduel de la fonte est à 400 millièmes.The residual magnesium of the cast iron is 400 thousandths.
La fonte a ensuite été coulée dans un moule de type BCIRA.The cast iron was then poured into a BCIRA type mould.
A une épaisseur de 6 mm, la fonte traitée présente les caractéristiques suivantes :
- Structure de la matrice : 45 % perlite, 50 % ferrite, 5 % cémentite
- Nombre de nodules par mm2 : 505
- Graphite de type VI : 59 %
- Nodularité moyenne : 87 %
- Diamètre moyen : 18,9 microns
- Matrix structure: 45% pearlite, 50% ferrite, 5% cementite
- Number of nodules per mm 2 : 505
- Type VI graphite: 59%
- Average nodularity: 87%
- Average diameter: 18.9 microns
Ainsi, on voit que pour obtenir sensiblement les mêmes résultats, il serait nécessaire d'augmenter largement les quantités de composants inoculants et d'introduire du zirconium, par rapport à un inoculant possédant une structure selon notre invention.Thus, it can be seen that to obtain substantially the same results, it would be necessary to greatly increase the quantities of inoculant components and to introduce zirconium, with respect to an inoculant having a structure according to our invention.
Traitement d'un bain de fonte de graphite lamellaire à 0,3 % en poids avec un produit base FeSi 75 avec Al = 1,0% en poids et Ca = 1,5 % en poids.Treatment of a 0.3% by weight lamellar graphite cast iron bath with an FeSi 75 base product with Al = 1.0% by weight and Ca = 1.5% by weight.
Le traitement s'effectue par ajout de l'inoculant dans la poche de fonte, avant remplissage du moule.The treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,3 %.The carbon equivalent amount of cast iron (Ceq) is 4.3%.
La fonte est coulée dans un moule BCIRA.The cast iron is cast in a BCIRA mould.
A l'épaisseur de 6 mm, la fonte présente les caractéristiques suivantes :
- Nombre de cellules eutectiques/mm2: 0,2
- 40 % cémentite
- Number of eutectic cells/mm 2 : 0.2
- 40% cementite
Traitement d'un bain de fonte de graphite lamellaire à 0,3 % en masse avec un produit constitué :
- d'un alliage support: FeSi 75 avec Al = 1,0 % en masse et Ca = 1,5 % en masse.
- de particules en surface : 5 % en masse de particules de sulfate de baryum BaSO4 de taille <100µm
- Liant : 5% en masse d'une solution aqueuse de ciment
- Dépôt des particules de surface par collage réalisé par fluidisation à 100°C.
- of a support alloy: FeSi 75 with Al = 1.0% by mass and Ca = 1.5% by mass.
- of particles on the surface: 5% by mass of particles of barium sulphate BaSO 4 of size <100µm
- Binder: 5% by mass of an aqueous solution of cement
- Deposition of surface particles by bonding carried out by fluidization at 100°C.
Le traitement s'effectue par ajout de l'inoculant dans la poche de fonte, avant remplissage du moule.The treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,3 %.The carbon equivalent amount of cast iron (Ceq) is 4.3%.
La fonte est coulée dans un moule BCIRA.The cast iron is cast in a BCIRA mould.
A l'épaisseur de 6 mm, la fonte présente les caractéristiques suivantes :
- Nombre de cellules eutectiques par mm2 : 2
- Pas de cémentite
- Number of eutectic cells per mm 2 : 2
- No cementite
Traitement d'un bain de fonte de graphite lamellaire à 0,3 % en masse avec un produit base FeSi75 avec FeSi 75 avec Al = 1,0 % en masse, Ca = 1,5% en masse et Zr = 1,5 % en masse.Treatment of a 0.3% by mass lamellar graphite cast iron bath with a base product FeSi75 with FeSi 75 with Al = 1.0% by mass, Ca = 1.5% by mass and Zr = 1.5% en masse.
Le traitement s'effectue par ajout de l'inoculant dans la poche de fonte, avant remplissage du moule.The treatment is carried out by adding the inoculant to the melting ladle, before filling the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,3 %.The carbon equivalent amount of cast iron (Ceq) is 4.3%.
La fonte est coulée dans un moule BCIRA.The cast iron is cast in a BCIRA mould.
A l'épaisseur de 6 mm, la fonte présente les caractéristiques suivantes :
- Nombre de cellules eutectiques par mm2 : 1,5.
- 5 % de cémentite
- Number of eutectic cells per mm 2 : 1.5.
- 5% cementite
Traitement d'un bain de fonte de graphite sphéroidal à 0,3 % en masse avec un produit constitué :
- d'un alliage support: FeSi 75 avec Al = 1,0 % en masse et Ca = 1,0 % en masse
- de particules en surface : 5 % d'un mélange de poudres d'aluminium (taille <75µm) et de CaSi (taille <75µm)
- Liant : 2% en masse d'une solution aqueuse de PVP
- Dépôt des particules de surface par collage réalisé par fluidisation à 100°C.
- of a support alloy: FeSi 75 with Al = 1.0% by mass and Ca = 1.0% by mass
- surface particles: 5% of a mixture of aluminum powders (size <75µm) and CaSi (size <75µm)
- Binder: 2% by mass of an aqueous solution of PVP
- Deposition of surface particles by bonding carried out by fluidization at 100°C.
Le traitement s'effectue par ajout de l'inoculant au jet lors du remplissage du moule.The treatment is carried out by adding the inoculant to the jet when filling the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,32 %.The carbon equivalent amount of cast iron (Ceq) is 4.32%.
La fonte est ensuite coulée dans un moule pour fabriquer une pièce ayant des épaisseurs différentes: 4 mm et 25 mm.The cast iron is then poured into a mold to make a piece with different thicknesses: 4 mm and 25 mm.
Sur la pièce coulée, sur la partie d'épaisseur de 4 mm, la fonte présente les caractéristiques suivantes :
- Nombre de nodules /mm2 : 502
- Diamètre moyen : 17µm
- Graphite de type VI : 85 %
- Nodularité : 98 %
- Cémentite : 0 %
- Ferrite : 48 %
- Perlite : 52 %
- Number of nodules/mm 2 : 502
- Average diameter: 17µm
- Type VI graphite: 85%
- Nodularity: 98%
- Cementite: 0%
- Ferrite: 48%
- Perlite: 52%
Sur la pièce coulée, sur la partie d'épaisseur de 25 mm, la fonte présente les caractéristiques suivantes :
- Nombre de nodules /mm2 : 250
- Diamètre moyen : 23 µm
- Graphite de type VI : 87 %
- Nodularité : 98.5 %
- Cémentite : 0 %
- Ferrite : 50 %
- Perlite : 50 %
- Number of nodules/mm 2 : 250
- Average diameter: 23 µm
- Type VI graphite: 87%
- Nodularity: 98.5%
- Cementite: 0%
- Ferrite: 50%
- Perlite: 50%
Traitement d'un bain de fonte de graphite sphéroidal à 0,3 % en masse avec un alliage FeSi75 obtenu classiquement, contenant 1,0% Al, 1.0 % Ca et 1.5 % Zr.Treatment of a spheroidal graphite cast iron bath at 0.3% by mass with an FeSi75 alloy obtained conventionally, containing 1.0% Al, 1.0% Ca and 1.5% Zr.
Le traitement s'effectue par ajout de l'inoculant au jet lors du remplissage du moule.The treatment is carried out by adding the inoculant to the jet when filling the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,31 %.The carbon equivalent amount of cast iron (Ceq) is 4.31%.
La fonte est ensuite coulée dans un moule pour fabriquer une pièce ayant des épaisseurs différentes: 4 mm et 25 mm.The cast iron is then poured into a mold to make a piece with different thicknesses: 4 mm and 25 mm.
Sur la pièce coulée, sur la partie d'épaisseur de 4 mm, la fonte présente les caractéristiques suivantes :
- Nombre de nodules /mm2 : 350.
- Diamètre moyen : 19 µm
- Graphite de type VI : 70 %
- Nodularité : 95 %
- Cémentite : 30 %
- Ferrite : 40 %
- Perlite : 30 %
- Number of nodules/mm 2 : 350.
- Average diameter: 19 µm
- Type VI graphite: 70%
- Nodularity: 95%
- Cementite: 30%
- Ferrite: 40%
- Perlite: 30%
Sur la pièce coulée, sur la partie d'épaisseur de 25 mm, la fonte présente les caractéristiques suivantes :
- Nombre de nodules /mm2 : 150.
- Diamètre moyen : 25 µm
- Graphite de type VI : 73 %
- Nodularité : 95.5 %
- Cémentite : 0 %
- Ferrite : 50 %
- Perlite : 50 %
- Number of nodules/mm 2 : 150.
- Average diameter: 25 µm
- Type VI graphite: 73%
- Nodularity: 95.5%
- Cementite: 0%
- Ferrite: 50%
- Perlite: 50%
Ainsi, on voit qu'il est possible avec l'inoculant selon l'invention d'inoculer efficacement les différentes parties d'une pièce avec différentes épaisseurs, alors qu'il est difficile d'y parvenir avec un inoculant fabriqué suivant l'art antérieur.Thus, we see that it is possible with the inoculant according to the invention to effectively inoculate the different parts of a part with different thicknesses, whereas it is difficult to achieve this with an inoculant manufactured according to the art prior.
Traitement d'un bain de fonte de graphite sphéroidal à 0,3 % en masse avec un produit constitué :
- d'un alliage support: FeSi75 avec Al = 1,0 % en masse et Ca = 1,0 % en masse
- de particules en surface : 5 % d'un mélange de poudres d'aluminium (taille <75µm) et de CaSi (taille <75µm)
- Liant : 10% en masse d'une solution aqueuse de ciment
- Dépôt des particules de surface par collage réalisé par fluidisation à 100°C.
- of a support alloy: FeSi 75 with Al = 1.0% by mass and Ca = 1.0% by mass
- surface particles: 5% of a mixture of aluminum powders (size <75µm) and CaSi (size <75µm)
- Binder: 10% by mass of an aqueous solution of cement
- Deposition of surface particles by bonding carried out by fluidization at 100°C.
Le traitement s'effectue par ajout de l'inoculant dans le bassin de coulée lors du remplissage du moule.The treatment is carried out by adding the inoculant in the casting basin during the filling of the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,33 %.The carbon equivalent amount of cast iron (Ceq) is 4.33%.
La fonte est ensuite coulée dans un moule pour fabriquer une pièce de forte épaisseur (170mm).The cast iron is then poured into a mold to make a very thick part (170mm).
Sur la pièce coulée d'épaisseur 170mm, au centre de la pièce, la fonte présente les caractéristiques suivantes :
- Nombre de nodules /mm2 : 160
- Graphite de type VI : 65 %
- Diamètre moyen : 25 µm
- Nodularité : 99.2 %
- Cémentite : 0 %
- Ferrite : 50 %
- Perlite : 50 %
- Number of nodules/mm 2 : 160
- Type VI graphite: 65%
- Average diameter: 25 µm
- Nodularity: 99.2%
- Cementite: 0%
- Ferrite: 50%
- Perlite: 50%
Traitement d'un bain de fonte de graphite sphéroidal à 0,3 % en masse avec un alliage FeSi75 obtenu classiquement, contenant 1.0 % de Bi, et 0.6 % de Terres Rares.Treatment of a bath of cast iron of spheroidal graphite at 0.3% by mass with an FeSi 75 alloy obtained conventionally, containing 1.0% of Bi, and 0.6% of Rare Earths.
Le traitement s'effectue par ajout de l'inoculant dans le bassin de coulée lors du remplissage du moule.The treatment is carried out by adding the inoculant in the casting basin during the filling of the mould.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,31 %.The carbon equivalent amount of cast iron (Ceq) is 4.31%.
La fonte est ensuite coulée dans un moule pour fabriquer une pièce de forte épaisseur : 170 mm.The cast iron is then poured into a mold to make a very thick part: 170 mm.
Sur la pièce coulée, en milieu de la pièce d'épaisseur 170 mm, la fonte présente les caractéristiques suivantes :
- Nombre de nodules /mm2 : 155.
- Diamètre moyen : 22 µm
- Graphite de type VI : 50 %
- Nodularité : 85 %
- Cémentite : 0 %
- Ferrite : 52 %
- Perlite : 48 %
- Number of nodules/mm 2 : 155.
- Average diameter: 22 µm
- Type VI graphite: 50%
- Nodularity: 85%
- Cementite: 0%
- Ferrite: 52%
- Perlite: 48%
Ainsi, on voit qu'il est possible avec l'inoculant selon l'invention d'inoculer efficacement des pièces de fortes épaisseurs, tout en conservant une bonne nodularité du graphite.Thus, it is seen that it is possible with the inoculant according to the invention to effectively inoculate very thick parts, while maintaining good nodularity of the graphite.
Claims (9)
- A powdered particulate inoculant for treating liquid cast-iron, characterized in thatit comprises,on the one hand, support particles which are made of a fusible material in the liquid cast-iron promoting the association of carbon with iron in the form of graphite and comprising at least one ferrosilicon alloy, aluminum and calcium, where the silicon is present in a content of at least 40% by mass relative to the mass of said support particles and aluminum and calcium are present, in alloyed form, each in a content of 0.2 to 5% by mass relative to the mass of said support particles, andon the other hand, surface particles which are made of a material promoting the germination and growth of graphite, selected, separately or in a mixture, among metallic elements, silicides, oxides, metallic sulphides, sulphates and carbon black, the material of the surface particles being different from the material of the support particles, said surface particles being arranged and distributed in a discontinuous manner on the surface of the support particles, the surface particles having a grain size distribution smaller than that of the support particles and such that their d50 is smaller than or equal to one-tenth of the d50 support particles.
- The inoculant according to claim 1, characterized in that the material of the surface particles is selected among aluminum, bismuth, manganese, iron silicides, rare earths silicides and calcium silicides, aluminum oxides, calcium oxides, silicon oxides and barium oxides, iron sulphides, calcium sulphides and rare earths sulphides and barium sulphate.
- The inoculant according to claim 1 or 2, characterized in that the proportion of the surface particles is comprised between 1 and 8% by mass, relative to the mass of the inoculant.
- The inoculant according to any one of claims 1 to 3, characterized in that, until the introduction into the cast-iron, the surface particles occupy between 80 and 90% of the surface of the support particles.
- The inoculant according to any one of claims 1 to 4, characterized in that the surface particles are inlaid in the surface of the support particles.
- The inoculant according to any one of claims 1 to 5, characterized in that the surface particles are bonded by means of a binder at the surface of the support particles.
- A method for manufacturing an inoculant for treating cast-iron according to any one of claims 1 to 12, comprising the following steps which consist in:Providingsupport particles which are made of a fusible material in the liquid cast-iron promoting the association of carbon with iron in the form of graphite and comprising at least one ferrosilicon alloy, aluminum and calcium, where the silicon is present in a content of at least 40% by mass relative to the mass of said support particles and aluminum and calcium are present, in alloyed form, each in a content of 0.2 to 5% by mass relative to the mass of said support particles, said particles, said support particles having a grain size distribution varying from 0, 2 to 7 mm, on the one hand, andsurface particles which are made of a material promoting the germination and growth of graphite, selected, separately or in a mixture, among metallic elements, such as aluminium, bismuth and manganese, silicides, in particular iron silicides, rare earths silicides and calcium silicides, oxides, such as aluminum oxides, calcium oxides, silicon oxides or barium oxides, metal sulphides, in particular iron sulphides, calcium sulphides and rare earths sulphides, sulphates, in particular barium sulphates, and carbon black sulphates, the material of the surface particles being different from the material of the support particles, said surface particles having a grain size distribution smaller than that of the support particles and such that their d50 is smaller than or equal to one-tenth of the d50 of the support particles, on the other hand, andDry mixing the support particles and the surface particles at high speed, for example at a speed ranging from 1000 to 1500 rpm, so as to obtain a deposit by inlaying the surface particles at the surface of the support particles, according to a discontinuous distribution.
- The method for manufacturing an inoculant according to any one of claims 1 to 6, comprising the following steps:Providingsupport particles which are made of a fusible material in the liquid cast-iron promoting the association of carbon with iron in the form of graphite and comprising at least one ferro-silicon alloy, aluminum and calcium, where the silicon is present in a content of at least 40% by mass relative to the mass of said support particles and aluminum and calcium are present, in alloyed form, each in a content of 0.2 to 5% by mass relative to the mass of said support particles, said particles, said support particles having a grain size distribution varying from 0, 2 to 7mm,surface particles which are made of a material promoting the germination and growth of graphite, selected, separately or in a mixture, among metallic elements, such as aluminium, bismuth and manganese, silicides, in particular iron silicides, rare earths silicides and calcium silicides, oxides, such as aluminum oxides, calcium oxides, silicon oxides or barium oxides, metal sulphides, in particular iron sulphides, calcium sulphides and rare earths sulphides, sulphates, in particular barium sulphates, and carbon black sulphates, the material of surface particles being different from the material of the support particles, said surface particles having a grain size distribution smaller than that of the support particles and such that their d50 is smaller than or equal to one-tenth of the d50 of the support particles,and of a binder in a solvent,Mixing the support particles, the surface particles and the binder, andRemoving the solvent from the binder, for example by evaporation.
- The method according to claim 8, characterized in that the binder is selected among organic and polymer binders, and in particular among polyvinyl alcohol (PVA), cellulose (CMC), polyvinylpyrrolidone (PVP) and cement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI201431959T SI2976172T1 (en) | 2013-03-19 | 2014-03-19 | Inoculant with surface particles |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1352419A FR3003577B1 (en) | 2013-03-19 | 2013-03-19 | INOCULANT WITH SURFACE PARTICLES |
| PCT/FR2014/050636 WO2014147342A1 (en) | 2013-03-19 | 2014-03-19 | Inoculant with surface particles |
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| Publication Number | Publication Date |
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| EP2976172A1 EP2976172A1 (en) | 2016-01-27 |
| EP2976172B1 true EP2976172B1 (en) | 2022-04-27 |
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| Country | Link |
|---|---|
| US (1) | US10351920B2 (en) |
| EP (1) | EP2976172B1 (en) |
| JP (2) | JP2016519714A (en) |
| KR (1) | KR20150131087A (en) |
| CN (1) | CN105121061A (en) |
| BR (1) | BR112015023924B8 (en) |
| CA (1) | CA2905802C (en) |
| DK (1) | DK2976172T3 (en) |
| ES (1) | ES2915375T3 (en) |
| FR (1) | FR3003577B1 (en) |
| MX (1) | MX2015013384A (en) |
| PT (1) | PT2976172T (en) |
| SI (1) | SI2976172T1 (en) |
| UA (1) | UA118555C2 (en) |
| WO (1) | WO2014147342A1 (en) |
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| FR3003577B1 (en) * | 2013-03-19 | 2016-05-06 | Ferropem | INOCULANT WITH SURFACE PARTICLES |
| EP2984490B1 (en) | 2013-06-14 | 2020-05-20 | Genomatica, Inc. | Methods of producing omega-hydroxylated fatty acid derivatives |
| WO2015195697A1 (en) | 2014-06-16 | 2015-12-23 | REG Life Sciences, LLC | Omega-hydroxylase-related fusion polypeptides with improved properties |
| WO2017101987A1 (en) | 2015-12-15 | 2017-06-22 | REG Life Sciences, LLC | Omega-hydroxylase-related fusion polypeptide variants with improved properties |
| NO20161094A1 (en) * | 2016-06-30 | 2018-01-01 | Elkem As | Cast Iron Inoculant and Method for Production of Cast Iron Inoculant |
| NO347571B1 (en) * | 2016-06-30 | 2024-01-15 | Elkem Materials | Cast Iron Inoculant and Method for Production of Cast Iron Inoculant |
| BR102016022690B1 (en) * | 2016-09-29 | 2022-02-08 | Tupy S.A. | VERMICULAR CAST IRON ALLOY FOR INTERNAL COMBUSTION ENGINE BLOCK AND HEAD |
| CN107326138A (en) * | 2017-07-10 | 2017-11-07 | 山东力得制动科技有限公司 | A kind of smelting technology for casting automobile brake hub casts gray cast iron |
| NO20172064A1 (en) | 2017-12-29 | 2019-07-01 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| NO20172065A1 (en) * | 2017-12-29 | 2019-07-01 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| NO346252B1 (en) | 2017-12-29 | 2022-05-09 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| NO20172061A1 (en) * | 2017-12-29 | 2019-07-01 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| NO20172063A1 (en) | 2017-12-29 | 2019-07-01 | Elkem Materials | Cast iron inoculant and method for production of cast iron inoculant |
| CN110396638A (en) * | 2019-07-10 | 2019-11-01 | 广西大学 | A kind of inovulant of gray cast iron and preparation method thereof |
| CN113061689B (en) * | 2021-03-24 | 2022-05-17 | 宁夏科通新材料科技有限公司 | Method for preparing silicon-calcium-barium-aluminum alloy from ore raw material |
| CN113174460A (en) * | 2021-03-31 | 2021-07-27 | 江苏亚峰合金材料有限公司 | Preparation process of silicon-added deoxidizing inoculant |
| CN113106186A (en) * | 2021-04-21 | 2021-07-13 | 江苏亚峰合金材料有限公司 | Preparation method of inoculant for tough cast iron |
| CN113789449B (en) * | 2021-09-28 | 2023-03-24 | 四川兰德高科技产业有限公司 | Refiner and preparation method and application thereof |
| CN114653902B (en) * | 2022-04-19 | 2024-03-22 | 江苏亚峰合金材料有限公司 | Environment-friendly casting inoculant containing rare earth elements |
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- 2014-03-19 KR KR1020157027366A patent/KR20150131087A/en not_active Application Discontinuation
- 2014-03-19 WO PCT/FR2014/050636 patent/WO2014147342A1/en active Application Filing
- 2014-03-19 EP EP14716891.8A patent/EP2976172B1/en active Active
- 2014-03-19 CA CA2905802A patent/CA2905802C/en active Active
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| EUN-HEE KIM ET AL: "Dual coating process for a high funtional reinforcement phase in metal matrix composites", 22 December 2010 (2010-12-22), pages 1 - 6, XP002628151, ISSN: 0300-9440, Retrieved from the Internet <URL:http://www.sciencedirect.com/science?_ob=MImg&_imagekey=B6THD-51S6FS0-3-9&_cdi=5280&_user=987766&_pii=S0300944010003309&_origin=gateway&_coverDate=12%2F22%2F2010&_sk=999999999&view=c&wchp=dGLzVtz-zSkWA&md5=2cbf5f60882e864557abe16aff1d6a3f&ie=/sdarticle.pdf> [retrieved on 20110314], DOI: 10.1016/J.PORGCOAT.2010.11.011 * |
| V Т KALININ ET AL: "Theory and Practice of Cast-Iron Inoculation by Ultra - and Nanodispersed Materials", 1 January 2010 (2010-01-01), pages 341 - 62107, XP055128013, Retrieved from the Internet <URL:http://metaljournal.com.ua/assets/Uploads/attachments/Kalinin341.pdf> [retrieved on 20140710] * |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2015013384A (en) | 2016-05-05 |
| UA118555C2 (en) | 2019-02-11 |
| PT2976172T (en) | 2022-07-18 |
| JP2016519714A (en) | 2016-07-07 |
| SI2976172T1 (en) | 2022-07-29 |
| BR112015023924B1 (en) | 2020-01-28 |
| JP2019073801A (en) | 2019-05-16 |
| FR3003577B1 (en) | 2016-05-06 |
| US20160047008A1 (en) | 2016-02-18 |
| KR20150131087A (en) | 2015-11-24 |
| CA2905802C (en) | 2020-12-08 |
| US10351920B2 (en) | 2019-07-16 |
| ES2915375T3 (en) | 2022-06-22 |
| BR112015023924A2 (en) | 2017-07-18 |
| EP2976172A1 (en) | 2016-01-27 |
| BR112015023924B8 (en) | 2020-05-05 |
| FR3003577A1 (en) | 2014-09-26 |
| CN105121061A (en) | 2015-12-02 |
| WO2014147342A1 (en) | 2014-09-25 |
| CA2905802A1 (en) | 2014-09-25 |
| DK2976172T3 (en) | 2022-07-04 |
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