EP2917377A1 - Cored wire for the metallurgical treatment of a bath of molten metal and corresponding method - Google Patents
Cored wire for the metallurgical treatment of a bath of molten metal and corresponding methodInfo
- Publication number
- EP2917377A1 EP2917377A1 EP13792869.3A EP13792869A EP2917377A1 EP 2917377 A1 EP2917377 A1 EP 2917377A1 EP 13792869 A EP13792869 A EP 13792869A EP 2917377 A1 EP2917377 A1 EP 2917377A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cored wire
- powder
- molten metal
- magnesium
- intermediate layer
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 238000011282 treatment Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000013543 active substance Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims description 72
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 60
- 229910052749 magnesium Inorganic materials 0.000 claims description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- 239000010959 steel Substances 0.000 claims description 28
- 229910000831 Steel Inorganic materials 0.000 claims description 27
- 229910052791 calcium Inorganic materials 0.000 claims description 27
- 239000011575 calcium Substances 0.000 claims description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 26
- 229910001018 Cast iron Inorganic materials 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 229910000676 Si alloy Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 description 17
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910001338 liquidmetal Inorganic materials 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005266 casting Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005562 fading Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000009749 continuous casting Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910004709 CaSi Inorganic materials 0.000 description 2
- 229910001141 Ductile iron Inorganic materials 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000005563 spheronization Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021348 calcium disilicide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 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
- 239000011344 liquid material Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
-
- 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
-
- 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
- C21C7/0006—Adding metallic additives
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- 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
- C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
- C21C2007/0062—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires with introduction of alloying or treating agents under a compacted form different from a wire, e.g. briquette, pellet
Definitions
- the invention relates to a cored wire for introduction into a bath of molten metal for metallurgical treatment, the cored wire comprising:
- a lining extending locally along a longitudinal axis, the lining comprising at least one active substance for treating the molten metal
- the molten metal is, for example, cast iron or steel.
- the objective of the metallurgical treatment is, for example, to add to the molten metal at least one substance intended to regulate the composition of the molten metal and / or the composition of the precipitates or non-metallic inclusions it contains.
- the flux-cored wire is generally composed of a lining comprising the active substance in pulverulent form, contained in a metallic envelope made of a metal whose composition is compatible with that of the molten metal to be treated.
- this envelope is itself advantageously made of steel.
- the flux-cored wire is introduced into the molten metal bath by means of an injection device, generally automatic, introducing a precise length of cored wire at an appropriate speed.
- cored wires whose packing consists of a pure calcium powder or calcium alloy, or a mixture of calcium powders and iron, or even aluminum.
- the introduction of a cored wire into the molten metal bath is an ingenious means for adding the active substance to the molten metal, the effectiveness of the introduction is sometimes limited.
- the calcium addition yield defined as the amount of calcium found in the steel after the injection of the cored wire divided by the amount of calcium introduced by the cored wire consumed is generally of the order of 10% to 15%, sometimes much less.
- the low efficiency of calcium comes mainly because of its low vaporization temperature. Indeed, of the order of 1480 ° C, the latter is generally lower than the working temperature of the liquid steel so that the calcium vaporizes while it is introduced into the liquid steel.
- An object of the invention is to provide a cored wire performing more effectively the metallurgical treatment, while remaining of a competitive cost.
- the subject of the invention is a cored wire of the type described above, in which the lining comprises:
- an intermediate layer extending longitudinally between the extruded bar and the outer envelope and comprising a powder comprising one or more of: a metal, a mixture of metals, a metal oxide, a mixture of metal oxides.
- the device may comprise one or more of the following characteristics, taken in isolation or in any technically possible combination:
- the lining further comprises a thermally insulating layer extending longitudinally between the extruded bar and the intermediate layer;
- the extruded bar has an outer equivalent diameter D1 in a transverse plane substantially perpendicular to the longitudinal axis, the intermediate layer having an outer equivalent diameter D2 in the transverse plane, with D2 lying in the range 1.3 times to 6.2 times D1; ;
- the outer casing comprises a strip of steel, aluminum, copper, nickel, or zinc, or an alloy of two or more thereof;
- the extruded bar mainly comprises magnesium;
- the powder of the intermediate layer mainly comprises an alloy of iron and silicon further comprising calcium and / or barium and / or one or more rare earths;
- the extruded bar mainly comprises calcium
- the powder of the intermediate layer comprises an iron powder or a mixture of iron powder and aluminum powder and / or magnesium powder and / or slag powder;
- the outer envelope is metallic
- the outer envelope mainly comprises one or more of: steel, copper, aluminum, nickel, zinc;
- the outer envelope has a transverse thickness of between 0.2 and 0.7 mm;
- the extruded bar has an external equivalent diameter of between 2 and 10 mm;
- the cored wire has an equivalent diameter of between 6 and 21 mm;
- the extruded bar is substantially cylindrical with a circular base
- the intermediate layer has a general shape of hollow cylinder, the cylinder being circular base;
- the outer casing has a substantially tubular general shape with a circular base.
- equivalent diameter of an element is meant the diameter of a surface disk equal to the surface presented by the sectional element in a transverse plane. If the given element has a circular cross-section along the transverse plane, the equivalent diameter is equal to the ordinary diameter.
- Metallurgical treatment means, for example:
- ⁇ a change in the chemical composition of molten metal, and / or ⁇ a modifying metal properties obtained after solidification due molten metal for example, changing the composition of inclusions or precipitates present before treatment, or the creation, as a result of the treatment, of such inclusions or precipitates, and / or
- the invention further relates to a method of metallurgically treating a bath of molten metal, the method comprising the step of introducing a flux-cored wire as described above into the molten metal bath.
- the method may comprise one or more of the following characteristics, taken in isolation or in any technically possible combination:
- the molten metal is cast iron and the filled cored wire is as described above;
- FIG. 1 shows schematically, in perspective, a cored wire according to the invention
- FIG. 2 shows schematically, in cross section, the cored wire shown in Figure 1;
- FIG. 3 represents a graph illustrating, in a particular application, the slowing down of the fading of the active substance (magnesium) when the flux-cored wire shown in FIGS. 1 and 2 is introduced into a bath of molten metal (liquid iron ).
- a cored wire 1 extending locally along a longitudinal axis L. Only a portion of the cored wire 1 is shown. The portion shown extends along the longitudinal axis L. This does not mean that all the cored wire 1 extends along the longitudinal axis L. Indeed, the cored wire 1 may have a certain curvature, for example s' it is rolled up to take up less space.
- transverse plane T perpendicular to the longitudinal axis L is defined. It will be understood that the transverse plane T is transversal for the portion of the cored wire 1 represented, that is to say, locally transverse.
- the cored wire 1 is for example intended to be introduced into a bath of molten iron (not shown).
- the cored wire 1 comprises a lining 2 and an outer envelope 4, both extending longitudinally.
- the outer casing 4 forms a peripheral portion of the cored wire 1, intended to be in contact with the molten metal bath when the cored wire 1 is introduced into the molten metal bath.
- the outer casing 4 is advantageously constituted by a metal strip 6 folded on itself around the longitudinal axis L.
- the strip 6 is for example steel, copper, aluminum, nickel, or zinc, or a mixture of two or more of these elements.
- the strip 6 advantageously comprises two longitudinal folds 6a, 6b (FIG.
- the strip 6, thus folded, has a generally tubular shape which envelops the lining 2.
- the shape tubular is substantially cylindrical with a circular base and has an equivalent diameter D.
- D is advantageously between 6 and 21 mm.
- D is 13 mm.
- the lining 2 comprises an extruded bar 8 extending longitudinally and an intermediate layer 10 extending longitudinally between the extruded bar 8 and the outer casing 4.
- the extruded bar 8 is advantageously substantially cylindrical with a circular base.
- the extruded bar 8 has a diameter D1 in the transverse plane T, with D1 advantageously between 2 and 10 mm, for example 8 mm.
- the extruded bar 8 comprises an active substance for carrying out a treatment of molten iron.
- the active substance is, for example, magnesium.
- the extruded bar 8 mainly comprises magnesium.
- the extruded bar 8 comprises at least
- magnesium 50% by weight of magnesium, preferably at least 90% by weight of magnesium.
- the extruded bar 8 is made of magnesium of industrial purity, for example 99.8% by weight.
- the extruded bar 8 is not a simple cluster of compacted powder material during the closure of the cored wire 1, nor even an agglomerate of powder grains (powder material) bonded together by a binder of any kind.
- the extruded bar 8 is for example obtained by extrusion of a solid cylinder (billet) of material through a die through a press.
- the bar 8 can also be obtained directly by a continuous casting method, the liquid material being solidified in the form of a continuous bar.
- the porosity of the extruded bar 8 is considered almost zero, the apparent density of the bar being close to the true density of the material.
- the intermediate layer 10 extends for example in the space between the extruded bar 8 and the outer shell 4.
- the intermediate layer 10 has an equivalent external diameter D2.
- D2 is for example such that the ratio D2 / D1 is 1, 3 and 6.2.
- the intermediate layer 10 is advantageously constituted by a powder.
- the intermediate layer 10 may also comprise a thermally insulating layer covering the bar 8.
- the intermediate layer 10 also comprises, mainly in the sense defined above, an active substance in the metallurgical treatment, for example a ferrosilicon alloy.
- the intermediate layer 10 can also comprise up to 12% by weight of calcium, barium and rare earths (lanthanum, cerium).
- the composition of the powder of the intermediate layer 10 depends of course on the type of metallurgical treatment to be performed. It can be neutral, that is to say without any metallurgical effect on the bath of liquid metal to be treated, in this chamber, the powder plays a unique thermal insulation of the bar 8. It can also participate directly in the treatment metallurgical and thus assume a dual role of thermal insulation and active treatment element.
- the cast iron to be treated is in the form of a bath of molten metal, for example contained in a container such as a pocket.
- the cored wire 1 is introduced into the molten melt bath in a manner known per se.
- the desulfurization reaction is as follows:
- magnesium is an energetic deoxidant.
- the remaining magnesium is incorporated into the melt.
- part of the magnesium vapor formed escapes to the surface of the melt and is oxidized in pure loss in the slag or in the atmosphere, giving rise for example to the formation of magnesia.
- the magnesium addition yield is defined as the ratio between, on the one hand, the difference between the Mg content actually found in the melt after the introduction of the cored wire 1 and the Mg content in the melt before the introduction of the cored wire 1.
- the magnesium contained in the extruded bar 8 has a nodulising role, that is to say that it makes it possible to obtain spheroidal graphite particles in the cast iron.
- the cored wire 1 performs the metallurgical treatment more efficiently, in the example, a nodularization of the cast iron, while remaining at a competitive cost.
- the intermediate layer 10 acts as a thermal protection for the extruded bar 8, slowing the rise in temperature of the magnesium contained in the extruded bar 8.
- the location of the intermediate layer 10 around the extruded bar 8 protects the latter.
- magnesium has a reduced surface area of heat exchange compared to that which would present a packing of simple grains of powder. Indeed, the specific surface is no longer the surface of the grains, but the lateral surface of the extruded bar 8. This slows the vaporization of the magnesium, which improves the addition efficiency and moderates the reaction of the Mg with the molten cast iron .
- the intermediate layer 10 has, in the example, also a metallurgical role.
- the intermediate layer 10 comprises a second active substance in the metallurgical treatment, ie for example a ferrosilicon alloy.
- This second active substance acts as an inoculant. Inoculation, as is known, regenerates the graphitic germination potential after the magnesium treatment. This makes it possible to avoid the formation of cementite and to contribute to obtaining the desired level of spheroidal graphite. For ferritic cast iron grades, this also promotes the formation of ferrite by increasing the density of spherules.
- the substance active against nodularization magnesium
- the extruded bar 8 it is possible to introduce the active substance more regularly than with son filled with the state of the art containing magnesium powder, whose density and compaction are difficult to control.
- the small mass variation of magnesium per meter in the flux-cored wire 1, advantageously of the order of +/- 2%, makes it possible to reduce the dispersion of the residual magnesium in the treated cast iron and, consequently, to reduce the consumption. of flux-cored wire for the same quantity of Mg actually introduced into the cast iron, as well as an improvement in the quality of the castings from the treated cast iron, in particular by reducing the porosities and / or the oxide sails.
- the metric weight of magnesium in the cored wire of the invention is much more accurate than the metric weight of magnesium contained in standard flux-cored wires, that is, made from magnesium powder.
- the ratio of diameters D2 / D1 is between 1.3 and 6.2. This interval was determined from the following criteria.
- the insulating intermediate layer In order for the insulating intermediate layer to be sufficiently effective, it must be sufficiently thick. It is therefore necessary that the space between the extruded bar and the outer sheath is large enough to contain the powder.
- a ratio D2 / D1 greater than or equal to 1, 3 guarantees the minimum space for the thermal protection of the powder of the intermediate layer is sufficient.
- a ratio D2 / D1 of less than or equal to 6.2 is based on both metallurgical and economic considerations. It ensures a minimum proportion of active substance (extruded bar 8) relative to the insulating substance. Too much imbalance generates significant thermal losses of the liquid metal bath to be treated (too much powder supply with respect to the supply of active substance), but also an increase in the cost price of the cored wire.
- the samples P1 to P4 are conventional filled cored wires, filled with powdery material whose characteristics are as follows:
- the samples P5 to P8 come from a cored wire according to the invention and whose characteristics are as follows:
- intermediate layer consisting of a mixture of FeSiBa, FeSiTR and CaSi powders
- the magnesium addition yield obtained with the samples P5 to P8 according to the invention is on average 26.7%, against 19.3% with the samples P1 to P4, an improvement of + 38%.
- range is the difference between the highest addition yield and the lowest addition yield. For samples P5 to P8, the range is reduced by 42% compared to samples P1 to P4. This improves the predictability of the magnesium injection and more certainly makes it possible to avoid a second injection due to an insufficient addition of Mg, thus to consume less active product and not to prolong the elaboration.
- the intermediate layer 10 can also play a major metallurgical role and makes it possible, for example, to limit the fading of magnesium over time, that is to say the decrease in the magnesium content of the molten iron after introduction of the wire. thicket. Since the solubility of magnesium in liquid iron is limited and this solubility is a function of temperature, its concentration decreases continuously with time.
- Magnesium is also a powerful deoxidizer and desulphurizer. Mg has a tendency to combine with oxygen to form MgO inclusions, becoming less and less effective with respect to the nodularization of graphite spherules. The effect of spheronization fades to sometimes become insufficient. The graphite then changes from a perfectly spheroidal shape to an irregular and jagged shape and finally vermicular if the magnesium content is too low. It is said that there is degeneration of the cast iron.
- the intermediate layer 10 may thus contain other deoxidizing elements than magnesium, for example cerium, but also the chemical elements of groups IIA and NIA of the periodic table, and / or inoculant elements such as silicon.
- deoxidizing elements for example cerium, but also the chemical elements of groups IIA and NIA of the periodic table, and / or inoculant elements such as silicon.
- Table 3 shows the samples tested and reference is made to Chart 3, which presents the results in which the curves C1 to C4 correspond to the evolution, as a function of time, of the proportion of Mg remaining in the cast, relative to the Mg introduced with the cored wire:
- Curve C5 corresponds to a lower limit below which it is not desired to go down in order to guarantee optimum quality of the castings.
- the four types of cored wires were tested under the same operating conditions (15 wire treatments), namely: a cylindrical treatment pocket whose height-to-diameter ratio of the metal column is 1, 5,
- the temperature of the melt is approximately 1470 to 1495 ° C
- the melting composition 3.70% C; 2, 40% Si; 0.006 - 0.013% S.
- the cored wires PFT25, PFT32 and PFT40 according to a preferred variant of the invention promote a slower fading of magnesium compared to the reference.
- the addition of 6% of barium in the intermediate layer thus makes it possible to extend the service life of the treated cast iron (residual value of Mg guaranteeing the quality of the castings) by 15 minutes (compared to the reference which does not is only 20 minutes).
- the intermediate layer 10 surrounding the extruded bar 8 significantly reduces the fading of magnesium over time. It has thus been shown that an intermediate layer 10 consisting of a powder comprising a combination of the cerium, calcium and barium elements makes it possible to obtain a longer residence time for the magnesium in the molten iron.
- the cored wire 1 may comprise an insulating layer extending longitudinally between the extruded bar 8 and the intermediate layer 10.
- the insulating layer includes, for example, paper, moistened paper, metallized paper or metal.
- the insulating layer makes it possible to adjust the overall heat transfer coefficient between the molten metal bath and the extruded bar 8.
- the insulating layer makes it possible to retard the complete melting of the cored wire 1.
- FIG. 1 there will now be described a cored wire 100 which is a variant of the cored wire 1 described above.
- the cored wire 100 is similar to the cored wire 1, so that it is the same Figures 1 and 2 which illustrate the cored wire 1 and the cored wire 100.
- Fluxed wire 100 differs mainly in its chemical composition and in its use.
- the cored wire 100 is for example intended to be introduced into a bath of molten steel (not shown).
- the outer shell 4 is made of steel. Alternatively, it can be aluminum, nickel, zinc or copper.
- the extruded bar 8 mainly comprises calcium.
- the extruded bar 8 is made of calcium of industrial purity of 98.5%.
- the extruded bar 8 may be wrapped with a thermally insulating layer extending longitudinally.
- the intermediate layer 10 comprises an iron powder. Alternatively, it may comprise powders of aluminum, magnesium and / or oxides such as slag.
- the outer envelope 4 has a thickness of about 0.4 mm
- the iron powder has a metric weight of approximately 300 g / m 2,
- the extruded bar 8 has a metric weight of 85 g / m and a diameter of about 8.5 mm.
- the cored wire 100 is implemented in a manner similar to the cored wire 1, for example to treat a molten steel bath with calcium.
- An interest of the cored wire 100 is that it develops the same metric weight of calcium as a standard flux cored wire CaFe 30% (mixture of calcium and iron powders in the proportions: 30% Ca - 70% Fe) . It can be used as a direct replacement for CaFe's standard flux-cored wires, with increased performances in terms of calcium treatment efficiency in the liquid steel ladle and a reduced standard deviation of efficiency, ie better predictability.
- the standard calcium treatment of molten steel ladles is done by injecting a CaFe cored wire of the state of the art. A pocket of 245 tons was used. A calcium content of the steel, before continuous casting, of 27 ppm was targeted.
- the outer casing of the cored wire has a thickness of 0.4 mm.
- the filling of the cored wire consists of a mixture of calcium and iron powders in the proportion by mass 30/70.
- the metric weight of the powder mixture is 275 g / m 2.
- the average length of cored wire injected is 620 m, at an injection speed of 290 m / min.
- the average addition yield is 12.9%.
- the standard deviation obtained in the tests is 7.6% (absolute percentage). Then, 152 pockets of the same molten steel were treated with the cored wire 100 according to the invention.
- the casing 4 of the cored wire 100 has a thickness of 0.4 mm.
- the lining of the cored wire 100 consists of a bar 8 of calcium whose diameter D1 is 8.5 mm and whose metric weight is 85 g / m and of an iron powder surrounding this bar 8 whose weight metric is 300 g / m.
- the diameter D of the cored wire 100 is similar to that of the standard cored wire, namely 13.6 mm.
- the average length of cored wire 100 injected was about 374 m, for the same injection speed of 290 m / min.
- the treatment time of the steel was reduced thanks to the flux-cored wire 100.
- the treatment lasted less than 80 seconds with the flux-cored wire 100, compared with 130 seconds with the CaFe wire of the state of the art.
- Reducing the amount of cored wire 100 consumed represents a significant saving in the cost of metallurgical treatment.
- a cored wire contains a powder or a mixture of powders whose purpose is to control the metric weight and the composition throughout the product.
- a conventional process for obtaining a cored wire comprises in particular the following steps:
- the dosage step of each of the powders makes it possible to respect the final proportion in each of the chemical elements in the packing. However, depending on the nature of the powders, this dosage is easily disturbed. For example, when using a supply treadmill, an overdose in one of the powders is possible by a falling effect. When the treadmill stops, the powder at the end can continue to flow due to its inertia. This effect is all the more marked as the powder has better flowability.
- the mixing step is the most complex. Most of the mixers present on the cored wire manufacturing lines are of the "plowshares" type. Blades integral with a central rotary axis mix the different powders dosed upstream. However, mixers of this type easily induce segregation phenomena powders they are supposed to mix. Depending on the densities of the powders considered relative to each other, some powders tend to accumulate in dead zones of the mixer, which locally changes the composition of the mixture. In addition, demixing phenomena between the powders can also take place.
- the removal of the mixture in the cored wire sometimes causes heterogeneities in the mixture. Indeed, during the removal of the mixture, segregation sometimes occurs, due in particular to the different trajectories of the powder particles or to the phenomenon of elutriation.
- an extruded bar reduces the risk of a wrong dosage of the powders and a bad mixture.
- the metric weight of the extruded bar is much better controlled.
- the metric weight of the active substance is much better controlled.
- this metric weight is independent of the density variations of the powders used.
- thermally insulating layer means an additional layer around the extruded bar.
- the additional layer makes it possible to delay the heat transfer from the outside of the cored wire towards its core when the cored wire is introduced into a bath of liquid metal.
- the additional layer is adapted to form an additional thermal barrier between the outer medium to the flux-cored wire (liquid metal) and the extruded bar. The propagation of heat is slowed down by the presence of the additional layer. The rise in temperature of the extruded bar is delayed.
- the effectiveness of the thermally insulating layer varies in particular according to its nature. Examples of thermally insulating layers are provided in the application FR-A-2871477 of the applicant.
- thermally insulating layer is advantageously located on the extruded bar and surrounding it for example completely further improves the thermal protection of the extruded bar.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL13792869T PL2917377T3 (en) | 2012-11-09 | 2013-11-08 | Cored wire for the metallurgical treatment of a bath of molten metal and corresponding method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1260678A FR2997963B1 (en) | 2012-11-09 | 2012-11-09 | OVEN WIRE FOR METALLURGICAL PROCESSING OF A FUSION METAL BATH AND METHOD THEREOF |
PCT/EP2013/073350 WO2014072456A1 (en) | 2012-11-09 | 2013-11-08 | Cored wire for the metallurgical treatment of a bath of molten metal and corresponding method |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2917377A1 true EP2917377A1 (en) | 2015-09-16 |
EP2917377B1 EP2917377B1 (en) | 2019-05-29 |
Family
ID=47598973
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13792869.3A Active EP2917377B1 (en) | 2012-11-09 | 2013-11-08 | Cored wire for the metallurgical treatment of a bath of molten metal and corresponding method |
Country Status (6)
Country | Link |
---|---|
US (1) | US20150267272A1 (en) |
EP (1) | EP2917377B1 (en) |
ES (1) | ES2743496T3 (en) |
FR (1) | FR2997963B1 (en) |
PL (1) | PL2917377T3 (en) |
WO (1) | WO2014072456A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024062016A1 (en) | 2022-09-22 | 2024-03-28 | Affival | Calcium-based flux-cored wire for the metallurgical treatment of a metal bath, and corresponding method |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3018524B1 (en) * | 2014-03-11 | 2017-03-10 | Affival | PROCESS FOR THE DESULFURATION OF A LIQUID IRON AND FILLED YARN FOR ITS IMPLEMENTATION |
CN104131136B (en) * | 2014-08-19 | 2016-03-16 | 马鞍山中科冶金材料科技有限公司 | A kind of molten iron, molten steel desulfurizing material and preparation method thereof |
US10927425B2 (en) * | 2017-11-14 | 2021-02-23 | P.C. Campana, Inc. | Cored wire with particulate material |
CA3031491C (en) * | 2019-01-03 | 2020-03-24 | 2498890 Ontario Inc. | Systems, methods, and cored wires for treating a molten metal |
CN110106310A (en) * | 2019-04-29 | 2019-08-09 | 无锡汇蓝新材料科技有限公司 | It is a kind of to fill out core high density composite core-spun yarn for the seamless of deoxidation in steel making |
RU2723863C1 (en) * | 2019-08-05 | 2020-06-17 | Общество с ограниченной ответственностью Новые перспективные продукты Технология | Wire with filler for out-of-furnace treatment of metallurgical melts |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3921700A (en) * | 1974-07-15 | 1975-11-25 | Caterpillar Tractor Co | Composite metal article containing additive agents and method of adding same to molten metal |
DE2923236C2 (en) * | 1979-06-08 | 1984-10-18 | Brown, Boveri & Cie Ag, 6800 Mannheim | Method and device for inoculating cast iron in a pressurized casting furnace |
US6053960A (en) * | 1997-12-30 | 2000-04-25 | Minerals Technologies, Inc. | Method of manufacture of cored wire for treating molten metal |
US6346135B1 (en) * | 1998-12-10 | 2002-02-12 | Minerals Technologies Inc. | Cored wire for treating molten metal |
DE19916235C2 (en) * | 1999-03-01 | 2001-03-08 | Odermath Stahlwerkstechnik | Cored wire for the treatment of melts by wire injection |
-
2012
- 2012-11-09 FR FR1260678A patent/FR2997963B1/en active Active
-
2013
- 2013-11-08 EP EP13792869.3A patent/EP2917377B1/en active Active
- 2013-11-08 WO PCT/EP2013/073350 patent/WO2014072456A1/en active Application Filing
- 2013-11-08 PL PL13792869T patent/PL2917377T3/en unknown
- 2013-11-08 US US14/441,148 patent/US20150267272A1/en not_active Abandoned
- 2013-11-08 ES ES13792869T patent/ES2743496T3/en active Active
Non-Patent Citations (1)
Title |
---|
See references of WO2014072456A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024062016A1 (en) | 2022-09-22 | 2024-03-28 | Affival | Calcium-based flux-cored wire for the metallurgical treatment of a metal bath, and corresponding method |
FR3140095A1 (en) | 2022-09-22 | 2024-03-29 | Affival | Calcium-based cored wire for metallurgical treatment of a metal bath and corresponding process |
Also Published As
Publication number | Publication date |
---|---|
WO2014072456A1 (en) | 2014-05-15 |
PL2917377T3 (en) | 2020-01-31 |
FR2997963A1 (en) | 2014-05-16 |
FR2997963B1 (en) | 2015-09-04 |
ES2743496T3 (en) | 2020-02-19 |
EP2917377B1 (en) | 2019-05-29 |
US20150267272A1 (en) | 2015-09-24 |
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