EP2976172A1 - Inoculant with surface particles - Google Patents

Inoculant with surface particles

Info

Publication number
EP2976172A1
EP2976172A1 EP14716891.8A EP14716891A EP2976172A1 EP 2976172 A1 EP2976172 A1 EP 2976172A1 EP 14716891 A EP14716891 A EP 14716891A EP 2976172 A1 EP2976172 A1 EP 2976172A1
Authority
EP
European Patent Office
Prior art keywords
particles
inoculant
cast iron
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.)
Granted
Application number
EP14716891.8A
Other languages
German (de)
French (fr)
Other versions
EP2976172B1 (en
Inventor
Thomas Margaria
Aurélie FAY
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ferroglobe France SAS
Original Assignee
Ferropem SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ferropem SAS filed Critical Ferropem SAS
Priority to SI201431959T priority Critical patent/SI2976172T1/en
Publication of EP2976172A1 publication Critical patent/EP2976172A1/en
Application granted granted Critical
Publication of EP2976172B1 publication Critical patent/EP2976172B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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 method of manufacturing said inoculant.
  • Cast iron is a well-known iron-carbon alloy and widely used for the manufacture of mechanical parts.
  • the melt is obtained by mixing the constituents of the alloy in the liquid state at a temperature of between 1150 ° C. and 1350 ° C. before pouring into a mold and cooling the alloy obtained.
  • the 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 iron undergoes an inoculation treatment to introduce graphitizing components into the cast iron which will favor the appearance of graphite rather than iron carbide when cooling the cast iron in the mold.
  • the formed graphite may 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.
  • the formation of spheroidal graphite can be promoted by a so-called nodulising treatment aimed primarily at providing the magnesium melt in sufficient quantity so that the graphite can grow so as to form round particles (spheroids).
  • nodulising components may be included in the inoculant alloy, for example.
  • Mention may also be made of the addition of desulphurizing products, or of products making it possible to specifically treat certain defects of the cast iron as a function of the initial composition of the molten bath, such as micro-shrinkage, which may appear during cooling. It may include lanthanum and rare earths.
  • These treatments can be performed in one or more times and at different times during the manufacture of the cast iron.
  • additions of inoculants are known in the bag, before casting of the cast iron in the mold (inoculation in the bag), during casting, or in the casting stream (late inoculation).
  • inoculants are conventionally made from a ferro-silicon type alloy FeSi6 5 or FeSi 75 with adjustment of chemistry according to target composition of the inoculant.
  • the adjustment is possible in oven or in pocket, with often poor yields depending on the elements to be added. It can also be mixtures of several alloys.
  • the inoculation efficiency of the cast iron part also depends on its thickness.
  • 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 (carbon content, silicon, initial sulfur, in particular, etc.) .
  • the present invention aims to provide a new product inoculant for the treatment of melting in the liquid phase, responding to all or part of these constraints.
  • a particulate inoculant in powder form, comprising, on the one hand, support particles made of a fusible material in liquid iron, and on the other hand, surface particles made of a material that promotes germination and growth of graphite, arranged and distributed discontinuously on the surface of the support particles, the surface particles having a particle size such that their d50 is less than or equal to one tenth of the d50 of the support particles.
  • 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 or coating, provided that the support particle is protected from access to the liquid iron when the inoculant is incorporated therein.
  • the surface particles have a particle size smaller than that of the support particles. It has been surprisingly found 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, had a profile of dissolution and inoculation responding to the problems mentioned.
  • the difference in kind between the support particles and the support particles can further be expressed in the constituent materials of the particles, respectively.
  • the inoculant effect is provided by the support particle / particle array disposed at the surface and not by adjusting the chemical composition of an alloy, the The incorporation efficiencies of the added elements are greatly improved.
  • the support particles have low inoculating properties.
  • low or medium inoculants that can be dope by this means.
  • the carrier particles have inoculant properties for compositions or conditions different from those for which the whole carrier particles and surface particles act.
  • the support particles are made from silicon, whose proportion is variable, up to 100% by weight relative to the mass of the support particles.
  • the support particles may be made from carbon, whose proportion is variable, up to 100% by weight relative to the mass of the support particles. If necessary, it is in the form of graphite. Associated with silicon, it can be in the form of silicon carbide, for example.
  • the carrier particles contain at least 40% by weight 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, especially in allied form, at least one addition element, such as aluminum or calcium, especially between 0.2 and 5% by weight for each element of addition, relative to the mass of the support particles.
  • the carrier particles comprise, especially in allied form, at least one treatment element with an anti-shrinkage effect, in particular in an amount of between 0.5 and 6% by weight, relative to the weight of the carrier particles.
  • the proportion of surface particles is 1 to 8% by weight, preferably 1 to 5%, relative to the mass of the inoculant.
  • the surface particles are distributed substantially homogeneously on the surface of the support particles, in particular within a batch of particles.
  • the surface particles, until the 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 metal elements, such as aluminum, bismuth and manganese, silicides, especially iron, rare earths and calcium, oxides, such as aluminum oxides. , calcium, silicon or barium, metal sulphides, especially iron, calcium and rare earths, sulphates, in particular barium, and carbon black.
  • metal elements such as aluminum, bismuth and manganese, silicides, especially iron, rare earths and calcium, oxides, such as aluminum oxides.
  • oxides such as aluminum oxides.
  • calcium, silicon or barium metal sulphides, especially iron, calcium and rare earths, sulphates, in particular barium, and carbon black.
  • the invention also relates to a method of manufacturing an inoculant of the invention.
  • a first step of the process there are support particles in a meltable material in liquid iron, having a particle size ranging from 0.2 to 7 mm, on the one hand, and surface particles 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 ranging from 0.2 to 7 mm By particle size ranging from 0.2 to 7 mm, the conventional particle sizes in the range of inoculants of cast iron, namely the particle sizes 0.2-0.5 mm, 0.4-2 mm and 2-7 mm, are included.
  • 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, by example of 1000 to 1500 revolutions / min, to obtain an encrustation deposition of the surface particles on the surface of the support particles, in a discontinuous distribution.
  • a binder in the first step, is also available in a solvent, then in the second step, the carrier particles, the surface particles and the binder are mixed, and the solvent of the binder, for example by evaporation.
  • the carrier particles, the surface particles and the binder can be added at the same time or successively, in any order. For example, premixing of the surface particles in the binder solution can be performed, to which the carrier 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
  • a preferred method of the invention consists in using support particles made of an FeSi material containing aluminum and calcium, and / or surface particles made of a material chosen from aluminum, bismuth and silicides, especially from iron, rare earths and calcium, oxides, such as oxides of aluminum, calcium, silicon or barium, metal sulphides, especially iron, calcium and rare earths, sulphates, in particular barium, and black of carbon.
  • FIG. 1 is an overall scanning electron microscope view of a batch of particulate inoculant according to the invention comprising support particles (black) on the surface of which are fixed surface particles (white) conferring on the together a strong inoculating power.
  • FIG. 2 is a zoom of FIG. 1 on an inoculant particle according to the invention.
  • An inoculant according to the invention may be manufactured in the following manner.
  • a FeSi alloy containing 1% by weight of aluminum and 1.5% by weight 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.
  • the minimum fluidization speed is determined conventionally, then the air flow rate is kept substantially constant and higher than this minimum speed.
  • the temperature inside the reactor is raised 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 on whose surface the inoculant particles will be fixed.
  • the surface particles will be particles of calcium silicide CaSi and metallic aluminum, both having particle sizes less than 400 micrometers.
  • the surface particles to be fixed are premixed with a binder in aqueous solution, and then injected into the reactor in about 30 minutes at a temperature of 100 ° C.
  • the whole surface particles, carrier particles and binder are fluidized and heated until the introduced water has been completely evaporated. It will be possible to control the evaporation of 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 to evaluate the effectiveness of the coating. This characterization can be made in particular by scanning electron microscope control.
  • the binder used may be of organic or polymeric binder type, such as, for example, binders of polyvinyl alcohol (PVA), cellulose (CMC) and polyvinylpyrrolidone (PVP) type.
  • PVA polyvinyl alcohol
  • CMC cellulose
  • PVP polyvinylpyrrolidone
  • the amount of water used for the dilution of the binder obviously depends on the solubility of the latter in the water and should be adapted accordingly.
  • inorganic binders in particular of sodium silicate type, as well as hydraulic binders of the cement or lime type.
  • the nature of the binder used may depend on the inoculant materials and supports used.
  • the amount of binder used will be calculated so as to best allow the almost total fixing 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 stickiness and will also have to be adapted accordingly. In particular, it will be possible to carry out tests and visual verification using a scanning electron microscope in particular.
  • the amount of binder used may be between 0.001 and 1% by weight of binder relative to the total mass of the particles (carrier particles and surface particles).
  • approximately 500 kg of FeSi 7 o containing 1% by mass of AI and 1, 5% by weight of Ca, of particle size 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 raised to 100 ° C.
  • These particles are the support particles.
  • a suspension is carried out with PVP and water. 8% of surface particles, containing Bi bismuth and ferro-silico-rare earth FeSiTR alloy, both with a particle size ⁇ 200 ⁇ are added to the PVP + water solution, and then suspended.
  • This suspension is then injected at a rate of 10% by weight into the reactor for about 40 minutes 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 is completely dried.
  • approximately 1000 kg of FeSi 7 o containing 1% by weight of AI and 1, 5% by weight of Ca, with a particle size of 2 - 7 mm and approximately 50 kg of aluminum powder of particle size ⁇ 300 ⁇ m are introduced into a fluidized bed reactor. All the particles are fluidized by injection of depleted air. The temperature inside the reactor is raised to 100 ° C. A suspension is carried out with PVP and water. This suspension is then injected at a rate of 10% by weight into the reactor for about 40 minutes 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 is completely dried.
  • the implementation of the process is not limited to the use of a fluidized bed reactor and other coating techniques can be used. In particular, the following methods may be mentioned.
  • 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 inlay of the fine surface particles into the larger particles of FeSi (carrier particles).
  • Such a mechanical incrustation does not require the use of a binder and it is then called dry coating and cold.
  • the FeSi 7 type support particles containing mainly the FeSi 2 , 4 and Si phases can be directly encrusted with the surface particles.
  • a second method is the use of a high shear mixer.
  • mixing is carried out at a greater or lesser speed (between 50 and 500 rpm, for example) in a mixer of the mixer granulator type, in the presence of a binder (examples mentioned above).
  • a drying step is performed to remove water from the binder.
  • Drying means can equip the mixer. It may especially be a burner ramp, for example gas, heating the outside of the mixer by conduction; a heating mat, for example silicone, surrounding in particular the walls of the mixer; or any other system for bringing the powder inside the mixer to a temperature between 80 and 150 ° C to remove water.
  • a burner ramp for example gas, heating the outside of the mixer by conduction
  • a heating mat for example silicone, surrounding in particular the walls of the mixer
  • the mixer systems used, of the drum or granulator type must allow movement of the powder inside said mixer resulting in efficient mixing and some regularity of the bonding.
  • the mixer may be equipped with stirring fins on its walls or a granulator mixer with central or remote rotation system along one or two axes.
  • the process of the invention can be carried out indifferently continuously, or discontinuously batchwise.
  • the support and surface particles may be added together or separately. When added together, it may be advantageously premixed before adding the binder to ensure the 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 introduced preferentially continuously.
  • support particles based on FeSi it is of course possible to use other materials conventionally used in foundry, and in particular SiC or graphite support particles. The manufacturing examples should simply be transposed to these materials.
  • the examples are given for most common use cases with an inoculant according to the invention, the support particle of which is of FeSi type.
  • inoculants according to the invention comprising other types of support particles such as silicon carbide or graphite, these materials are, however, used less frequently in the foundry.
  • a spheroidal graphite cast iron bath was treated at a rate of 0.3% by weight with an alloy inoculant type FeSi May 7, and containing 0.8% by weight of aluminum and 0.7% by mass of calcium .
  • the treatment is carried out by adding the inoculant into the cast iron bag, before filling the mold.
  • the residual magnesium of the cast iron is 400 thousandths.
  • the cast iron was then poured into a mold of the BCIRA type.
  • the treated cast has the following characteristics:
  • a spheroidal graphite cast iron bath was treated at a level of 0.3% by weight with an inoculant according to the invention having the following composition:
  • Binder 10% by weight of an aqueous solution of PVP - Deposition of the surface particles by bonding carried out by fluidization at 100 ° C.
  • the treatment is carried out by adding the inoculant into the cast iron bag, before filling the mold.
  • the amount of carbon equivalent of the cast iron (Ceq) is 4.32%.
  • the residual magnesium of the cast iron is 400 thousandths.
  • the cast iron was then poured into a mold of the BCIRA type.
  • the treated cast has the following characteristics:
  • Example 3 inoculant according to the invention
  • FeSiTR ferro-silico-rare earth alloy
  • Binder 10% by weight of an aqueous solution of PVP - Deposition of the surface particles by bonding carried out by fluidization at
  • the treatment is carried out by adding the inoculant into the cast iron bag, before filling the mold.
  • the amount of carbon equivalent (Ceq) of the cast iron is 4.32%.
  • the residual magnesium is 420 thousandths.
  • the cast iron is cast in a BCIRA mold.
  • the cast iron has the following characteristics:
  • a bath of spheroidal graphite cast iron was treated at a rate of 0.3% by weight with an inoculant conventionally developed type FeSi May 7, and containing 1, 2% by weight of aluminum, 1, 5% by mass calcium and 1.5% by weight of zirconium.
  • the treatment is carried out by adding the inoculant into the cast iron bag, before filling the mold.
  • the amount of carbon equivalent of the cast iron (Ceq) is 4.32%.
  • the residual magnesium of the cast iron is 400 thousandths.
  • the cast iron was then poured into a mold of the BCIRA type.
  • the treated cast has the following characteristics:
  • the treatment is carried out by adding the inoculant into the cast iron bag, before filling the mold.
  • the amount of carbon equivalent of the cast iron (Ceq) is 4.3%.
  • the cast iron is cast in a BCIRA mold.
  • the cast iron has the following characteristics:
  • Binder 5% by weight of an aqueous solution of cement
  • the treatment is carried out by adding the inoculant into the cast iron bag, before filling the mold.
  • the amount of carbon equivalent of the cast iron (Ceq) is 4.3%.
  • the cast iron is cast in a BCIRA mold.
  • the cast iron has the following characteristics:
  • the treatment is carried out by adding the inoculant into the cast iron bag, before filling the mold.
  • the cast iron has the following characteristics:
  • Example 8 Pieces of different thicknesses - inoculant according to the invention
  • Binder 2% by weight of an aqueous solution of PVP
  • the treatment is carried out by adding the inoculant to the jet during filling of the mold.
  • the amount of carbon equivalent of the cast iron (Ceq) is 4.32%.
  • the cast iron is then cast in a mold to manufacture a part having different thicknesses: 4 mm and 25 mm.
  • the cast iron On the casting on the 4 mm thick part, the cast iron has the following characteristics:
  • the cast iron On the casting, on the 25 mm thick part, the cast iron has the following characteristics:
  • Example 9 Parts of different thicknesses - inoculant according to the prior art
  • the treatment is carried out by adding the inoculant to the jet during filling of the mold.
  • the amount of carbon equivalent of the cast iron (Ceq) is 4.31%.
  • the cast iron is then cast in a mold to manufacture a part having different thicknesses: 4 mm and 25 mm.
  • the cast iron On the casting on the 4 mm thick part, the cast iron has the following characteristics:
  • the cast iron On the casting, on the 25 mm thick part, the cast iron has the following characteristics:
  • Type VI graphite 73 '
  • Binder 10% by weight of an aqueous solution of cement
  • the treatment is carried out by adding the inoculant into the tundish during the filling of the mold.
  • the amount of carbon equivalent of the cast iron (Ceq) is 4.33%.
  • the cast iron is then poured into a mold to make a thick piece (170mm).
  • the cast iron has the following characteristics:
  • the treatment is carried out by adding the inoculant into the tundish during the filling of the mold.
  • the amount of carbon equivalent of the cast iron (Ceq) is 4.31%.
  • the cast iron is then cast in a mold to make a thick piece: 170 mm.
  • the cast iron has the following characteristics:

Abstract

The invention relates to a particulate inoculant for treating a melt in a liquid phase, comprising support particles in a meltable material in the liquid melt, and surface particles in a material that stimulates the nucleation and growth of graphite, that are arranged and distributed discontinuously on the surface of the support particles, the surface particles having a particle size distribution such that the d50 thereof is lower than, or equal to, a tenth of the d50 of the support particles.

Description

INOCULANT A PARTICULES DE SURFACE  INOCULANT WITH SURFACE PARTICLES
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 method of manufacturing 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 1 135°C et 1350°C avant coulée dans un moule et refroidissement de l'alliage obtenu.  Cast iron is a well-known iron-carbon alloy and widely used for the manufacture of mechanical parts. The melt is obtained by mixing the constituents of the alloy in the liquid state at a temperature of between 1150 ° C. and 1350 ° C. before pouring into 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, the 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 associates with iron and forms iron carbide FesC (also called cementite), the resulting iron is called white cast 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 melt is called gray cast 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 of carbon in graphite form and to limit as much as possible the formation of these iron carbides which harden and weaken 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 associate 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 melt 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 iron undergoes an inoculation treatment to introduce graphitizing components into the cast iron which will favor the appearance of graphite rather than iron carbide when cooling the cast iron in the mold.
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, ... 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. In general, the components of an inoculant are elements promoting the formation of graphite during the solidification of the cast iron. By way of example, mention may be made of carbon, silicon, calcium, aluminum, etc. Of course, an inoculant may also be designed to perform other functions and include for this purpose 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. Ainsi, 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).  In particular, it may be desired, depending on the desired properties, for the formed graphite 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. Thus, for example, the formation of spheroidal graphite can be promoted by a so-called nodulising treatment aimed primarily at providing the magnesium melt in sufficient quantity so that the graphite can grow so as to form round particles (spheroids).
Ces composants nodulisants peuvent être inclus dans l'alliage inoculant, par exemple.  These nodulising components may be included in the inoculant alloy, for example.
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 desulphurizing products, or of products making it possible to specifically treat certain defects of the cast iron as a function of the initial composition of the molten bath, such as micro-shrinkage, which may appear during cooling. It may include 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 performed in one or more times and at different times during the manufacture of the cast iron. In particular, additions of inoculants are known in the bag, before casting of the cast iron in the mold (inoculation in the bag), during casting, or in the casting stream (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 made from a ferro-silicon type alloy FeSi6 5 or FeSi 75 with adjustment of chemistry according to target composition of the inoculant. The adjustment is possible in oven or in pocket, with often poor yields depending on the elements to be added. It 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. 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. Conversely, in areas of greater thickness, cooling will be slower and promote the formation of graphite. However, in the thick parts, the cooling may be too slow and the formed graphite may lose its nodularity near the center of the room. It follows that the parts with areas of different thickness may have physico-chemical structures different from one area 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 for inoculating cast iron parts of different thicknesses by limiting the risk of degeneration of the graphite and the formation of carbides, and to ensure a good uniformity of the metallurgical structure of an area 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 ...).  Moreover, 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 (carbon content, silicon, initial sulfur, 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 is obviously desirable that such an inoculant does not require a higher addition rate to known products and that it retains good dissolution properties in the cast iron, similar to these products and does not generate substantially more than dross and dairy than these.
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, et d'autre part, des particules de surface en un matériau favorisant la germination et la croissance de graphite, disposées et réparties de manière discontinue à la surface des particules support, les particules de surface présentant une granulométrie telle que leur d50 est inférieur ou égal à un dixième du d50 des particules support..  To do this, the present invention aims to provide a new product inoculant for the treatment of melting in the liquid phase, responding to all or part of these constraints. For this purpose, it supplies a particulate inoculant, in powder form, comprising, on the one hand, support particles made of a fusible material in liquid iron, and on the other hand, surface particles made of a material that promotes germination and growth of graphite, arranged and distributed discontinuously on the surface of the support particles, the surface particles having a particle size 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.  Thus disposed, 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 or coating, provided that the support particle is protected from access to the liquid 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 above, the surface particles have a particle size smaller than that of the support particles. It has been surprisingly found 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, had a profile of dissolution and inoculation responding to the problems mentioned. The difference in kind between the support particles and the 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.  In particular, it has been found that such a physico-chemical structure strongly limits the degeneration of graphite in the center of pieces of high thickness. Such a structure also makes it possible to greatly improve the homogeneity of the inoculation, and more particularly for the pieces 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.  Moreover, compared to a conventional oven-baking technique, since the inoculant effect is provided by the support particle / particle array disposed at the surface and not by adjusting the chemical composition of an alloy, the The incorporation efficiencies 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 inoculating properties. Thus, thanks to the invention, it will be possible to use low or medium inoculants that can be dope 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 carrier particles have inoculant properties for compositions or conditions different from those for which the whole carrier particles and surface particles act.
Avantageusement, les particules support sont réalisées à partir de silicium, dont la proportion est variable, pouvant atteindre 100% en masse par rapport à la masse des particules support.  Advantageously, the support particles are made from silicon, whose proportion is variable, up to 100% by weight relative to the mass of the support particles.
De manière complémentaire ou alternative, les particules support pourront être réalisées à partir de carbone, dont la proportion est variable, pouvant atteindre 100% en masse par rapport à la masse des particules support. Le cas échéant, il est sous forme de graphite. Associé au silicium, il peut se présenter sous la forme de carbure de silicium par exemple.  Complementarily or alternatively, the support particles may be made from carbon, whose proportion is variable, up to 100% by weight relative to the mass of the support particles. If necessary, it is in the form of graphite. Associated with silicon, it can be in the form of silicon carbide, for example.
Avantageusement encore, les particules support contiennent au moins 40 % en masse de silicium par rapport à la masse des particules support.  Advantageously, the carrier particles contain at least 40% by weight of silicon relative to the mass of the support particles.
De manière préférentielle, les particules support sont réalisées à partir d'un alliage, plus particulièrement ferreux.  Preferably, 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, tel que de aluminium ou du calcium, 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, especially in allied form, at least one addition element, such as aluminum or calcium, especially between 0.2 and 5% by weight for each element of addition, 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.  Advantageously, the carrier particles comprise, especially in allied form, at least one treatment element with an anti-shrinkage effect, in particular in an amount of between 0.5 and 6% by weight, relative to the weight of the carrier 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 1 to 8% by weight, preferably 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 substantially homogeneously 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 the 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, parmi des éléments métalliques, tels qu'aluminium, bismuth et manganèse, des siliciures, notamment de fer, terres rares et calcium, des oxydes, tels qu'oxydes d'aluminium, de calcium, de silicium ou de baryum, des sulfures métalliques, notamment de fer, calcium et terres rares, des sulfates, notamment de baryum, et du noir de carbone.  Advantageously, the surface particles are chosen, individually or as a mixture, from metal elements, such as aluminum, bismuth and manganese, silicides, especially iron, rare earths and calcium, oxides, such as aluminum oxides. , calcium, silicon or barium, metal sulphides, especially iron, calcium and rare earths, sulphates, in particular barium, and carbon black.
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 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 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 œuvre par toute technique bien connue de l'homme du métier.  The invention also relates to a method of manufacturing an inoculant of the invention. According to a first step of the process, there are support particles in a meltable material in liquid iron, having a particle size ranging from 0.2 to 7 mm, on the one hand, and surface particles 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 ranging from 0.2 to 7 mm, the conventional particle sizes in the range of inoculants of cast iron, namely the particle sizes 0.2-0.5 mm, 0.4-2 mm and 2-7 mm, are included.
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 one variant of the invention, the deposition of the surface particles is carried out mechanically, by incrustation. For this purpose, the support particles and the surface particles are mixed, dry, at high speed, by example of 1000 to 1500 revolutions / min, to obtain an encrustation deposition of the surface particles on the surface of the support particles, in 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, a binder is also available in a solvent, then in the second step, the carrier particles, the surface particles and the binder are mixed, and the solvent of the binder, for example by evaporation. As will be described in more detail, the carrier particles, the surface particles and the binder can be added at the same time or successively, in any order. For example, premixing of the surface particles in the binder solution can be performed, to which the carrier 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.
Un procédé préféré de l'invention consiste à utiliser des particules support en un matériau FeSi contenant de l'aluminium et du calcium, et/ou des particules de surface en un matériau choisi parmi l'aluminium, le bismuth, les siliciures, notamment de fer, terres rares et calcium, des oxydes, tels qu'oxydes d'aluminium, de calcium, de silicium ou de baryum, des sulfures métalliques, notamment de fer, calcium et terres rares, des sulfates, notamment de baryum, et du noir de carbone.  A preferred method of the invention consists in using support particles made of an FeSi material containing aluminum and calcium, and / or surface particles made of a material chosen from aluminum, bismuth and silicides, especially from iron, rare earths and calcium, oxides, such as oxides of aluminum, calcium, silicon or barium, metal sulphides, especially iron, calcium and rare earths, sulphates, in particular barium, and black of carbon.
La présente invention sera mieux comprise à la lumière de la description détaillée et des exemples de mises en œuvre qui suivent en regard du dessin annexé dans lequel :  The present invention will be better understood in the light of the detailed description and examples of implementations which follow with reference to the appended drawing in which:
- 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.  FIG. 1 is an overall scanning electron microscope view of a batch of particulate inoculant according to the invention comprising support particles (black) on the surface of which are fixed surface particles (white) conferring on the together a strong inoculating power.
- la figure 2 est un zoom de la figure 1 sur une particule inoculante selon l'invention.  FIG. 2 is a zoom of FIG. 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 manner.
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 a FeSi alloy containing 1% by weight of aluminum and 1.5% by weight 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 rate is kept substantially constant and higher 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 raised 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 on whose surface 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.  In the present example, the surface particles will be 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.  We will use 5% by weight of these surface particles, about 25 kilograms of this mixture of particles CaSi and Al.
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 fixation on the support particles, the surface particles to be fixed are premixed with a binder in aqueous solution, and 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 the binder, the whole surface particles, carrier particles and binder are fluidized and heated until the introduced water has been completely evaporated. It will be possible to control the evaporation of 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 to evaluate the effectiveness of the coating. This characterization can be made in particular by scanning electron microscope control.
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 organic or polymeric binder type, such as, for example, binders of polyvinyl alcohol (PVA), cellulose (CMC) and polyvinylpyrrolidone (PVP) type. Of course, this list is not limiting.
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 amount of water used for the dilution of the binder obviously depends on the solubility of the latter in the water and should 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. Bien évidemment, la nature du liant utilisé pourra dépendre des matériaux inoculants et supports utilisés. It is also possible to envisage the use of inorganic binders, in particular of sodium silicate type, as well as hydraulic binders of the cement or lime type. Of course, 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 amount of binder used will be calculated so as to best allow the almost total fixing 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 stickiness and will also have to be adapted accordingly. In particular, it will be possible to carry out tests and visual verification using a scanning electron microscope in particular. Typically, the amount of binder used may be between 0.001 and 1% by weight of binder relative to the total mass of the particles (carrier particles and surface particles).
Selon un autre exemple possible de fabrication de l'inoculant selon l'invention, environ 500 kg de FeSi7o 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 <200μηη 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 7 o containing 1% by mass of AI and 1, 5% by weight of Ca, of particle size 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 raised to 100 ° C. These particles are the support particles. A suspension is carried out with PVP and water. 8% of surface particles, containing Bi bismuth and ferro-silico-rare earth FeSiTR alloy, both with a particle size <200μηη are added to the PVP + water solution, and then suspended. This suspension is then injected at a rate of 10% by weight into the reactor for about 40 minutes 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 is completely dried.
Selon encore un autre exemple possible de fabrication de l'inoculant selon l'invention, environ 1000 kg de FeSi7o 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 <300μηη 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. Bien évidemment, la mise en œuvre 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. According to yet another possible example of manufacture of the inoculant according to the invention, approximately 1000 kg of FeSi 7 o containing 1% by weight of AI and 1, 5% by weight of Ca, with a particle size of 2 - 7 mm and approximately 50 kg of aluminum powder of particle size <300 μm are introduced into a fluidized bed reactor. All the particles are fluidized by injection of depleted air. The temperature inside the reactor is raised to 100 ° C. A suspension is carried out with PVP and water. This suspension is then injected at a rate of 10% by weight into the reactor for about 40 minutes 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 is completely dried. Of course, the implementation of the process is not limited to the use of a fluidized bed reactor and other coating techniques can be used. In particular, the following methods may be mentioned.
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 inlay of the fine surface particles into the larger particles of FeSi (carrier particles). Such a mechanical incrustation does not require the use of a binder and it is then called dry coating and cold. The FeSi 7 type support particles containing mainly the FeSi 2 , 4 and Si phases can be directly encrusted with 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, mixing is carried out at a greater or lesser speed (between 50 and 500 rpm, for example) in a mixer of the mixer granulator type, in the presence of a binder (examples mentioned above). After mixing, a drying step is performed to remove 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.  Drying means can equip the mixer. It may especially be a burner ramp, for example gas, heating the outside of the mixer by conduction; a heating mat, for example silicone, surrounding in particular the walls of the mixer; or any other system for bringing the powder inside the mixer to a temperature between 80 and 150 ° C to remove 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 efficient mixing and some 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.  For this purpose, the mixer may be equipped with stirring fins on its walls or a granulator mixer with central or remote 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 process of the invention can be carried out indifferently continuously, or discontinuously batchwise.
Lors de la mise en œuvre, les particules support et de surface peuvent être ajoutées soit ensemble, soit de manière séparée. Lorsqu'elles sont ajoutées ensemble, elle pourront être avantageusement pré-mélangées, avant ajout du liant pour assurer le collage. During implementation, the support and surface particles may be added together or separately. When added together, it may be advantageously premixed before adding the binder to ensure the 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 introduced preferentially 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 SiC or graphite support particles. The manufacturing examples should simply be transposed 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 melt 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 method, the examples are given for most common use cases with an inoculant according to the invention, the support particle of which is of 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 does not in any way prevent the use of inoculants according to the invention comprising other types of support particles such as silicon carbide or graphite, these materials are, however, used less frequently in the foundry.
Exemple 1 : inoculant selon l'art antérieur (référence) Example 1 Inoculant According to the Prior Art (Reference)
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 spheroidal graphite cast iron bath was treated at a rate of 0.3% by weight with an alloy inoculant type FeSi May 7, and containing 0.8% by weight 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 into the cast iron bag, before filling the mold.
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 amount of carbon equivalent of the 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 the 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 mold of the BCIRA type.
A une épaisseur de 6 mm, la fonte traitée présente les caractéristiques suivantes :  At a thickness of 6 mm, the treated cast has the following characteristics:
- Structure de la matrice : 55 % perlite, 15 % ferrite, 30 % cémentite - Matrix structure: 55% perlite, 15% ferrite, 30% cementite
- Nombre de nodules par mm2 : 270 - Graphite de type VI : 57 % - Number of nodules per mm 2 : 270 - Type VI graphite: 57%
- Nodularité moyenne : 85 %  - Average nodularity: 85%
- Diamètre moyen : 16,2 microns Exemple 2 : inoculant selon l'invention  - Average diameter: 16.2 microns Example 2: inoculant according to the invention
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 :  A spheroidal graphite cast iron bath was treated at a level of 0.3% by weight with an inoculant according to the invention having the following composition:
- Alliage de particule support : FeSi75, et contenant 0,8 % en masse d'aluminium et 0,7 % en masse de calcium - Support particle alloy: FeSi 7 5, and containing 0.8% by weight of aluminum and 0.7% by weight of 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 Surface particles: 1.5% by weight of CaSi particles having a size of less than 50 microns and 1.5% by weight of metal aluminum particles smaller than 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. Binder: 10% by weight of an aqueous solution of PVP - Deposition of the 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 into the cast iron bag, before filling the mold.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,32 %. Le magnésium résiduel de la fonte est à 400 millièmes. The amount of carbon equivalent of the cast iron (Ceq) is 4.32%. 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 mold of the BCIRA type.
A une épaisseur de 6 mm, la fonte traitée présente les caractéristiques suivantes :  At a thickness of 6 mm, the treated cast has the following characteristics:
- Structure de la matrice : 45 % perlite, 50 % ferrite, 5 % cémentite - Nombre de nodules par mm2 : 540 - Matrix structure: 45% perlite, 50% ferrite, 5% cementite - Number of nodules per mm 2 : 540
- Graphite de type VI : 59 %  - Type VI graphite: 59%
- Nodularité moyenne : 92 %  - Average nodularity: 92%
- Diamètre moyen : 18,7 microns Exemple 3 : inoculant suivant l'invention  - Average diameter: 18.7 microns Example 3: inoculant according to the invention
Traitement d'un bain de fonte à graphite sphéroïdal à 0,3 % en masse avec un produit constitué :  Treatment of a spheroidal graphite cast iron bath at 0.3% by weight with a product consisting of:
- 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 <10Όμηη, et 2,5 % en masse de particules de l'alliage ferro-silico-terres rares (FeSiTR) de taille <100μηη. a support alloy: FeSi 75 with Al = 0.8% by weight and Ca = 0.7% by weight particles on the surface: 2.5% of Bismuth Bi particles of size <10Όμηη, and 2.5% by weight of particles of the ferro-silico-rare earth alloy (FeSiTR) of size <100μηη.
- Liant : 10% en masse d'une solution aqueuse de PVP - Dépôt des particules de surface par collage réalisé par fluidisation à Binder: 10% by weight of an aqueous solution of PVP - Deposition of the surface particles by bonding carried out by fluidization at
100°C. 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 into the cast iron bag, before filling the mold.
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 the cast iron is 4.32%. The residual magnesium is 420 thousandths.
La fonte est coulée dans un moule BCIRA.  The cast iron is cast in a BCIRA mold.
A l'épaisseur de 6 mm, la fonte présente les caractéristiques suivantes :  At a thickness of 6 mm, the cast iron has the following characteristics:
- Structure de la matrice = 50 % Perlite - 50 % Ferrite - 0 % de cémentite  - Structure of the matrix = 50% Perlite - 50% Ferrite - 0% cementite
- Nombre de nodules/mm2 = 570 - Number of nodules / mm 2 = 570
- Graphite de type VI = 62 %  - Type VI graphite = 62%
- Nodularité moyenne = 92 %  - Average nodularity = 92%
- Diamètre moyen = 17,8μηη  - Average diameter = 17.8μηη
Exemple 4 : inoculant suivant l'art antérieur Example 4 Inoculant According to the Prior Art
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 bath of spheroidal graphite cast iron was treated at a rate of 0.3% by weight with an inoculant conventionally developed type FeSi May 7, and containing 1, 2% by weight of aluminum, 1, 5% by mass 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 into the cast iron bag, before filling the mold.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,32 %. The amount of carbon equivalent of the cast iron (Ceq) is 4.32%.
Le magnésium résiduel de la fonte est à 400 millièmes. La fonte a ensuite été coulée dans un moule de type BCIRA. The residual magnesium of the cast iron is 400 thousandths. The cast iron was then poured into a mold of the BCIRA type.
A une épaisseur de 6 mm, la fonte traitée présente les caractéristiques suivantes :  At a thickness of 6 mm, the treated cast has the following characteristics:
- Structure de la matrice : 45 % perlite, 50 % ferrite, 5 % cémentite - Matrix structure: 45% perlite, 50% ferrite, 5% cementite
- Nombre de nodules par mm2 : 505 - Number of nodules per mm 2 : 505
- Graphite de type VI : 59 %  - Type VI graphite: 59%
- Nodularité moyenne : 87 % - Diamètre moyen : 18,9 microns - 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 is seen that to obtain substantially the same results, it would be necessary to greatly increase the amounts of inoculant components and introduce zirconium, compared to an inoculant having a structure according to our invention.
Exemple 5: inoculant suivant l'art antérieur Example 5 Inoculant According to the Prior Art
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 lamellar graphite cast iron bath at 0.3% by weight with a base product FeSi 75 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 into the cast iron bag, before filling the mold.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,3 %. The amount of carbon equivalent of the cast iron (Ceq) is 4.3%.
La fonte est coulée dans un moule BCIRA. The cast iron is cast in a BCIRA mold.
A l'épaisseur de 6 mm, la fonte présente les caractéristiques suivantes :  At a thickness of 6 mm, the cast iron has the following characteristics:
- Nombre de cellules eutectiques/mm2: 0,2 - Number of eutectic cells / mm 2 : 0.2
- 40 % cémentite Exemple 6: inoculant suivant l'invention  - 40% cementite Example 6: inoculant according to the invention
Traitement d'un bain de fonte de graphite lamellaire à 0,3 % en masse avec un produit constitué :  Treatment of a lamellar graphite cast iron bath at 0.3% by weight with a product consisting of:
- d'un alliage support: FeSi 75 avec Al = 1 ,0 % en masse et Ca = 1 ,5 % en masse.  a support alloy: FeSi 75 with Al = 1.0% by weight and Ca = 1.5% by weight.
- de particules en surface : 5 % en masse de particules de sulfate de baryum BaSO4 de taille <100μηη surface particles: 5% by mass of BaSO 4 barium sulphate particles of size <100μηη
- Liant : 5% en masse d'une solution aqueuse de ciment Binder: 5% by weight of an aqueous solution of cement
- Dépôt des particules de surface par collage réalisé par fluidisation à 100°C. - 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 into the cast iron bag, before filling the mold.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,3 %. La fonte est coulée dans un moule BCIRA.  The amount of carbon equivalent of the cast iron (Ceq) is 4.3%. The cast iron is cast in a BCIRA mold.
A l'épaisseur de 6 mm, la fonte présente les caractéristiques suivantes :  At a thickness of 6 mm, the cast iron has the following characteristics:
- Nombre de cellules eutectiques par mm2 : 2 - Pas de cémentite - Number of eutectic cells per mm 2 : 2 - No cementite
Exemple 7: inoculant suivant l'art antérieur Example 7 Inoculant According to the Prior Art
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 lamellar graphite cast iron bath at 0.3% by weight with a base product FeSi75 with FeSi 75 with Al = 1.0% by weight, Ca = 1.5% by weight and Zr = 1.5% in mass.
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 into the cast iron bag, before filling the mold.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,3 %. La fonte est coulée dans un moule BCIRA.  The amount of carbon equivalent of the cast iron (Ceq) is 4.3%. The cast iron is cast in a BCIRA mold.
A l'épaisseur de 6 mm, la fonte présente les caractéristiques suivantes :  At a thickness of 6 mm, the cast iron has the following characteristics:
- Nombre de cellules eutectiques par mm2 : 1 ,5. - Number of eutectic cells per mm 2 : 1, 5.
- 5 % de cémentite  - 5% cementite
Exemple 8: Pièces d'épaisseurs différentes - inoculant selon l'invention Example 8: Pieces of different thicknesses - inoculant according to the invention
Traitement d'un bain de fonte de graphite sphéroidal à 0,3 % en masse avec un produit constitué :  Treatment of a spherical graphite cast iron bath at 0.3% by weight with a product consisting of:
- d'un alliage support: FeSi 75 avec Al = 1 ,0 % en masse et Ca = a support alloy: FeSi 75 with Al = 1.0% by weight and Ca =
1 ,0 % en masse 1, 0% by weight
- de particules en surface : 5 % d'un mélange de poudres d'aluminium (taille <75μηη) et de CaSi (taille <75μηη)  surface particles: 5% of a mixture of aluminum powders (size <75μηη) and CaSi (size <75μηη)
- Liant : 2% en masse d'une solution aqueuse de PVP  Binder: 2% by weight of an aqueous solution of PVP
- Dépôt des particules de surface par collage réalisé par fluidisation à 100°C.  - 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 during filling of the mold.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,32 %. La fonte est ensuite coulée dans un moule pour fabriquer une pièce ayant des épaisseurs différentes: 4 mm et 25 mm.  The amount of carbon equivalent of the cast iron (Ceq) is 4.32%. The cast iron is then cast in a mold to manufacture a part having 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 :  On the casting on the 4 mm thick part, the cast iron has the following characteristics:
- Nombre de nodules /mm2 : 502 - Number of nodules / mm 2 : 502
- Diamètre moyen : 17μηη  - Average diameter: 17μηη
- Graphite de type VI : 85 % - Nodularité : 98 % - Type VI graphite: 85% - Nodularity: 98%
- Cémentite : 0 %  - Cementite: 0%
- Ferrite : 48 %  - Ferrite: 48%
- Perlite : 52 %  - Perlite: 52%
Sur la pièce coulée, sur la partie d'épaisseur de 25 mm, la fonte présente les caractéristiques suivantes :  On the casting, on the 25 mm thick part, the cast iron has the following characteristics:
- Nombre de nodules /mm2 : 250 - Number of nodules / mm 2 : 250
- Diamètre moyen : 23 μιτι  - Average diameter: 23 μιτι
- Graphite de type VI : 87 %  - Type VI graphite: 87%
- Nodularité : 98.5 %  - Nodularity: 98.5%
- Cémentite : 0 %  - Cementite: 0%
- Ferrite : 50 %  - Ferrite: 50%
- Perlite : 50 % Exemple 9: Pièces d'épaisseurs différentes - inoculant selon l'art antérieur  - Perlite: 50% Example 9: Parts of different thicknesses - inoculant according to the prior art
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 0.3% by weight spherical graphite cast iron bath with a conventionally obtained FeSi75 alloy 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 during filling of the mold.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,31 %. La fonte est ensuite coulée dans un moule pour fabriquer une pièce ayant des épaisseurs différentes: 4 mm et 25 mm.  The amount of carbon equivalent of the cast iron (Ceq) is 4.31%. The cast iron is then cast in a mold to manufacture a part having 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 :  On the casting on the 4 mm thick part, the cast iron has the following characteristics:
- Nombre de nodules /mm2 : 350. - Number of nodules / mm 2 : 350.
- Diamètre moyen : 19 μιτι  - Average diameter: 19 μιτι
- Graphite de type VI : 70 %  - Type VI graphite: 70%
- Nodularité : 95 %  - Nodularity: 95%
- Cémentite : 30 %  - Cementite: 30%
- Ferrite : 40 %  - Ferrite: 40%
- Perlite : 30 %  - Perlite: 30%
Sur la pièce coulée, sur la partie d'épaisseur de 25 mm, la fonte présente les caractéristiques suivantes :  On the casting, on the 25 mm thick part, the cast iron has the following characteristics:
- Nombre de nodules /mm2 : 150. Diamètre moyen : 25 μιτι - Number of nodules / mm 2 : 150. Average diameter: 25 μιτι
Graphite de type VI : 73 '  Type VI graphite: 73 '
Nodularité : 95.5 %  Nodularity: 95.5%
Cémentite : 0 %  Cementite: 0%
Ferrite : 50 %  Ferrite: 50%
Perlite : 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, it can be seen 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.
Exemple 10: Pièces de forte épaisseur - inoculant selon l'invention Traitement d'un bain de fonte de graphite sphéroidal à 0,3 % en masse avec un produit constitué : EXAMPLE 10 Thick Pieces - Inoculant According to the Invention Treatment of a spherical graphite cast iron bath at 0.3% by weight with a product consisting of:
- d'un alliage support: FeSi75 avec Al = 1 ,0 % en masse et Ca = 1 ,0- a support alloy: FeSi July 5 with Al = 1, 0 mass% and Ca = 1, 0
% en masse % by weight
- de particules en surface : 5 % d'un mélange de poudres d'aluminium (taille <75μηη) et de CaSi (taille <75μηη)  surface particles: 5% of a mixture of aluminum powders (size <75μηη) and CaSi (size <75μηη)
- Liant : 10% en masse d'une solution aqueuse de ciment  Binder: 10% by weight of an aqueous solution of cement
- Dépôt des particules de surface par collage réalisé par fluidisation à 100°C.  - 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 into the tundish during the filling of the mold.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,33 %. La fonte est ensuite coulée dans un moule pour fabriquer une pièce de forte épaisseur (170mm).  The amount of carbon equivalent of the cast iron (Ceq) is 4.33%. The cast iron is then poured into a mold to make a thick piece (170mm).
Sur la pièce coulée d'épaisseur 170mm, au centre de la pièce, la fonte présente les caractéristiques suivantes :  On the casting 170mm thick in the center of the piece, the cast iron has the following characteristics:
- Nombre de nodules /mm2 : 160 - Number of nodules / mm 2 : 160
- Graphite de type VI : 65 %  - Type VI graphite: 65%
Diamètre moyen : 25  Average diameter: 25
Nodularité : 99.2 %  Nodularity: 99.2%
Cémentite : 0 %  Cementite: 0%
Ferrite : 50 %  Ferrite: 50%
Perlite : 50 % Exemple 1 1 : Pièces de forte épaisseur - inoculant selon l'art antérieur Perlite: 50% Example 1 1: Thick pieces - inoculant according to the prior art
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 0.3% by weight spherical graphite cast iron bath with a conventionally obtained FeSi 75 alloy containing 1.0% Bi and 0.6% Rare Earth.
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 into the tundish during the filling of the mold.
La quantité de carbone équivalent de la fonte (Ceq) est à 4,31 %. The amount of carbon equivalent of the 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 cast in a mold to make a thick piece: 170 mm.
Sur la pièce coulée, en milieu de la pièce d'épaisseur 170 mm, la fonte présente les caractéristiques suivantes :  On the casting, in the middle of the 170 mm thick piece, the cast iron has the following characteristics:
- Nombre de nodules /mm2 : 155. - Number of nodules / mm 2 : 155.
- Diamètre moyen : 22 μιτι  - Average diameter: 22 μιτι
- Graphite de type VI : 50 %  - Type VI graphite: 50%
- Nodularité : 85 %  - Nodularity: 85%
- Cémentite : 0 %  - Cementite: 0%
- Ferrite : 52 %  - Ferrite: 52%
- Perlite : 48 %  - 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 parts of high thicknesses, while maintaining a good nodularity of the graphite.
Bien que l'invention ait été décrite avec un exemple particulier de réalisation, il est bien évident qu'elle n'y est nullement limitée et qu'elle comprend tous les équivalents techniques des moyens décrits, ainsi que leurs combinaisons si celles-ci entrent dans le cadre de l'invention.  Although the invention has been described with a particular embodiment, it is obvious that it is in no way limited and that it includes all the technical equivalents of the means described, and their combinations if they enter in the context of the invention.

Claims

REVENDICATIONS
1 . Inoculant particulaire en poudre pour le traitement de la fonte en phase liquide, caractérisé en ce qu'il comprend, d'une part, des particules support en un matériau fusible dans la fonte liquide, et d'autre part, des particules de surface en un matériau favorisant la germination et la croissance de graphite, disposées et réparties de manière discontinue à la surface des particules support, les particules de surface présentant une granulométrie telle que leur d50 est inférieur ou égal à un dixième du d50 des particules support.  1. Inoculant particulate powder for the treatment of melting in liquid phase, characterized in that it comprises, on the one hand, support particles in a fusible material in the liquid iron, and secondly, surface particles in a material promoting the germination and growth of graphite, arranged and distributed discontinuously on the surface of the support particles, the surface particles having a particle size such that their d50 is less than or equal to one-tenth of the d50 of the support particles.
2. Inoculant selon la revendication 1 , caractérisé en ce que les particules support sont en un matériau favorisant l'association du carbone au fer sous forme de graphite.  2. Inoculant according to claim 1, characterized in that the carrier particles are made of a material promoting the association of carbon with iron in the form of graphite.
3. Inoculant selon la revendication 1 ou 2, caractérisé en ce que les particules support sont en un matériau à base de silicium et/ou de carbone.  3. Inoculant according to claim 1 or 2, characterized in that the carrier particles are made of a material based on silicon and / or carbon.
4. Inoculant selon la revendication 3, caractérisé en ce que les particules support contiennent au moins 40 % en masse de silicium par rapport à la masse desdites particules.  4. Inoculant according to claim 3, characterized in that the carrier particles contain at least 40% by weight of silicon relative to the mass of said particles.
5. Inoculant selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les particules support sont réalisées à partir d'un alliage ferreux.  5. Inoculant according to any one of claims 1 to 4, characterized in that the carrier particles are made from a ferrous alloy.
6. Inoculant selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les particules support comprennent, notamment sous forme alliée, au moins un élément d'addition, tel que de l'aluminium ou du calcium, notamment entre 0,2 et 5 % en masse pour chaque élément d'addition, par rapport à la masse des particules support.  6. Inoculant according to any one of claims 1 to 5, characterized in that the carrier particles comprise, especially in the form of an alloy, at least one addition element, such as aluminum or calcium, in particular between 0, 2 and 5% by weight for each addition element, relative to the mass of the support particles.
7. Inoculant selon l'une quelconque des revendications 1 à 6, caractérisé en ce que 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.  7. Inoculant according to any one of claims 1 to 6, characterized in that the carrier particles comprise, in particular in the form of alloy, at least one anti-shrink treatment element, in particular in an amount between 0.5 and 6% by weight, based on the mass of the carrier particles.
8. Inoculant selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la proportion des particules de surface est comprise en 1 et 8 % en masse, par rapport à la masse d'inoculant.  8. Inoculant according to any one of claims 1 to 7, characterized in that the proportion of surface particles is 1 to 8% by weight, relative to the mass of inoculant.
9. Inoculant selon l'une quelconque des revendications 1 à 8, caractérisé en ce que, jusqu'à l'introduction dans la fonte, les particules de surface occupent entre 80 et 90 % de la surface des particules support. 9. Inoculant according to any one of claims 1 to 8, characterized in that, until introduction into the cast iron, the surface particles occupy between 80 and 90% of the surface of the carrier particles.
10. Inoculant selon l'une quelconque des revendications 1 à 9, caractérisé en ce que les particules de surface sont choisies, individuellement ou en mélange, parmi des éléments métalliques, tels qu'aluminium, bismuth et manganèse, des siliciures, notamment de fer, terres rares et calcium, des oxydes, tels qu'oxydes d'aluminium, de calcium, de silicium ou de baryum, des sulfures métalliques, notamment de fer, calcium et terres rares, des sulfates, notamment de baryum, et du noir de carbone. 10. Inoculant according to any one of claims 1 to 9, characterized in that the surface particles are chosen, individually or in mixture, from metal elements, such as aluminum, bismuth and manganese silicides, including iron , rare earths and calcium, oxides, such as oxides of aluminum, calcium, silicon or barium, metal sulphides, especially iron, calcium and rare earths, sulphates, in particular barium, and black carbon.
1 1 . Inoculant selon l'une quelconque des revendications 1 à 10, caractérisé en ce que les particules de surface sont incrustées à la surface des particules support.  1 1. Inoculant according to any one of claims 1 to 10, characterized in that the surface particles are encrusted on the surface of the carrier particles.
12. Inoculant selon l'une quelconque des revendications 1 à 10, caractérisé en ce que les particules de surface sont collées par l'intermédiaire d'un liant à la surface des particules support.  12. Inoculant according to any one of claims 1 to 10, characterized in that the surface particles are bonded through a binder to the surface of the carrier particles.
13. Procédé de fabrication d'un inoculant pour le traitement de la fonte selon l'une quelconque des revendications 1 à 12, comprenant les étapes suivantes :  13. A method of manufacturing an inoculant for treating cast iron according to any one of claims 1 to 12, comprising the following steps:
On dispose de particules support 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 présentant une granulométrie telle que leur d50 est inférieur ou égal à un dixième du d50 des particules support, d'autre part,  Support particles are available in fusible material in molten iron, having a particle size ranging from 0.2 to 7 mm, on the one hand, and surface particles having a particle size such that their d50 is less than or equal to one tenth the d50 of the carrier particles, on the other hand,
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.  The carrier particles and the surface particles are mixed, dry, at high speed, for example from 1000 to 1500 revolutions / min, to obtain an incrustation deposition of the surface particles on the surface of the support particles, in a discontinuous distribution.
14. Procédé de fabrication d'un inoculant selon l'une quelconque des revendications 1 à 12, comprenant les étapes suivantes :  14. A method of manufacturing an inoculant according to any one of claims 1 to 12, comprising the following steps:
On dispose de particules support présentant une granulométrie variant de 0,2 à 7 mm, de particules de surface présentant une granulométrie telle que leur d50 est inférieur ou égal à un dixième du d50 des particules support, et d'un liant dans un solvant,  Support particles having a particle size ranging from 0.2 to 7 mm, surface particles having a particle size such that their d50 is less than or equal to one-tenth of the d50 of the support particles, and a binder in a solvent, are available.
On mélange les particules support, les particules de surface et le liant, et  The carrier particles, the surface particles and the binder are mixed, and
On élimine le solvant du liant, par exemple par évaporation.  The solvent is removed from the binder, for example by evaporation.
15. Procédé selon la revendication 14, caractérisé en ce que le liant est choisi parmi les liants organiques et polymères, et notamment, parmi l'alcool polyvinylique (APV), la cellulose (CMC), la polyvinyipyrrolidone (PVP) et le ciment. 15. Process according to claim 14, characterized in that the binder is chosen from organic and polymeric binders, and in particular from polyvinyl alcohol (PVA), cellulose (CMC), polyvinylpyrrolidone (PVP) and cement.
16. Procédé selon l'une quelconque des revendications 13 à 15, caractérisé en ce que les particules support sont en un matériau FeSi contenant de l'aluminium et du calcium.  16. Method according to any one of claims 13 to 15, characterized in that the support particles are made of a FeSi material containing aluminum and calcium.
17. Procédé selon l'une quelconque des revendications 13 à 16, caractérisé en ce que les particules de surface sont en un matériau choisi parmi l'aluminium, le bismuth, les siliciures, notamment de fer, terres rares et calcium, des oxydes, tels qu'oxydes d'aluminium, de calcium, de silicium ou de baryum, des sulfures métalliques, notamment de fer, calcium et terres rares, des sulfates, notamment de baryum, et du noir de carbone.  17. Method according to any one of claims 13 to 16, characterized in that the surface particles are of a material selected from aluminum, bismuth, silicides, especially iron, rare earths and calcium, oxides, such as oxides of aluminum, calcium, silicon or barium, metal sulphides, especially iron, calcium and rare earths, sulphates, in particular barium, and carbon black.
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