EP2836318A2 - Noyaux à base de sel, procédé de fabrication de ces noyaux et leur utilisation - Google Patents

Noyaux à base de sel, procédé de fabrication de ces noyaux et leur utilisation

Info

Publication number
EP2836318A2
EP2836318A2 EP13728105.1A EP13728105A EP2836318A2 EP 2836318 A2 EP2836318 A2 EP 2836318A2 EP 13728105 A EP13728105 A EP 13728105A EP 2836318 A2 EP2836318 A2 EP 2836318A2
Authority
EP
European Patent Office
Prior art keywords
salt
binder
cores
binder system
water
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.)
Withdrawn
Application number
EP13728105.1A
Other languages
German (de)
English (en)
Inventor
Thorsten Hartig
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.)
Emil Mueller GmbH
Original Assignee
Emil Mueller GmbH
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 Emil Mueller GmbH filed Critical Emil Mueller GmbH
Publication of EP2836318A2 publication Critical patent/EP2836318A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/10—Cores; Manufacture or installation of cores
    • B22C9/105—Salt cores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/167—Mixtures of inorganic and organic binding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
    • B22C1/185—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents containing phosphates, phosphoric acids or its derivatives

Definitions

  • Salt-based cores process for their preparation and their
  • the invention relates to salt-based cores, to processes for the preparation of salt-based cores, and to the use of such cores as cavity locators in the production of metallic castings, preferably in die casting technology, which is completely and easily solidified by solvents without fusing Remove residues from the workpieces.
  • Cores which are used in the casting of metal workpieces into the molds in order to keep the cavities provided in the workpieces free when filling the molds with the melt place great demands.
  • the cores must be easy to produce, dimensionally stable and contour-accurate, and the materials used for their production and the solvent dissolving them should not affect the casting quality, the environment or cause any health hazards.
  • the surface of the cores must be particularly smooth and contoured and the cores must dissolve completely in a suitable solvent and can be easily removed without leaving solid residue from the cavities of the workpieces , Residues of cores containing non-dissolvable components such as quartz sand can cause damage to surfaces to be refined or cause the failure of an aggregate, for example, when core residues lead to blockage of an injector in the common rail system of a diesel engine.
  • Object of the present invention is to produce cores based on salt with low porosity, good surface quality and the highest possible strength, which can be easily and completely removed from the workpieces after casting of the workpieces.
  • Another object of the present invention is to produce such cores in a simple and inexpensive forming process, preferably by the so-called dry pressing process.
  • Another object of the present invention is to improve this T rocke npre ssclar and provide cores that are significantly improved in strength and yet can easily be dissolved out of the casting after casting, and leave a good, smooth surface finish in the casting.
  • the cores according to the invention consist of a salt, to which a special binder system and, optionally, auxiliaries such as fillers, additives, wetting agents and catalysts can be admixed. These cores are preferably intended for workpieces made by non-ferrous metal die casting cast, such as aluminum, brass or copper.
  • the cores according to the invention are composed of substances which can be removed without residue from the cavities of the workpieces with water, as a preferred solvent for reasons of environmental protection.
  • the quality of the castings is improved by casting defects such as voids, gas pores or the like can be avoided by resulting core gases.
  • the substances can be recovered by suitable processes from the liquid phase, for example the salt by spray drying or evaporation.
  • All compositions of the core materials can be processed in conventional mechanical or hydraulic presses by compacting.
  • the complexity of the geometry of the cores determines the manufacturing parameters as well as the design and constructive design of the tool for making the cores and the press.
  • Suitable core materials for the cores according to the invention are the salts of alkali metal and alkaline earth metal elements, in particular sodium chloride, potassium chloride and magnesium chloride, the sulfates and nitrates of the alkali metal and alkaline earth metal elements, in particular potassium sulfate, magnesium sulfate and ammonium salts, in particular ammonium sulfate.
  • the water-soluble representatives of these core materials are preferred. These substances can be used individually or as a mixture, as far as they do not react with each other and so on have negative effects on the desired properties, because the core material should not undergo a material conversion during the core production, which negatively influences its residue-free removal.
  • all easily soluble salts are suitable whose decomposition or melting point is above the temperature of the liquid molten metal.
  • the core materials can be easily and simply divided into the desired grain sizes or grain classes.
  • the selected particle size distribution and the degree of compaction selected influence in particular the surface properties of the cores. The smaller the grain size, the smoother the surface.
  • the highest possible degree of compaction is desired, which can be achieved by mixing different salts and optionally the additional substances with different distribution curves, for example by a bi- or trimodal grain distribution in the mixture.
  • grain sizes in the range of 0.01 mm to 2 mm are preferred, depending on the core material, desired surface quality and contour accuracy of the workpiece to be cast.
  • grain size fractions of 0.01 mm to 0.29 mm, 0.3 mm to 1, 3 mm and / or 1, 31 mm to 2.0 mm are mixed in different proportions.
  • Fillers which can also be removed completely by water as a solvent and residue-free, may optionally replace part of the salt so far as this does not adversely affect the density and strength. According to the invention, it has been found that up to 30% by weight of the salt can be replaced by corresponding fillers.
  • the grain size of the filler is suitably adjusted to the grain size or the particle size distribution of the salt.
  • at least one suitable binder system is added to the salt before compacting.
  • the solution according to the invention of the object underlying the invention provides for the use of a special binder system consisting of a binder / binder and a drying agent adapted thereto.
  • binder / binder in principle, all binder / binder can be used, which can be removed without residue after the curing process with water as the solvent and the well and optionally wet the additives, the mixture of these substances must be malleable by means of compression to lost cores.
  • binders / binders, inorganic phosphates, inorganic borates, silicate compounds or mixtures of these binders are suitable if they can be removed without residue with water as solvent.
  • inorganic phosphate for example, alkali metal or ammonium phosphate, monoaluminum phosphate, boron phosphate, trisodium phosphate, tetrapotassium pyrophosphate or sodium polyphosphate can be used.
  • Binder / binders of water-soluble silicates such as water-soluble waterglass with a waterglass modulus of 1 to 5, may preferably be used, and waterglasses with different waterglass modulus may also be present as a mixture.
  • the amount added depends on the water glass module used and, depending on the wetting behavior, is between 0.5% by weight and 15% by weight, preferably between 5% by weight and 8% by weight.
  • For the further processing of the core material to the usable core it is of fundamental importance in which form the core material is present.
  • core materials are agglomerated or deagglomerated and whether they are present in free-flowing form.
  • free-flowing core material mixtures are capable of automatically and completely filling the so-called filling shoes used in the dry pressing process, the preferred shaping process according to the invention.
  • free-flowing mixtures of the salt, the binder system used and the other admixtures are therefore suitable as a core material for use in the dry pressing process.
  • this is surprisingly achieved by adding suitable drying agents in a suitable amount, depending on the chosen binders / binders.
  • suitable drying agents in a suitable amount, depending on the chosen binders / binders.
  • the combination of binders / binders and the drying agent forms the special binder system provided according to the invention.
  • this binder system With this binder system, the object underlying the invention is surprisingly to be solved.
  • Suitable drying agents according to the invention are all hydrophilic substances which are capable of reversibly binding water, ie which are capable of releasing the absorbed water by suitable treatment.
  • suitable treatment for example, highly disperse silicas such as Aerosil, silica gel, zeolites, anhydrous sodium sulfate and / or magnesium sulfate in question.
  • These drying agents close due to their chemical and structural properties of water molecules, and then change their spatial molecular structure through intermolecular forces. Water molecules can no longer escape from the structure and remain bound during the processing of the core materials. By heat, the bound water can be released again.
  • the addition amount of the drying agent according to the invention is always dependent on the type used and the amount of binder / binder and can be easily determined by simple experiments. A slight overdose of the drying agent is tolerable.
  • a drying agent which can be used according to the invention not only to ensure the flowability of the core material, but to allow an improvement in the flowability of the core material compared to core materials containing 1 to 5 wt .-% of water glass binder / binder based on the amount of salt used but no desiccant.
  • binder / binder By using the special binder system according to the invention from the combination of binder / binder and drying agent, it is also possible for the first time to use binder / binder in liquid form in the preparation of the core materials.
  • the use of liquid binder / binder significantly improves the wetting of the core material constituents with the binder / binder.
  • the core material constituents, in particular the salt grains are coated by the binder / binder.
  • the result is a much improved finished salt core in its strength.
  • a liquid binder according to the invention for example, an aqueous, 60% Tetrakaiiumpyrophosphat solution can be used.
  • Relative to the used Amount of salt is added in this variant 1 to 5 wt .-%, preferably 2 to 4 wt .-%, particularly preferably 2.5 wt .-% aqueous, 60% tetrapotassium pyrophosphate solution.
  • the desiccant provided according to the invention is added in sufficient quantity to the core material coated in this way with the binder. A slight overdose of the drying agent is also tolerable in this case.
  • aqueous, 60% strength tetrapotassium pyrophosphate solution is additionally added tetrapotassium pyrophosphate in solid form in the same or even greater amount.
  • the properties of the mixture of salt according to the invention, optionally excipients such as additives, fillers, wetting agents and / or catalysts and the special binder system according to the invention can be influenced by the targeted addition of additives. It is also a prerequisite here that these additives or the reaction products of these additives with water as the solvent are completely removable from the cavity of a workpiece completely and without residues, and that during casting no gasses adversely affecting the casting process are released, which can lead to casting defects.
  • these additives may be selected from: wetting agents, for example surfactants, additives which influence the consistency of the mixture, lubricants, deagglomerating additives, gelling agents, additives which alter the thermophysical properties of the core, for example the thermal conductivity, additives which adhere of the metal at the cores, additives that lead to better homogenization and miscibility, additives that increase the shelf life, additives that prevent premature curing, additives that prevent the formation of smoke and condensation Prevent pouring and additives that accelerate curing.
  • wetting agents for example surfactants, additives which influence the consistency of the mixture, lubricants, deagglomerating additives, gelling agents, additives which alter the thermophysical properties of the core, for example the thermal conductivity, additives which adhere of the metal at the cores, additives that lead to better homogenization and miscibility, additives that increase the shelf life, additives that prevent premature curing, additives that prevent the formation of smoke and condensation Prevent pouring and additives that accelerate curing.
  • These additives
  • the gas influencing the core material preferably C0 2 or air
  • the pressure can be up to 5 bar.
  • thermal post-treatment of the cores at temperatures up to 600 ° C, preferably at temperatures between 500 ° C and 600 ° C, more preferably at temperatures of 580 ° C.
  • the core material is composed of the salt and the binder system and, if necessary, the additives such as fillers, additives and catalysts, wherein the fillers and the binder system are inorganic.
  • Purpose of the cores and determines the surface quality and the density and strength of the cores.
  • the processing of the core materials is carried out separately from the manufacturing process, whereby appropriate protective measures must be provided to prevent agglomeration and premature curing, if necessary.
  • protective measures For example, depending on the composition of the core material, treatment, transport and storage can also take place under protective gas or vacuum.
  • composition and properties of a core have a significant impact on the quality of the casting.
  • the salt cores according to the invention on the basis of sodium chloride typically have a density of 1, 5 g / cm 3 to 1, 9 g / cm 3, preferably from 1, 2 g / cm 3 to 1, 8 g / cm 3 determined according to the buoyancy method. This corresponds to a porosity of 10% to 35%, preferably from 5% to 25%.
  • the flexural strength, measured according to VDG leaflet P73, is between 400 N / cm 2 and 1500 N / cm 2 . With reference to an embodiment, therefore, the most important properties are listed below. The properties given refer to cores that are not coated with a size.
  • the core uses a core of NaCl with the following additional substances such as waterglass binder, Aerosil as drying agent and other additives such as release agents, setting retardants, wetting agents, etc.
  • the core was molded at a pressure of 50 to 120 bar on a hydraulic press. It was subjected to a thermal after-treatment of 60 min duration at 580 ° C for curing.
  • the present core is particularly suitable for use in aluminum chill casting. In order to withstand the temperatures and forces that occur during casting, the core must be dimensionally stable. On a sample measuring 180 mm in length, 22 mm in width and 22 mm in height, the determined mechanical properties of the core.
  • the flexural strength, measured according to VDG leaflet P73 (February 1996) is 400 and 1500 N / cm 2
  • the porosity also plays a decisive role.
  • the pore content is 30% in this embodiment.
  • the core After the casting is completely solidified, the core must be removed. It is important that the core completely and easily dissolves immediately and without solid residues. (Note: in the context of the present invention, the term “water-soluble”, “dissolve” or “dissolve” does not necessarily mean the chemical term of dissolution.) It is crucial that the constituents of the cores according to the invention are readily dissolved by water as the solvent The dissolution rate of the core naturally depends on the core materials and their pretreatment, as well as the size of the core, which may be different for a pure salt than for a composition with binders and fillers have shown that a core measuring 22 mm x 22 mm x 180 mm can be completely washed out of the casting with hot water within 1 minute to 2 minutes.
  • Kemtechnik mixture whose core materials are selected from at least one salt, at least one binder system of binder / binder and
  • Desiccants and optionally excipients such as additives, fillers, Wetting agents and catalysts, wherein the salt, the binder system and the optional adjuvants are inorganic, these core materials are soluble with water as a solvent and the core material mixture is formed into cores and compressed in the dry pressing process.
  • salts are used whose decomposition or melting point is above the temperature of the liquid metal surrounding the cores; in which as salts chlorides of alkali and alkaline earth elements, in particular sodium chloride, potassium chloride and / or magnesium chloride, sulfates and nitrates of alkali and alkaline earth elements, in particular potassium sulfate and / or magnesium sulfate, ammonium salts, in particular ammonium sulfate or mixtures of these salts are used;
  • the salt used is in a particle size distribution of 0.01 to 0.29 mm, 0.3 to 1, 3 mm and / or 1, 31 to 2.0 mm; > in which in the binder system as binders / binders with water residue-free removable, inorganic phosphates, inorganic borates, silicate compounds or mixtures of these binders / binders are used; > In which in the binder system as binders / binders with water residue-free removable alkali or ammonium phosphate, monoaluminum phosphate, boron phosphate, trisodium phosphate, tetrapotassium pyrophosphate or sodium polyphosphate or mixtures of these binders / binders are used; > in which in the binder system as binder / binder water-soluble silicate compounds, preferably water glasses are used;
  • the binder is a water glass with a water glass module of 1 to 5 and / or a mixture of water glasses with different water glass modules; in which the proportion of binder / binders between 0.5 wt .-%, and 15 wt .-% based on the salt used;
  • binder tetrapotassium pyrophosphate in which binder binder tetrapotassium pyrophosphate in liquid form is used in the binder system; in which binder binder tetrapotassium pyrophosphate in aqueous, 60% solution is used in the binder system; in which in the binder system, the binder tetrapotassium pyrophosphate in aqueous, 60% solution and in amounts of 1 to 5 wt .-%, preferably in amounts of 2 to 4 wt
  • the binder tetrapotassium pyrophosphate in aqueous, 60% solution and in amounts of 1 to 5 wt .-%, preferably in amounts of 2 to 4 wt .-%, particularly preferably in amounts of 2.5 parts by weight.
  • % based on the amount of salt used, and in addition tetrapotassium pyrophosphate in solid form in the same or greater amount is used; in which in the binder system, the binder in a proportion of 1 to 15 wt .-%, based on the amount of salt used, and the desiccant 0.3 to 4.5 wt .-%, based on the amount of salt used, is included; in which in the binder system as a drying agent hydrophilic substances are used, which are able to reversibly bind water; > in which in the binder system as a drying agent highly disperse silicas such as Aerosil, silica gel, zeolites, anhydrous sodium sulfate and / or magnesium sulfate are used;
  • catalyst a catalyst is added; > in which the catalyst is particularly fine-grained salt, preferably powdered salt with a particle size below 100 nm;
  • the salt is sodium chloride, preferably in bi- or trimodal grain size distribution particularly preferably in a particle size distribution of 0.01 to 0.29 mm, 0.3 to 1, 3 mm and / or 1, 31 to 2.0 mm is present, the binder system from the combination of
  • the catalyst is particularly fine-grained salt, preferably powdered salt having a particle size below 100 nm, that optionally further auxiliaries such as additives, fillers, wetting agents and / or other catalysts are included and that the mixture of core materials flowable is;
  • the cores are heat-treated after shaping; in which the cores are heat-treated after shaping at a temperature of up to 600 ° C, preferably at temperatures of 500 to 600 ° C, preferably at a temperature of 580 ° C;
  • the shaped cores have a density of 1, 5 g / cm 3 to 2.1 g / cm 3 , preferably from 1.2 g / cm 3 to 1.8 g / cm 3 ; > wherein the shaped cores have a porosity of 10% to 40%, preferably 5% to 25%;
  • the teaching according to the invention furthermore relates to:
  • a core material mixture whose core materials are selected from at least one salt, at least one binder system of a combination of binder / binder and desiccant and optionally excipients such as additives, fillers, wetting agents and or catalysts homogenously mixed, formed into a core, compacted by dry pressing and optionally heat treated.
  • chlorides of alkali and alkaline earth elements in particular sodium chloride, potassium chloride and / or magnesium chloride, sulfates and nitrates of alkali and alkaline earth elements, in particular potassium sulfate and / or magnesium sulfate, and ammonium salts, in particular
  • Ammonium sulfate or mixtures of these salts are selected;
  • binder / binder in the binder system with water-free removable inorganic phosphates, inorganic borates, Silicate compounds or mixtures of these binders / binders are used; as binder / binder in the binder system with water residue-free removable alkali or ammonium phosphate, monoaluminum phosphate, boron phosphate, trisodium phosphate, tetrapotassium pyrophosphate or
  • binders / binders in the binder system water-soluble silicate compounds, preferably water glasses are used; > the binder in the binder system is a water glass with a water glass module of 1 to 5 and / or a mixture of water glasses with different water glass modules;
  • binder / binders between 0.5 wt .-%, and 15 wt .-% based on the salt used; > The proportion of binder / binder depending on the wetting behavior and water glass module between 0.5 wt .-% and 15 wt .-% based on the salt used; as binder / binder water glass in a proportion of 0.5 wt .-% to 15 wt .-% based on the salt used, depending on the particle size distribution and matched to the water glass module, is included; as drying agents in the binder system hydrophilic substances are used, which are able to reversibly bind water; > are used as drying agents in the binder system finely divided silicas such as Aerosil, silica gel, zeolites, anhydrous sodium sulfate and / or magnesium sulfate;
  • a catalyst is added as auxiliary;
  • the catalyst is a particularly fine-grained salt, preferably a powdery salt with a particle size below 100 nm;
  • the salt is sodium chloride, which is preferably present in bi- or trimodal grain size distribution particularly preferably in a particle size distribution of 0.01 to 0.29 mm, 0.3 to 1.3 mm and / or 1.1.3 to 2.0 mm
  • the binder system consists of the combination of the binder water glass and the drying agent Aerosil
  • the catalyst is particularly fine-grained salt, preferably powdered salt with a particle size below 100 nm, that optionally further auxiliaries such as additives, fillers, wetting agents and / or other catalysts are included and that the mixture of core materials is free-flowing;
  • the core materials are homogeneously mixed, formed into a core and compacted in a dry pressing process
  • the core materials depending on the material, desired surface quality and contour accuracy of the workpiece to be cast from metal, be used with grain sizes in the range of 0.01 mm to 2 mm, molded into the core and compacted by dry pressing;
  • the cores are heat treated after shaping; the cores after shaping at a temperature of up to 600 ° C, preferably at temperatures of 500 to 600 ° C, preferably at a temperature 580 ° C are heat treated.
  • the cores according to the invention can be used, for example, as cavity locators in the production of metallic castings, preferably in gravity casting technology.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Mold Materials And Core Materials (AREA)
  • Catalysts (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

Des noyaux qui, lors du moulage sous pression de pièces en métal, sont insérés dans le moule pour maintenir libres les cavités prévues dans les pièces lors du remplissage des moules avec la matière en fusion, font l'objet d'exigences élevées en ce qui concerne leur indéformabilité et leur aptitude à être extraits des cavités. L'invention concerne ainsi des noyaux à base de sel qui peuvent être réalisés par moulage et compression d'un mélange de matières de noyau, les matières de noyau étant choisies entre au moins un sel, au moins un système de liants résultant d'une combinaison de liants / agents liants, et éventuellement des matières auxiliaires telles que des additifs, des matières de charge, des agents de réticulation et des catalyseurs. Le sel, le système de liants et les matières auxiliaires éventuellement employées du mélange de matières de noyau sont d'origine minérale et ces matières de noyau sont solubles dans l'eau en tant que solvant.
EP13728105.1A 2012-04-10 2013-04-10 Noyaux à base de sel, procédé de fabrication de ces noyaux et leur utilisation Withdrawn EP2836318A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012205767 2012-04-10
PCT/EP2013/001054 WO2013152851A2 (fr) 2012-04-10 2013-04-10 Noyaux à base de sel, procédé de fabrication de ces noyaux et leur utilisation

Publications (1)

Publication Number Publication Date
EP2836318A2 true EP2836318A2 (fr) 2015-02-18

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EP13728105.1A Withdrawn EP2836318A2 (fr) 2012-04-10 2013-04-10 Noyaux à base de sel, procédé de fabrication de ces noyaux et leur utilisation

Country Status (7)

Country Link
US (1) US20150060005A1 (fr)
EP (1) EP2836318A2 (fr)
CN (1) CN104428082A (fr)
DE (1) DE102013006135A1 (fr)
MX (1) MX2014012219A (fr)
RU (1) RU2014144721A (fr)
WO (1) WO2013152851A2 (fr)

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RU2014144721A (ru) 2016-06-10
WO2013152851A2 (fr) 2013-10-17
DE102013006135A1 (de) 2013-10-10
CN104428082A (zh) 2015-03-18
MX2014012219A (es) 2015-06-05
WO2013152851A3 (fr) 2014-03-20
US20150060005A1 (en) 2015-03-05

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