EP2892670B1 - Method for obtaining a foundry body from a granular mixture including a modified polycondensed resin and a formaldehyde sensor - Google Patents
Method for obtaining a foundry body from a granular mixture including a modified polycondensed resin and a formaldehyde sensor Download PDFInfo
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- EP2892670B1 EP2892670B1 EP13774731.7A EP13774731A EP2892670B1 EP 2892670 B1 EP2892670 B1 EP 2892670B1 EP 13774731 A EP13774731 A EP 13774731A EP 2892670 B1 EP2892670 B1 EP 2892670B1
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- 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
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- 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
- B22C1/20—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 organic agents
- B22C1/22—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 organic agents of resins or rosins
- B22C1/2233—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 organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/12—Treating moulds or cores, e.g. drying, hardening
- B22C9/123—Gas-hardening
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
- B22D21/04—Casting aluminium or magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
Definitions
- the present invention relates to a process for obtaining a foundry body from a granular mixture comprising a modified polycondensed resin, and a formaldehyde sensor, and the foundry body obtained by said method.
- hot box type industrial processes use resins.
- the resins are intimately mixed with the substance or substances to be agglomerated, or spread on the surface to be bonded, in association with a hardening agent whose function is most often to render the solid reaction medium in situ.
- granular or fibrous filler such as, for example, mineral or synthetic sands, glass micro-beads, ceramic micro-beads and fibers which are most often ligno-lined. cellulose.
- the substance to be agglomerated is generally fluid, most often viscous.
- the substance to be agglomerated is then brought into contact with or in a forming tool, and then heated, the heat being generally provided by the heating of the forming tool (or forming tooling).
- body is meant according to the invention a material object occupying a portion of space and having particular properties.
- the body according to the invention is most often in a solid continuous medium, that is to say of clean form and substantially invariable volume.
- a fluid body is generally a body constituting a deformable continuous medium.
- thermoset resins hot and in acidic medium, by polymerization.
- molds and cores are generally solid bodies, which can be manufactured by a " hot box” type process from a granular charge.
- the corresponding mold or core is destroyed by burning the resin in contact with the metal. This involves producing a set of molds or kernels per piece produced.
- the resins content calculated as dry extract, are extremely low, most often in a range of 0.3 to 3% by weight by weight. relative to the mass of the granular charge to be agglomerated.
- the chemical nature of the combustion gases is important, both for the quality of cast metal parts and for the health of workers.
- the production of molds and cores must be done at high speeds of up to a few thousand pieces per day.
- the forming tools or core boxes are metallic because the heating temperatures to obtain rapid polymerization of the resins are high, generally greater than 150 ° C and up to 380 ° C. This involves significant tooling costs and especially dimensional accuracy problems of molds and cores, related to the expansion of tools under the effect of heat.
- respiratory nuisances for people working in this environment have been deemed inadmissible.
- the French patent application FR 2948307 relates to a process for producing a body comprising a conventional polycondensed resin, preferably a urea-formaldehyde resin, and a free formaldehyde sensor, which is preferably carbohydrazide.
- the patent application US 2007/0149644 discloses the use of tannin extract in a foundry mixture comprising an aggregate and a binder of tannin extract and furfuryl alcohol.
- This binder does not necessarily contain resin, because the two components of the binder react together at a temperature above 40 ° C.
- this invention can not be used in industry because furfuryl alcohol is a compound now classified as carcinogenic.
- the foundry mix of this document apparently does not generate free formaldehyde or phenol free. Thus, according to the text of this document, no formaldehyde sensor seems necessary in this context.
- the patent application WO 2004/058843 discloses a resin-based composition comprising tannin, an amine compound, an aldehyde and a stabilizer.
- the compound containing amino groups may be urea or an oligomer derived from the urea-formaldehyde condensation.
- the stabilizer is preferably an amino-based heterocyclic compound.
- a method for preparing this composition as well as the use of this composition for producing a mixture comprising particles, for the purpose of creating particle boards, including wood particles.
- the compositions of this document do not include a formaldehyde sensor, since it is explained that the free formaldehyde from the resin will react with the tannin during the formation of the composition. In fact, the presence of free formaldehyde is proven and is problematic.
- the polycondensed resin with formaldehyde and / or its derivatives (component b -) is modified by the presence of aromatic and / or polyaromatic groups in the mixture.
- the polycondensed resin with formaldehyde and / or its derivatives is preferably a furanic resin, an aminoplast, a phenoplast or a copolymer of at least two of these three compounds.
- the formaldehyde sensor (component d -) is generally, according to the invention, a compound of the family of hydrazides, preferably chosen from the group formed by mono and dihydrazides, the said sensor being even more preferably the dihydrazide of the acid. adipic acid, succinic acid dihydrazide, or carbohydrazide. In a particularly preferred manner, the formaldehyde sensor is carbohydrazide.
- the resin selected from the group consisting of tannins, natural polyphenols, and lignins (component e -) is preferably a tannin type resin, more preferably a condensed tannin type resin.
- the component e) is a resin by itself, and is generally added to the component b) premix (such a diluent if the two components are liquid). Its presence modifies the behavior of the polycondensed resin (component b), which is therefore a "modified" resin during its use) in the mixture during the implementation of the process according to the invention.
- the component f), which is water may be previously incorporated, in whole or in part, at least one of the other components.
- the blowing step makes it possible to implement at least partially at least one chemical reaction which ensures the at least partial hardening of said mixture.
- the process according to the invention makes it particularly possible, in the case of the use of the body thus obtained for cast iron casting, to reduce the production of formaldehyde during the reaction, to reduce the nitrogen content generated. in the formed body, to enrich the formed body in carbon and to improve the thermal resistance during the process.
- the granular mixture may comprise any other additive known to those skilled in the art.
- the granular mixture may comprise any additive, liquid or powder, known to those skilled in the art to promote the physico-chemical behavior of the mixture during its processing and its subsequent use.
- the grains of the granular mixture according to the invention are generally natural or synthetic.
- the grains are grains of inorganic oxide (s), most often natural siliceous sandy mixtures whose grains are composed mainly of silicon oxide and whose particle size AFS (acronym for " American Foundry Society”). Can range from 30 to 140.
- the water is generally provided in the granular mixture mainly as a solvent of components b) to d), optionally e), of the granular mixture.
- the curing agent is generally incorporated at a very low level in the granular mixture, its dispersion is improved if it is previously diluted in aqueous solution. It is the same for the formaldehyde sensor and the component e), if it is provided in powder form.
- the granular mixture according to the invention is generally in the form of at least one fluid aggregate.
- the surface of the forming tool with which the granular mixture is in contact generally represents the "negative" of the part to be formed in the body manufactured according to the invention.
- the step of blowing a flow of hot gas is generally such that the temperature and the flow rate of said flow are adjusted to cause the temperature rise in the heart of the granular mixture, substantially above ambient temperature (which is about 20 ° C) and preferably above 45 ° C.
- the process according to the invention by the presence in the granular mixture of at least one formaldehyde sensor and a modified polycondensed resin, advantageously makes it possible to significantly improve the thermal properties of the granular mixture and to limit the emission of formaldehyde free when performing formed bodies.
- the presence of a modified polycondensed resin makes it possible to significantly improve the thermal properties and to reduce the nitrogen content of the bodies formed.
- the method according to the invention is such that, in addition, the forming tool is heated to a temperature in the range of 40 ° C to 180 ° C, preferably 50 ° C to 150 ° C. This is generally done in the contacting step, and at the latest during the blowing step.
- the heat provided by the hot gas is supplemented by the heat of heating of the forming tool, so as to optimize, in a preferred version of the invention, the heating of the granular mixture.
- the gas is preferably selected from the group consisting of air, a neutral gas and a gas involved in the acidification of the reaction medium.
- neutral gas means a gas which does not participate in the reaction, for example chosen from dinitrogen and the so-called noble gases such as helium, neon and argon.
- gas involved in the acidification of the reaction medium is meant according to the invention a gas for decreasing in situ the pH of the medium such as carbon dioxide or sulfur dioxide.
- the method also comprises an additional step during which a stream of at least one gas is circulated within the at least partially hardened granular mixture at a temperature within a range of 5 ° C to 45 ° C, for a time in a range of 1 to 300 seconds, the gas being preferably selected from the group consisting of air, nitrogen and carbon dioxide.
- This step is most often carried out before the optional step of removing the body from the forming tool.
- the gas is usually not previously heated, and therefore substantially at room temperature, or possibly cooled.
- formaldehyde by blocking the polymerization reaction of the modified polycondensed resin by cooling the body after partial curing.
- this flow of gas advantageously makes it possible to wash with a flow of air, of nitrogen or of carbon dioxide, the free formaldehyde which may be residual.
- polycondensed resin or polycondensed resin with formaldehyde and / or its derivatives a composition of at least one resin having undergone a chemical reaction between a first element selected from urea and its derivatives, melamine, benzoguanamine, glycoluril, phenol and / or its derivatives, and furfuryl alcohol and / or its derivatives, and a second element selected from formaldehyde and / or its derivatives, wherein preferably the chain growth generally causes at each stage the release of a molecule of water.
- This polycondensed resin is generally a thermosetting polymer, such as a furan resin or an aminoplast or a phenoplast or a copolymer of these compounds, preferably an aminoplast or a phenoplast or an aminoplast-phenoplast copolymer.
- the aminoplasts are obtained by polycondensation of the first comonomer which is formaldehyde and the second comonomer carrying amino groups NH 2 -. They are usually divided into two families compounds, namely urea-formaldehyde (or urea-formaldehyde) (UF) and melamine-formaldehyde (or melamine-formaldehyde) resins (MF).
- urea-formaldehyde or urea-formaldehyde
- MF melamine-formaldehyde
- Phenoplasts or phenol-formaldehyde resins are obtained by polycondensation between a first comonomer that is formaldehyde and a second comonomer that is phenol.
- phenolic resins There are two types of phenolic resins: novolacs, prepared by acid catalysis, and the resols, obtained by basic catalysis.
- the best known phenoplast is bakelite ® (or polyoxybenzylmethylene glycol anhydride), which is the oldest industrial synthetic polymer material.
- the furanic resin is obtained by polycondensation of the first comonomer furfuryl alcohol and the second comonomer is formaldehyde.
- the component (s) of the polycondensed resin may remain free in excess in the polycondensed resin, or may have been added thereto after the polycondensation.
- the polycondensed resin with formaldehyde and / or its derivatives is generally such that it thermosets in acidic medium.
- Such a polycondensed resin is generally commercially available.
- the polycondensed resin may, according to the invention, be modified by the presence during its synthesis of a compound comprising at least one phenolic and / or polyphenolic unit, at a content of 1 to 30% by weight, preferably from 5 to 20% by weight, relative to the total weight of the modified polycondensate resin.
- a compound comprising at least one phenolic and / or polyphenolic unit, at a content of 1 to 30% by weight, preferably from 5 to 20% by weight, relative to the total weight of the modified polycondensate resin.
- This is not the polycondensed resin described in the French patent application FR 2948307 . Indeed, it comprises groups which are derived from the precursor groups that are the phenolic units and / or polyphenolic, preferably present in a compound such as vanillin and phloroglucinol. This compound is generally mixed with the resin prior to its synthesis and the derived groups "hang" on the resin during its synthesis.
- the polycondensed resin may thus have been premixed with a compound, most often synthetic, such as vanillin or phloroglucinol.
- a component e) according to the invention ie the resin selected from the group formed by tannins, natural polyphenols, and lignins, is optional.
- the phenolic and / or polyphenolic unit may be of natural or synthetic origin.
- the resin is thus in the form of a formophenolic copolymer.
- the polycondensed resin with formaldehyde and / or its derivatives according to the invention may also optionally contain at least one additive chosen from solvents, diluents, stabilizers and solid particle fillers, which are usually used and known to those skilled in the art to obtain a particular effect.
- said polycondensed resin may contain at least one silane, which generally makes it possible to bridge, and thus optimize, the bond between the resin and the grains.
- the resin selected from the group consisting of tannins, natural polyphenols, and lignins is a natural polymer rich in aromatic rings (ie having at least two aromatic rings). In reality, this resin contains at least one aromatic nucleus per monomer unit of the polymer, thus a plurality of aromatic nuclei.
- This resin is chosen according to the invention from the group formed by tannins, which are generally of natural origin, preferably condensed and / or modified to make them soluble in water, such as extracts from the Quebracho tree, natural polyphenols, such as those extracted from araucaria angustifolia (Paraná pine) or pinus palustris (swamp pine), and lignins, modified or not.
- the resin selected from the group formed by tannins, natural polyphenols, and lignins is most often renewable.
- renewable resin means, according to the invention, either a natural resin whose stock can be reconstituted over a short period on a human scale, or a synthetic resin whose main synthetic starting materials are renewable components; in theory renewal must be done at least as fast as consumption.
- the resin selected from the group consisting of tannins, natural polyphenols, and lignins is a tannin-type resin, and even more preferably it is a condensed tannin-type resin.
- the tannin type resin is usually a natural phenolic substance. It is usually a secondary metabolite of superior plant that is found practically in all parts of plants (bark, roots, leaves, stems, etc.).
- the tannins are polyphenol natural resins either monosaccharide type polyols and galloyl units or derivatives thereof, linked to flavonoids or triterpenoids, or oligomers or flavanol polymers.
- the tannins used according to the invention are polyflavonoids, for example of the tannin type of the Quebracho tree.
- Lignins are polymers based on one or more monolignols, such as paracoumaryl alcohol, coniferyl alcohol and sinapyl alcohol.
- the lignins may, for example, be modified to lignosulphonates by reactions with bisulphites.
- the resin selected from the group consisting of tannins, natural polyphenols, and lignins may also be a thermoplastic resin, for example, an extract of araucaria angustifolia (Paraná pine) or pinus palustris (swamp pine).
- the resin selected from the group consisting of tannins, natural polyphenols, and lignins can be composed of long-chain aliphatic phenols such as cashew nut shell extract.
- the resin selected from the group formed by tannins, natural polyphenols, and lignins may be a commercial compound such as the following commercial products: Respine RLP from the company POLYTRADE (natural aromatic resin derived from araucaria angustifolia ); VINSOL ® from HERCULES (consisting of approximately 57% polyphenols, 28% rosin and 15% terpenoid); QSF (alcohol-soluble part of tannins de Quebracho), FINTAN 737B (modified condensed tannin from Schinopsis lorentzii or Quebracho colorado powder) and FINTAN 737C (stabilized condensed tannin from Schinopsis lorentzii or Quebracho colorado in 45% solution) from INDUNOR; and CARDANOL (long-chain aliphatic phenols from cashew shells) from SAI CHEMICALS.
- Respine RLP natural aromatic resin derived from araucaria angustifolia
- VINSOL ®
- the curing agent is more generally such that it renders the reaction medium of the acid mixture, either by its own acidity, or by its ability to release acid during the polymerization process.
- the curing agent is selected from the group consisting of hydroxylamine salts, and even more preferably, the curing agent is hydroxylamine sulfate.
- the hydroxylamine salts advantageously release an acid in the presence of formaldehyde.
- the curing agent is a hydroxylamine salt
- the free formaldehyde available combines primarily with this hydroxylamine salt to release an acid, and that the formaldehyde sensor does not inhibit or little acid formation by said salt during the curing reaction.
- hydroxylamine salt significantly and advantageously improves the process according to the invention, by accelerating the hardening kinetics and by increasing the acidity of the reaction medium as the thermosetting reaction releases formaldehyde.
- the production of the granular mixture according to the first step of the process of the invention is generally carried out in a manner known to those skilled in the art.
- those skilled in the art first introduce the granular part or parts into a mixer and then proceed to the introduction of liquid parts, the mixing time being a function of the material and preferably from 15 s to 5 min.
- the invention particularly relates to a method of manufacturing a casting piece of metal, or metal alloy, molded, which comprises casting a metal, or metal alloy, liquid in at least one mold and / or core, characterized in that said mold is a body obtained by the process according to the invention as described above.
- such a method is such that the metal, or metal alloy, is selected from the group formed by aluminum, the ferrous alloys selected from the group consisting of steels and cast irons, non-ferrous metals, non-alloys ferrous, and, more preferably, the metal or metal alloy is selected from the group formed by the fonts.
- the invention also relates to any molded metal part obtained by a manufacturing method as described above.
- the invention further relates to any mechanical assembly comprising at least one such piece.
- the Figure 1 represents curves A, B, C, D and E passing P (in percentage) as a function of time t (in minutes) for five different resins described in the examples, that is to say that each curve represents the percentage passing as a function of time for the resin concerned. This makes it possible to evaluate the thermal resistance.
- a premix was made comprising mainly the polycondensed resin (component b) and optionally a resin selected from the group consisting of tannins, natural polyphenols, and lignins (component e)), and a second premix a was performed comprising the curing agent (component c)) and optionally a formaldehyde sensor compound (component d)). Water was generally present in these two premixes. Then, the granular mixture was made by mixing the siliceous sand, the first premix and the second premix. This granular mixture was carried out in a vibratory bowl mixer with a mixing time of 60 seconds.
- the granular mixture was then blown into a box equipped with a heating system and a supply of hot air (at 100-120 ° C) under a pressure of 1.5 bar (0.15 MPa), for a period of 60 seconds, containing two test pieces of standardized mechanical characteristics of square section 5 cm 2 , on a ROPER machine.
- Curing was performed according to the data indicated for each granular mixture.
- the measurement of formaldehyde during mixing was carried out using the DRAGER model Accuro pump equipment equipped with DRAGER "formaldehyde” dosing tubes (0.2 / a). The range of measurements is 0.2 to 5 ppm. The measurements were made above the vibrating bowl of the mixer.
- the formaldehyde removal measurement was carried out using the DRAGER model Accuro pump equipment fitted with DRAGER "formaldehyde" dosing tubes (0.2 / a or 2 / a), depending on the concentration to be measured in a 10 liter chamber in which circulated a flow of nitrogen of 0.5 L / min.
- a test tube was placed in the enclosure as soon as it came out of the box.
- the flexural strengths were measured both hot and cold after a cooking time of 15 seconds, 30 seconds, 60 seconds and 120 seconds in a can.
- the detection at the end of dislocation (or extraction) of a content of formaldehyde (free) more than 20 times lower than the conventional hot box process is considered to make the shaped body suitable for industrial use.
- the dry extract expressed in% by weight is the residue produced after heating one gram of product at 135 ° C. for one hour.
- test pieces obtained are solid formed bodies that can be assimilated to nuclei.
- the cubes were placed separately in crucibles closed by a lid.
- the crucibles were spotted.
- the crucibles were then placed in a muffle furnace regulated at 450 ° C, a timer having been triggered when the oven was closed.
- the crucibles were taken out of the oven at regular intervals (eg 5-10-20-30-40 minutes ...) and allowed to cool to room temperature.
- each crucible was then placed on a 1 mm mesh screen, and vibrated by a Retsch brand VS1000 laboratory sieve for 30 seconds.
- the pass-through portion was recovered, weighed and the resulting mass converted to percent.
- the thermal resistance expressed by this percentage, is incompatible with the casting of cast iron casting parts.
- the thermal resistance is sufficient for the casting of cast iron casting parts.
- This resin is characteristic of the "hot box” process, and was used at 2% compared to sand.
- Catalyst Commercial product Harter AT3B from Hüttenes Albertus France (50% magnesium lignosulfonate solution), urea and ammonium nitrate.
- This catalyst was used at 0.5% with respect to the sand.
- Hot bending resistance at the box outlet at 30, 60 and 120 seconds respectively: 34, 51 and 61 daN / cm 2
- Cold bending strength at 30, 60 and 120 seconds respectively: 70, 70 and 59 daN / cm 2
- Formaldehyde emissions during mixing and disintegration are incompatible with changes in hygiene and safety standards.
- Urea-formaldehyde resin comprising vanillin, which has been synthesized in an acidic medium with a formaldehyde / urea mole ratio of 2.37, and to which vanillin has been added in a molar ratio of urea to vanillin of 4, 5.
- the vanillin content with respect to the resin is 11.3% by weight.
- Catalyst consisting of 1.4% hydroxylamine in 50% solution, 1.7% p-toluenesulphonic acid in 65% solution, 15.1% carbohydrazide, 2.2% hydroxylamine sulfate and 79.7% water.
- Hot bending resistance at the box outlet at 30, 60 and 120 seconds respectively: 15, 30 and 45 daN / cm 2
- the thermal resistance expressed by this percentage, is considered sufficient for the casting of cast iron casting parts.
- Urea-melamine / formaldehyde resin which was synthesized with a formaldehyde / urea molar ratio of 2.95 and to which was added melamine in a formaldehyde / melamine molar ratio of 3.45 then in which was added 3% modified tannin Fintan 737B, commercial product of the company Indunor (modified condensed tannin from Schinopsis lorentzii or Quebracho colorado powder).
- Catalyst Catalyst containing 14% hydroxylamine sulfate, 20% carbohydrazide and 66% water.
- Hot bending resistance at the box outlet at 30, 60 and 120 seconds respectively: 15, 24 and 42 daN / cm 2
- the thermal resistance expressed by this percentage, is considered sufficient for the casting of cast iron casting parts.
- Tannin-modified urea / formaldehyde resin which was synthesized with a formaldehyde / urea molar ratio of 2.37, and in which 25% of modified tannin Fintan 737C, a commercial product of Indunor (stabilized condensed tannin derived from Schinopsis lorentzii or Quebracho colorado in 45% solution).
- the thermal resistance expressed by this percentage is considered sufficient for the casting of cast iron casting parts.
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Description
La présente invention concerne un procédé d'obtention d'un corps pour fonderie à partir d'un mélange granulaire comprenant une résine polycondensée modifiée, et un capteur de formaldéhyde, ainsi que le corps pour fonderie obtenu par ledit procédé.The present invention relates to a process for obtaining a foundry body from a granular mixture comprising a modified polycondensed resin, and a formaldehyde sensor, and the foundry body obtained by said method.
Les procédés de formage à chaud de substances granulaires ou fibreuses sont des procédés industriels conduisant à la fabrication de corps le plus souvent solides. Parmi ceux-ci, les procédés industriels de type « hot box » (ou boîte chaude) utilisent des résines. En général, les résines sont mélangées intimement avec la ou les substances à agglomérer, ou étalées sur la surface à coller, en association avec un agent durcisseur dont la fonction est le plus souvent de rendre le milieu réactionnel solide in situ.The processes for hot forming granular or fibrous substances are industrial processes leading to the manufacture of bodies that are most often solid. Among these, hot box type industrial processes (or hot box) use resins. In general, the resins are intimately mixed with the substance or substances to be agglomerated, or spread on the surface to be bonded, in association with a hardening agent whose function is most often to render the solid reaction medium in situ.
Les substances à former ou agglomérer, généralement solides, comportent le plus souvent au moins une charge granulaire ou fibreuse tels que par exemple des sables minéraux ou synthétiques, des micro billes de verre, des micro billes de céramique et des fibres le plus souvent ligno-cellulosiques.The substances to be formed or agglomerated, generally solid, most often comprise at least one granular or fibrous filler such as, for example, mineral or synthetic sands, glass micro-beads, ceramic micro-beads and fibers which are most often ligno-lined. cellulose.
Après l'incorporation de la résine et d'un éventuel agent durcisseur, et éventuellement d'au moins un autre additif, la substance à agglomérer est généralement fluide, le plus souvent visqueuse. La substance à agglomérer est alors mise en contact avec ou dans un outil de formage, puis chauffée, la chaleur étant généralement apportée par le chauffage de l'outillage de formage (ou outillage de mise en forme).After the incorporation of the resin and a possible hardening agent, and possibly at least one other additive, the substance to be agglomerated is generally fluid, most often viscous. The substance to be agglomerated is then brought into contact with or in a forming tool, and then heated, the heat being generally provided by the heating of the forming tool (or forming tooling).
La chaleur initie le durcissement des résines par polymérisation, puis le corps solide ainsi formé est généralement retiré de l'outil de formage pour son utilisation ultérieure. Par « corps », on entend selon l'invention un objet matériel occupant une portion d'espace et présentant des propriétés particulières. Le corps selon l'invention consiste le plus souvent en milieu continu solide, c'est-à-dire de forme propre et de volume sensiblement invariable. Par opposition, un corps fluide est généralement un corps constituant un milieu continu déformable.The heat initiates curing of the resins by polymerization, and then the solid body thus formed is generally removed from the forming tool for later use. By "body" is meant according to the invention a material object occupying a portion of space and having particular properties. The body according to the invention is most often in a solid continuous medium, that is to say of clean form and substantially invariable volume. In contrast, a fluid body is generally a body constituting a deformable continuous medium.
Un des procédés industriels est dit de type « hot box » et utilise des résines condensées avec du formaldéhyde. Ces résines thermodurcissent à chaud et en milieu acide, par polymérisation.One of the industrial processes is called " hot box" and uses resins condensed with formaldehyde. These thermoset resins hot and in acidic medium, by polymerization.
Dans le domaine de la fonderie, les moules et noyaux sont des corps généralement solides, qui peuvent être fabriqués par un procédé de type « hot box » à partir d'une charge granulaire. A la coulée de chaque pièce métallique dans ou en contact avec le moule ou le noyau, le moule ou noyau correspondant est détruit par combustion de la résine au contact du métal. Cela implique la production d'un jeu de moule ou noyau par pièce produite. Pour favoriser cette destruction, à cadence industrielle, et limiter les nuisances des gaz de combustion, les taux de résines, calculés en extrait sec, sont extrêmement bas, le plus souvent compris dans une fourchette de 0,3 à 3%, en poids par rapport à la masse de la charge granulaire à agglomérer. De plus, la nature chimique des gaz de combustion a son importance, tant pour la qualité des pièces de métal coulées, que pour la santé des travailleurs.In the field of foundry, molds and cores are generally solid bodies, which can be manufactured by a " hot box" type process from a granular charge. When casting each metal part into or in contact with the mold or core, the corresponding mold or core is destroyed by burning the resin in contact with the metal. This involves producing a set of molds or kernels per piece produced. To promote this destruction, at industrial rate, and to limit the nuisance of the combustion gases, the resins content, calculated as dry extract, are extremely low, most often in a range of 0.3 to 3% by weight by weight. relative to the mass of the granular charge to be agglomerated. In addition, the chemical nature of the combustion gases is important, both for the quality of cast metal parts and for the health of workers.
Enfin, dans certains domaines d'industrie, tel que celui de l'industrie automobile de série, la production de moules et de noyaux doit se faire à des cadences élevées pouvant aller jusqu'à quelques milliers de pièces par jour. Dans ce cas, les outillages de formage ou boîtes à noyaux sont métalliques car les températures de chauffage pour obtenir une polymérisation rapide des résines sont élevées, généralement supérieure à 150°C et pouvant aller jusqu'à 380°C. Cela implique des coûts importants d'outillages et surtout des problèmes de précision dimensionnelle des moules et des noyaux, liés à la dilatation des outillages sous l'effet de la chaleur. D'autre part, les nuisances respiratoires pour les personnes travaillant dans ce milieu ont été jugées inadmissibles.Finally, in certain industries, such as the mass production industry, the production of molds and cores must be done at high speeds of up to a few thousand pieces per day. In this case, the forming tools or core boxes are metallic because the heating temperatures to obtain rapid polymerization of the resins are high, generally greater than 150 ° C and up to 380 ° C. This involves significant tooling costs and especially dimensional accuracy problems of molds and cores, related to the expansion of tools under the effect of heat. On the other hand, respiratory nuisances for people working in this environment have been deemed inadmissible.
C'est pourquoi les procédés de type « hot box » ont été abandonnés il y a une quarantaine d'années par l'industrie, au profit de procédés de type « cold box » (ou boîte froide). Ces procédés de type « cold box » proposaient l'utilisation de liants alternatifs, à froid, générant à cette époque peu de nuisances, en termes d'hygiène et de sécurité, et surtout compatibles avec une cadence de fabrication industrielle élevée.This is why " hot box" processes were abandoned some forty years ago by the industry, in favor of " cold box" processes (or cold boxes). These "cold box" type processes proposed the use of cold binders, which at that time generated little nuisance, in terms of hygiene and safety, and above all compatible with a high industrial production rate.
Cependant, à l'heure actuelle, ces liants alternatifs de type « cold box » posent eux aussi problème dans les procédés industriels, car ils sont devenus incompatibles avec des normes plus sévères en termes d'hygiène, de sécurité et d'environnement.However, at present, these cold box type alternative binders are also problematic in industrial processes because they have become incompatible with more stringent standards in terms of hygiene, safety and the environment.
Dans ce contexte, la demande de brevet français
Ainsi, la demande de brevet français
Cependant, cette amélioration revendiquée dans la demande de brevet français
D'autre part, la demande de brevet
La demande de brevet
C'est dans le contexte développé ci-dessus, que la demanderesse a découvert un procédé amélioré du procédé de la demande de brevet
La présente invention concerne un procédé pour la réalisation d'un corps, de préférence d'un moule et/ou noyau de pièce de fonderie, ledit procédé comprenant au moins les étapes successives suivantes :
- la préparation d'un mélange granulaire, comprenant :
- a- au moins 90%, de préférence de 96 à 99%, en poids de grains, lesdits grains étant principalement composés d'au moins un oxyde minéral, et au moins 80% desdits grains ayant une taille de 10 à 3000 µm,
- b- de 0,3 à 3%, de préférence de 0,6 à 1,5%, en poids d'au moins une résine polycondensée avec du formaldéhyde et/ou ses dérivés, le pourcentage étant calculé en extrait sec de résine,
- c- de 0,001 à 3%, de préférence de 0,005 à 1%, en poids d'au moins un agent durcisseur, le pourcentage étant calculé en extrait sec d'agent durcisseur,
- d- de 0,003 à 1%, de préférence de 0,01 à 0,15%, en poids d'au moins un composé capteur de formaldéhyde, et
- f- de 0,2 à 3%, de préférence de 0,7 à 2%, en poids d'eau;
- la mise en contact dudit mélange granulaire avec au moins une surface d'un outil de formage, et
- l'insufflage dans le mélange granulaire d'au moins un flux de gaz à une température de 50°C à 380°C, pour une durée comprise de 1 à 300 secondes, pour assurer au moins partiellement le durcissement dudit mélange.
- de 0,003% à 1,5%, de préférence de 0,15% à 1%, en poids d'au moins une résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines ;
- Soit par la présence d'un composant e- dans le mélange, à une teneur de 0,003% à 1,5%, de préférence de 0,15% à 1%, en poids par rapport au poids total du mélange, d'au moins une résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines,
- Soit par la présence lors de sa synthèse d'un composé comprenant au moins une unité phénolique et/ou polyphénolique, à une teneur de 1 à 30 % en poids par rapport au poids total de la résine polycondensée.
- the preparation of a granular mixture, comprising:
- a- at least 90%, preferably from 96 to 99% by weight of grains, said grains being composed mainly of at least one inorganic oxide, and at least 80% of said grains having a size of 10 to 3000 microns,
- b- from 0.3 to 3%, preferably from 0.6 to 1.5%, by weight of at least one polycondensed resin with formaldehyde and / or its derivatives, the percentage being calculated as solids content of resin,
- c- from 0.001 to 3%, preferably from 0.005 to 1% by weight of at least one curing agent, the percentage being calculated as solids curing agent,
- d- from 0.003 to 1%, preferably from 0.01 to 0.15%, by weight of at least one formaldehyde-sensing compound, and
- f- from 0.2 to 3%, preferably from 0.7 to 2% by weight of water;
- contacting said granular mixture with at least one surface of a forming tool, and
- blowing into the granular mixture at least one gas stream at a temperature of 50 ° C to 380 ° C, for a period of from 1 to 300 seconds, to at least partially cure said mixture.
- from 0.003% to 1.5%, preferably from 0.15% to 1%, by weight of at least one resin selected from the group consisting of tannins, natural polyphenols, and lignins;
- Either by the presence of a component e- in the mixture, at a content of 0.003% to 1.5%, preferably from 0.15% to 1%, by weight relative to the total weight of the mixture, from less a resin selected from the group consisting of tannins, natural polyphenols, and lignins,
- Or by the presence during its synthesis of a compound comprising at least one phenolic unit and / or polyphenol, at a content of 1 to 30% by weight relative to the total weight of the polycondensed resin.
Il est ainsi possible selon l'invention de modifier la résine par l'une et/ou l'autre des deux possibilités décrites ci-dessus : présence d'un composant e-et/ou présence d'un composé comprenant au moins une unité phénolique et/ou polyphénolique lors de la synthèse de la résine. Il faut au minimum que l'une des deux possibilités soit présente, mais les deux possibilités peuvent être présentes (simultanément).It is thus possible according to the invention to modify the resin by one and / or the other of the two possibilities described above: presence of a component e- and / or presence of a compound comprising at least one unit phenolic and / or polyphenolic during the synthesis of the resin. At a minimum, one must both possibilities are present, but both possibilities can be present (simultaneously).
Ainsi, selon l'invention, la résine polycondensée avec du formaldéhyde et/ou ses dérivés (composant b-) est modifiée par la présence de groupes aromatiques et/ou polyaromatiques dans le mélange.Thus, according to the invention, the polycondensed resin with formaldehyde and / or its derivatives (component b -) is modified by the presence of aromatic and / or polyaromatic groups in the mixture.
La résine polycondensée avec du formaldéhyde et/ou ses dérivés (composant b-) est de préférence une résine furanique, un aminoplaste, un phénoplaste ou un copolymère d'au moins deux de ces trois composés.The polycondensed resin with formaldehyde and / or its derivatives (component b -) is preferably a furanic resin, an aminoplast, a phenoplast or a copolymer of at least two of these three compounds.
Le capteur de formaldéhyde (composant d-) est généralement selon l'invention un composé de la famille des hydrazides, de préférence choisi dans le groupe formé par les mono et dihydrazides, ledit capteur étant de façon encore plus préférée le dihydrazide de l'acide adipique, le dihydrazide de l'acide succinique, ou le carbohydrazide. De façon particulièrement préférée, le capteur de formaldéhyde est le carbohydrazide.The formaldehyde sensor (component d -) is generally, according to the invention, a compound of the family of hydrazides, preferably chosen from the group formed by mono and dihydrazides, the said sensor being even more preferably the dihydrazide of the acid. adipic acid, succinic acid dihydrazide, or carbohydrazide. In a particularly preferred manner, the formaldehyde sensor is carbohydrazide.
La résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines (composant e-) est de préférence une résine de type tanin, de façon encore plus préférée d'une résine de type tanin condensé.The resin selected from the group consisting of tannins, natural polyphenols, and lignins (component e -) is preferably a tannin type resin, more preferably a condensed tannin type resin.
Dans le cas, le composant e) est une résine par lui-même, et est généralement ajouté au composant b) en prémélange (tel un diluant si les deux composants sont liquides). Sa présence modifie le comportement de la résine polycondensée (composant b), qui est donc une résine « modifiée » lors de sa mise en oeuvre) dans le mélange lors de la mise en oeuvre du procédé selon l'invention.In the case, the component e) is a resin by itself, and is generally added to the component b) premix (such a diluent if the two components are liquid). Its presence modifies the behavior of the polycondensed resin (component b), which is therefore a "modified" resin during its use) in the mixture during the implementation of the process according to the invention.
Selon l'invention, il est possible d'ajouter les composants b), c) d) et f), et éventuellement e), au composant a) de façon séparée (i.e. chaque composant b), c) d) et f), et éventuellement e), est ajouté un à un au composant a), ou par au moins un prémélange. Ainsi, il est possible d'effectuer un prémélange des composants b) et e) ; ou bien b), e) et f) ; ou bien c) et e) ; ou bien c), e) et f) ; ou bien d) et e) ; ou bien d), e) et f) ; ou bien b) et f) ; ou bien b), c) et f) ; ou bien b) c) d) et f) ; puis de mélanger ce prémélange avec au moins le composant a). En outre, le composant f), qui est de l'eau, peut être préalablement incorporé, tout ou partie, à au moins un des autres composants.According to the invention, it is possible to add components b), c) d) and f), and possibly e) to component a) separately (ie each component b), c) d) and f) and optionally e) is added one by one to the component a), or by at least one premix. Thus, it is possible to premix the components b) and e); or b), e) and f); or c) and e); or c), e) and f); or d) and e); or d), e) and f); or b) and f); or b), c) and f); or b) c) d) and f); and then mixing this premix with at least component a). In addition, the component f), which is water, may be previously incorporated, in whole or in part, at least one of the other components.
L'étape d'insufflage permet de mettre en oeuvre au moins partiellement au moins une réaction chimique qui assure le durcissement au moins partiel dudit mélange.The blowing step makes it possible to implement at least partially at least one chemical reaction which ensures the at least partial hardening of said mixture.
Ainsi qu'il est connu de l'homme du métier, ces étapes sont généralement suivies d'un retrait du corps sensiblement solide de l'outillage de formage.As is known to those skilled in the art, these steps are generally followed by removal of the substantially solid body from the forming tool.
De façon particulièrement avantageuse, le procédé selon l'invention permet particulièrement, dans le cas de l'utilisation du corps ainsi obtenu pour fonderie de pièce en fonte, de diminuer la production de formaldéhyde durant la réaction, de diminuer le taux d'azote généré dans le corps formé, d'enrichir en carbone le corps formé et d'améliorer la tenue thermique lors du procédé.In a particularly advantageous manner, the process according to the invention makes it particularly possible, in the case of the use of the body thus obtained for cast iron casting, to reduce the production of formaldehyde during the reaction, to reduce the nitrogen content generated. in the formed body, to enrich the formed body in carbon and to improve the thermal resistance during the process.
Bien entendu, le mélange granulaire peut comporter tout autre additif connu de l'homme du métier. En particulier le mélange granulaire peut comporter tout additif, liquide ou pulvérulent, connu de l'homme du métier pour favoriser le comportement physico-chimique du mélange lors de sa transformation et son utilisation ultérieure.Of course, the granular mixture may comprise any other additive known to those skilled in the art. In particular the granular mixture may comprise any additive, liquid or powder, known to those skilled in the art to promote the physico-chemical behavior of the mixture during its processing and its subsequent use.
Les grains du mélange granulaire selon l'invention sont généralement naturels ou synthétiques. De préférence, les grains sont des grains d'oxyde(s) minéral(aux), le plus souvent des mélanges sableux siliceux naturels dont les grains sont composés principalement d'oxyde de silicium et dont la granulométrie AFS (acronyme de « American Foundry Society ») peut aller de 30 à 140.The grains of the granular mixture according to the invention are generally natural or synthetic. Preferably, the grains are grains of inorganic oxide (s), most often natural siliceous sandy mixtures whose grains are composed mainly of silicon oxide and whose particle size AFS (acronym for " American Foundry Society"). Can range from 30 to 140.
L'eau est généralement apportée dans le mélange granulaire principalement comme solvant des composants b) à d), éventuellement e), du mélange granulaire.The water is generally provided in the granular mixture mainly as a solvent of components b) to d), optionally e), of the granular mixture.
En effet, dans la mesure où l'agent durcisseur est généralement incorporé à un taux très faible dans le mélange granulaire, sa dispersion est améliorée s'il est préalablement dilué en solution aqueuse. Il en est de même pour le capteur de formaldéhyde et pour le composant e) éventuel, si celui-ci est fourni sous forme de poudre.Indeed, insofar as the curing agent is generally incorporated at a very low level in the granular mixture, its dispersion is improved if it is previously diluted in aqueous solution. It is the same for the formaldehyde sensor and the component e), if it is provided in powder form.
Le mélange granulaire selon l'invention est généralement sous forme d'au moins un agrégat fluide.The granular mixture according to the invention is generally in the form of at least one fluid aggregate.
La surface de l'outil de formage avec laquelle est en contact le mélange granulaire représente généralement le « négatif » de la pièce à former dans le corps fabriqué selon l'invention.The surface of the forming tool with which the granular mixture is in contact generally represents the "negative" of the part to be formed in the body manufactured according to the invention.
L'étape d'insufflage d'un flux de gaz chaud est généralement telle que la température et le débit dudit flux sont ajustés pour provoquer l'élévation de la température au coeur du mélange granulaire, substantiellement au-dessus de la température ambiante (qui est d'environ 20°C) et de préférence au-dessus de 45°C.The step of blowing a flow of hot gas is generally such that the temperature and the flow rate of said flow are adjusted to cause the temperature rise in the heart of the granular mixture, substantially above ambient temperature (which is about 20 ° C) and preferably above 45 ° C.
Le procédé selon l'invention, par la présence dans le mélange granulaire d'au moins un capteur de formaldéhyde et d'une résine polycondensée modifiée, permet avantageusement d'améliorer significativement les propriétés thermiques du mélange granulaire et de limiter l'émission de formaldéhyde libre lors de la réalisation des corps formés. En outre, la présence d'une résine polycondensée modifiée permet d'améliorer significativement les propriétés thermiques, et de diminuer le taux d'azote, des corps formés. Ces caractéristiques rendent l'utilisation du corps ainsi obtenu particulièrement avantageuse pour la coulée de pièces en fonte et en particulier adaptable à la fonderie en grande série.The process according to the invention, by the presence in the granular mixture of at least one formaldehyde sensor and a modified polycondensed resin, advantageously makes it possible to significantly improve the thermal properties of the granular mixture and to limit the emission of formaldehyde free when performing formed bodies. In addition, the presence of a modified polycondensed resin makes it possible to significantly improve the thermal properties and to reduce the nitrogen content of the bodies formed. These characteristics make the use of the body thus obtained particularly advantageous for the casting of cast iron parts and in particular adaptable to the foundry mass production.
De préférence, le procédé selon l'invention est tel que, en outre, l'outil de formage est chauffé à une température comprise dans une fourchette de 40°C à 180°C, de préférence de 50°C à 150°C. Cela est généralement réalisé dès l'étape de mise en contact, et au plus tard lors de l'étape d'insufflage.Preferably, the method according to the invention is such that, in addition, the forming tool is heated to a temperature in the range of 40 ° C to 180 ° C, preferably 50 ° C to 150 ° C. This is generally done in the contacting step, and at the latest during the blowing step.
Ainsi, la chaleur apportée par le gaz chaud est complétée par la chaleur de chauffage de l'outillage de formage, de façon à optimiser, dans une version préférée de l'invention, le chauffage du mélange granulaire.Thus, the heat provided by the hot gas is supplemented by the heat of heating of the forming tool, so as to optimize, in a preferred version of the invention, the heating of the granular mixture.
Le gaz est de préférence choisi dans le groupe formé par l'air, un gaz neutre et un gaz participant à l'acidification du milieu réactionnel.The gas is preferably selected from the group consisting of air, a neutral gas and a gas involved in the acidification of the reaction medium.
Par « gaz neutre », on entend selon l'invention un gaz ne participant pas à la réaction par exemple choisi parmi le diazote et les gaz dits nobles tels que l'hélium, le néon, et l'argon. Par « gaz participant à l'acidification du milieu réactionnel », on entend selon l'invention un gaz permettant de diminuer in situ le pH du milieu comme le dioxyde de carbone ou le dioxyde de soufre.According to the invention, the term "neutral gas" means a gas which does not participate in the reaction, for example chosen from dinitrogen and the so-called noble gases such as helium, neon and argon. By "gas involved in the acidification of the reaction medium" is meant according to the invention a gas for decreasing in situ the pH of the medium such as carbon dioxide or sulfur dioxide.
Dans un mode de réalisation préféré de l'invention, le procédé comporte en outre une étape supplémentaire au cours de laquelle on fait circuler au sein du mélange granulaire au moins partiellement durci un flux d'au moins un gaz à température comprise dans une fourchette de 5°C à 45°C, pendant une durée comprise dans une fourchette de 1 à 300 secondes, le gaz étant de préférence choisi dans le groupe formé par l'air, le diazote et le dioxyde de carbone. Cette étape est le plus souvent réalisée avant l'étape éventuelle de retrait du corps de l'outil de formage. Le gaz est le plus souvent non chauffé au préalable, et donc sensiblement à température ambiante, voire éventuellement refroidi.In a preferred embodiment of the invention, the method also comprises an additional step during which a stream of at least one gas is circulated within the at least partially hardened granular mixture at a temperature within a range of 5 ° C to 45 ° C, for a time in a range of 1 to 300 seconds, the gas being preferably selected from the group consisting of air, nitrogen and carbon dioxide. This step is most often carried out before the optional step of removing the body from the forming tool. The gas is usually not previously heated, and therefore substantially at room temperature, or possibly cooled.
En effet, comme les nuisances du formaldéhyde peuvent s'exercer postérieurement à la fabrication du corps, durant son stockage ou sa manipulation ultérieure, il s'avère très utile et avantageux dans le cadre de l'invention de compléter l'action du capteur de formaldéhyde en bloquant la réaction de polymérisation de la résine polycondensée modifiée, par refroidissement du corps après son durcissement partiel. De plus ce flux de gaz permet avantageusement de laver par un flux d'air, de diazote ou de dioxyde de carbone, le formaldéhyde libre éventuellement résiduel.Indeed, since the nuisance of formaldehyde can be exerted after the manufacture of the body during storage or subsequent handling, it is very useful and advantageous in the context of the invention to complete the action of the sensor. formaldehyde by blocking the polymerization reaction of the modified polycondensed resin by cooling the body after partial curing. In addition, this flow of gas advantageously makes it possible to wash with a flow of air, of nitrogen or of carbon dioxide, the free formaldehyde which may be residual.
On entend par résine polycondensée ou résine polycondensée avec du formaldéhyde et/ou ses dérivés, une composition d'au moins une résine ayant subi une réaction chimique entre un premier élément choisi parmi l'urée et ses dérivés, la mélamine, la benzoguanamine, le glycolurile, le phénol et/ou ses dérivés, et l'alcool furfurylique et/ou ses dérivés, et un second élément choisi parmi le formaldéhyde et/ou ses dérivés, dans laquelle de préférence la croissance de chaîne provoque généralement à chaque étape la libération d'une molécule d'eau.The term polycondensed resin or polycondensed resin with formaldehyde and / or its derivatives, a composition of at least one resin having undergone a chemical reaction between a first element selected from urea and its derivatives, melamine, benzoguanamine, glycoluril, phenol and / or its derivatives, and furfuryl alcohol and / or its derivatives, and a second element selected from formaldehyde and / or its derivatives, wherein preferably the chain growth generally causes at each stage the release of a molecule of water.
Cette résine polycondensée est généralement un polymère thermodurcissable, tel qu'une résine furanique ou un aminoplaste ou un phénoplaste ou un copolymère de ces composés, de préférence un aminoplaste ou un phénoplaste ou un copolymère aminoplaste-phénoplaste.This polycondensed resin is generally a thermosetting polymer, such as a furan resin or an aminoplast or a phenoplast or a copolymer of these compounds, preferably an aminoplast or a phenoplast or an aminoplast-phenoplast copolymer.
Les aminoplastes sont obtenus par polycondensation du premier comonomère qu'est le formaldéhyde et du second comonomère portant des groupements amino NH2-. Ils sont généralement divisés en deux familles principales de composés, à savoir les résines urée-formaldéhyde (ou urée-formol) (sigle UF) et mélamine-formaldéhyde (ou mélamine-formol) (sigle MF).The aminoplasts are obtained by polycondensation of the first comonomer which is formaldehyde and the second comonomer carrying amino groups NH 2 -. They are usually divided into two families compounds, namely urea-formaldehyde (or urea-formaldehyde) (UF) and melamine-formaldehyde (or melamine-formaldehyde) resins (MF).
Les phénoplastes ou résines phénol-formaldéhyde (sigle PF) sont obtenus par polycondensation entre un premier comonomère qu'est le formaldéhyde et un second comonomère qu'est le phénol. On distingue deux types de résines phénoplastes : les novolaques, préparées par catalyse acide, et les résols, obtenus par catalyse basique. Le phénoplaste le plus connu est la bakélite® (ou anhydrure de polyoxybenzylmethylèneglycol), qui est le plus ancien matériau polymère synthétique industriel.Phenoplasts or phenol-formaldehyde resins (PF) are obtained by polycondensation between a first comonomer that is formaldehyde and a second comonomer that is phenol. There are two types of phenolic resins: novolacs, prepared by acid catalysis, and the resols, obtained by basic catalysis. The best known phenoplast is bakelite ® (or polyoxybenzylmethylene glycol anhydride), which is the oldest industrial synthetic polymer material.
La résine furanique est obtenue par polycondensation du premier comonomère qu'est l'alcool furfurylique et du second comonomère qu'est le formaldéhyde.The furanic resin is obtained by polycondensation of the first comonomer furfuryl alcohol and the second comonomer is formaldehyde.
Le ou les composants de la résine polycondensée peu(ven)t rester libre en excès dans la résine polycondensée, ou encore y avoir été ajouté(s) après la polycondensation.The component (s) of the polycondensed resin may remain free in excess in the polycondensed resin, or may have been added thereto after the polycondensation.
La résine polycondensée avec du formaldéhyde et/ou ses dérivés est généralement telle qu'elle thermodurcit en milieu acide. Une telle résine polycondensée est généralement disponible commercialement.The polycondensed resin with formaldehyde and / or its derivatives is generally such that it thermosets in acidic medium. Such a polycondensed resin is generally commercially available.
La résine polycondensée peut, selon l'invention, être modifiée par la présence lors de sa synthèse d'un composé comprenant au moins une unité phénolique et/ou polyphénolique, à une teneur de 1 à 30 % en poids, de préférence de 5 à 20% en poids, par rapport au poids total de la résine polycondensée modifiée. Ce n'est donc pas la résine polycondensée décrite dans la demande de brevet français
La résine polycondensée peut ainsi avoir été prémélangée avec un composé, le plus souvent synthétique, tel que la vanilline ou le phloroglucinol. Dans ce cas, la présence dans le mélange granulaire utilisé dans le procédé selon l'invention d'un composant e) selon l'invention, i.e. la résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines, est optionnelle.The polycondensed resin may thus have been premixed with a compound, most often synthetic, such as vanillin or phloroglucinol. In this case, the presence in the granular mixture used in the process according to the invention a component e) according to the invention, ie the resin selected from the group formed by tannins, natural polyphenols, and lignins, is optional.
L'unité phénolique et/ou polyphénolique peut être d'origine naturelle ou synthétique. La résine est ainsi sous forme d'un copolymère formophénolique. Dans le cadre de ce mode de réalisation, il est particulièrement préféré que l'unité phénolique et/ou polyphénolique soit présente dans un composé choisi dans le groupe formé par la vanilline (4-hydroxy-3-méthoxybenzaldéhyde) et le phloroglucinol (benzène-1,3,5-triol).The phenolic and / or polyphenolic unit may be of natural or synthetic origin. The resin is thus in the form of a formophenolic copolymer. In the context of this embodiment, it is particularly preferred that the phenolic and / or polyphenolic unit be present in a compound selected from the group consisting of vanillin (4-hydroxy-3-methoxybenzaldehyde) and phloroglucinol (benzene- 1,3,5-triol).
La résine polycondensée avec du formaldéhyde et/ou ses dérivés selon l'invention peut en outre contenir éventuellement au moins un additif choisi parmi les solvants, les diluants, les stabilisants et les charges de particules solides, utilisé(e)(s) habituellement et connu(e)(s) de l'homme du métier pour obtenir un effet particulier. Ainsi ladite résine polycondensée peut contenir au moins un silane, qui permet généralement de ponter, et donc d'optimiser, la liaison entre la résine et les grains.The polycondensed resin with formaldehyde and / or its derivatives according to the invention may also optionally contain at least one additive chosen from solvents, diluents, stabilizers and solid particle fillers, which are usually used and known to those skilled in the art to obtain a particular effect. Thus, said polycondensed resin may contain at least one silane, which generally makes it possible to bridge, and thus optimize, the bond between the resin and the grains.
La résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines, est un polymère naturel riche en noyaux aromatiques (i.e. comportant au moins deux noyaux aromatiques). En réalité, cette résine contient au moins un noyau aromatique par unité monomère du polymère, donc une pluralité de noyaux aromatiques. Cette résine est choisie selon l'invention dans le groupe formé par les tanins, qui sont généralement d'origine naturelle, de préférence condensés et/ou modifiés pour les rendre solubles dans l'eau, tels que les extraits de l'arbre Quebracho, les polyphénols naturels, tels que ceux extrait de araucaria angustifolia (pin du Paraná) ou de pinus palustris (pin des marais), et les lignines, modifiées ou non.The resin selected from the group consisting of tannins, natural polyphenols, and lignins, is a natural polymer rich in aromatic rings (ie having at least two aromatic rings). In reality, this resin contains at least one aromatic nucleus per monomer unit of the polymer, thus a plurality of aromatic nuclei. This resin is chosen according to the invention from the group formed by tannins, which are generally of natural origin, preferably condensed and / or modified to make them soluble in water, such as extracts from the Quebracho tree, natural polyphenols, such as those extracted from araucaria angustifolia (Paraná pine) or pinus palustris (swamp pine), and lignins, modified or not.
La résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines, est le plus souvent renouvelable. Par résine renouvelable, on entend selon l'invention soit une résine naturelle dont le stock peut se reconstituer sur une période courte à l'échelle humaine, soit une résine synthétique dont les principaux matériaux de départ de synthèse sont des composants renouvelables ; en théorie le renouvellement doit être effectué au moins aussi vite que la consommation.The resin selected from the group formed by tannins, natural polyphenols, and lignins, is most often renewable. The term "renewable resin" means, according to the invention, either a natural resin whose stock can be reconstituted over a short period on a human scale, or a synthetic resin whose main synthetic starting materials are renewable components; in theory renewal must be done at least as fast as consumption.
Dans un mode de réalisation préféré, la résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines, est une résine de type tanin, et de façon encore plus préférée c'est une résine de type tanin condensé.In a preferred embodiment, the resin selected from the group consisting of tannins, natural polyphenols, and lignins, is a tannin-type resin, and even more preferably it is a condensed tannin-type resin.
La résine de type tanin est usuellement une substance naturelle phénolique. C'est généralement un métabolite secondaire de plante supérieure que l'on trouve pratiquement dans toutes les parties des végétaux (écorce, racines, feuilles, tiges, etc). Les tanins sont des résines naturelles polyphénoliques soit de polyols de type monosaccharide et d'unités galloyles ou leurs dérivés, liés à des flavonoïdes ou des triterpénoïdes, soit des oligomères ou des polymères de flavanols. De préférence les tanins utilisés selon l'invention sont des polyflavonoïdes, par exemple de type tanin de l'arbre Quebracho.The tannin type resin is usually a natural phenolic substance. It is usually a secondary metabolite of superior plant that is found practically in all parts of plants (bark, roots, leaves, stems, etc.). The tannins are polyphenol natural resins either monosaccharide type polyols and galloyl units or derivatives thereof, linked to flavonoids or triterpenoids, or oligomers or flavanol polymers. Preferably, the tannins used according to the invention are polyflavonoids, for example of the tannin type of the Quebracho tree.
Les lignines sont des polymères basés sur un ou plusieurs monolignols, comme l'alcool paracoumarylique, l'alcool coniférylique et l'alcool sinapylique. Les lignines peuvent par exemple être modifiées en lignosulfonates par réactions avec des bisulfites.Lignins are polymers based on one or more monolignols, such as paracoumaryl alcohol, coniferyl alcohol and sinapyl alcohol. The lignins may, for example, be modified to lignosulphonates by reactions with bisulphites.
La résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines, peut aussi être une résine thermoplastique, par exemple, un extrait de araucaria angustifolia (pin du Paraná) ou de pinus palustris (pin des marais).The resin selected from the group consisting of tannins, natural polyphenols, and lignins, may also be a thermoplastic resin, for example, an extract of araucaria angustifolia (Paraná pine) or pinus palustris (swamp pine).
La résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines, peut être composée de phénols à longue chaîne aliphatique comme un extrait de coquilles de noix de cajou.The resin selected from the group consisting of tannins, natural polyphenols, and lignins, can be composed of long-chain aliphatic phenols such as cashew nut shell extract.
Ainsi, la résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines, peut être un composé commercial tel que les produits commerciaux suivants: Respine RLP de la société POLYTRADE (résine aromatique naturelle issue de araucaria angustifolia) ; VINSOL® de la société HERCULES (composé d'environ 57% de polyphénols, 28% de colophanes et 15% de terpenoïdes) ; QSF (partie soluble à l'alcool des tanins de Quebracho), FINTAN 737B (tanin condensé modifié issu du Schinopsis lorentzii ou Quebracho colorado en poudre) et FINTAN 737C (tanin condensé stabilisé issu du Schinopsis lorentzii ou Quebracho colorado en solution à 45%) de la société INDUNOR ; et CARDANOL (phénols à longue chaîne aliphatique issus de coquilles de noix de cajou) de la société SAI CHEMICALS.Thus, the resin selected from the group formed by tannins, natural polyphenols, and lignins, may be a commercial compound such as the following commercial products: Respine RLP from the company POLYTRADE (natural aromatic resin derived from araucaria angustifolia ); VINSOL ® from HERCULES (consisting of approximately 57% polyphenols, 28% rosin and 15% terpenoid); QSF (alcohol-soluble part of tannins de Quebracho), FINTAN 737B (modified condensed tannin from Schinopsis lorentzii or Quebracho colorado powder) and FINTAN 737C (stabilized condensed tannin from Schinopsis lorentzii or Quebracho colorado in 45% solution) from INDUNOR; and CARDANOL (long-chain aliphatic phenols from cashew shells) from SAI CHEMICALS.
L'agent durcisseur est généralement choisi dans le groupe formé par les composés suivants :
- les sels naturellement acides, tels que les sels d'ammonium, notamment les persulfates, les nitrates, les bisulfates, les sulfates et les chlorures ;
- les sels générant un acide par réaction avec un aldéhyde, tels que les sels d'hydroxylamine, notamment les sulfates, les chlorhydrates, les phosphates, les sulfonates et les nitrates d'hydroxylamine ;
- les acides sublimables, notamment l'acide oxalique et l'acide benzoïque ; et, éventuellement,
- les acides organiques compatibles avec le procédé au regard de leur réactivité et de leur toxicité, comme par exemple l'acide lactique et l'acide citrique.
- naturally acidic salts, such as ammonium salts, especially persulfates, nitrates, bisulphates, sulphates and chlorides;
- salts generating an acid by reaction with an aldehyde, such as hydroxylamine salts, especially sulphates, hydrochlorides, phosphates, sulphonates and hydroxylamine nitrates;
- sublimable acids, especially oxalic acid and benzoic acid; and eventually,
- organic acids compatible with the process with regard to their reactivity and toxicity, such as lactic acid and citric acid.
L'agent durcisseur est plus généralement tel qu'il rend le milieu réactionnel du mélange acide, soit par son acidité propre, soit par sa capacité à libérer de l'acide au cours du processus de polymérisation.The curing agent is more generally such that it renders the reaction medium of the acid mixture, either by its own acidity, or by its ability to release acid during the polymerization process.
De façon particulièrement préférée, l'agent durcisseur est choisi dans le groupe formé par les sels d'hydroxylamine, et de façon encore plus préférée, l'agent durcisseur est le sulfate d'hydroxylamine. Les sels d'hydroxylamine libèrent avantageusement un acide en présence de formaldéhyde.Particularly preferably, the curing agent is selected from the group consisting of hydroxylamine salts, and even more preferably, the curing agent is hydroxylamine sulfate. The hydroxylamine salts advantageously release an acid in the presence of formaldehyde.
Dans le cas préféré où l'agent durcisseur est un sel d'hydroxylamine, il apparaît de façon surprenante selon l'invention que le formaldéhyde libre disponible se combine prioritairement avec ce sel d'hydroxylamine pour libérer un acide, et que le capteur de formaldéhyde n'inhibe pas ou peu la formation d'acide par ledit sel au cours de la réaction de durcissement.In the preferred case where the curing agent is a hydroxylamine salt, it surprisingly appears according to the invention that the free formaldehyde available combines primarily with this hydroxylamine salt to release an acid, and that the formaldehyde sensor does not inhibit or little acid formation by said salt during the curing reaction.
En outre, la demanderesse a constaté que l'utilisation de sel d'hydroxylamine améliore significativement et avantageusement le procédé selon l'invention, en accélérant la cinétique de durcissement et en augmentant l'acidité du milieu réactionnel au fur et à mesure que la réaction de thermodurcissement libère du formaldéhyde.In addition, the Applicant has found that the use of hydroxylamine salt significantly and advantageously improves the process according to the invention, by accelerating the hardening kinetics and by increasing the acidity of the reaction medium as the thermosetting reaction releases formaldehyde.
De plus, l'ajout du capteur de formaldéhyde améliore sensiblement les caractéristiques mécaniques des corps formés.In addition, the addition of the formaldehyde sensor significantly improves the mechanical characteristics of the formed bodies.
L'homme du métier est à même de choisir les résines b) et e), ainsi que l'agent durcisseur, qui conviennent au cas qui le concerne, en particulier en prenant en compte la réactivité du système de liant, c'est-à-dire des résine(s) et agent(s) durcisseur(s) incorporés dans le mélange granulaire.Those skilled in the art are able to choose the resins b) and e), as well as the curing agent, which are suitable for the case which concerns it, in particular taking into account the reactivity of the binder system, that is to say that is, the resin (s) and hardening agent (s) incorporated in the granular mixture.
La réalisation du mélange granulaire selon la première étape du procédé de l'invention s'effectue généralement de façon connue de l'homme du métier. Ainsi, de façon classique, en présence de matériel de malaxage usuel, l'homme du métier introduit d'abord la ou les parties granulaires dans un mélangeur et procède ensuite à l'introduction de parties liquides, le temps de mélange étant fonction du matériel, et de préférence de 15 s à 5 min.The production of the granular mixture according to the first step of the process of the invention is generally carried out in a manner known to those skilled in the art. Thus, conventionally, in the presence of conventional mixing equipment, those skilled in the art first introduce the granular part or parts into a mixer and then proceed to the introduction of liquid parts, the mixing time being a function of the material and preferably from 15 s to 5 min.
L'invention concerne tout particulièrement un procédé de fabrication d'une pièce de fonderie en métal, ou alliage métallique, moulé, qui comprend la coulée d'un métal, ou alliage métallique, liquide dans au moins un moule et/ou noyau, caractérisé en ce que ledit moule est un corps obtenu par le procédé selon l'invention tel que décrit précédemment.The invention particularly relates to a method of manufacturing a casting piece of metal, or metal alloy, molded, which comprises casting a metal, or metal alloy, liquid in at least one mold and / or core, characterized in that said mold is a body obtained by the process according to the invention as described above.
De préférence, un tel procédé est tel que le métal, ou alliage métallique, est choisi dans le groupe formé par l'aluminium, les alliages ferreux choisi dans le groupe formé par les aciers et les fontes, les métaux non ferreux, les alliages non ferreux, et, de façon plus préférée, le métal ou alliage métallique est choisi dans le groupe formé par les fontes.Preferably, such a method is such that the metal, or metal alloy, is selected from the group formed by aluminum, the ferrous alloys selected from the group consisting of steels and cast irons, non-ferrous metals, non-alloys ferrous, and, more preferably, the metal or metal alloy is selected from the group formed by the fonts.
L'invention concerne aussi toute pièce métallique moulée obtenue par un procédé de fabrication tel que décrit précédemment. L'invention concerne, en outre, tout ensemble mécanique comportant au moins une telle pièce.The invention also relates to any molded metal part obtained by a manufacturing method as described above. The invention further relates to any mechanical assembly comprising at least one such piece.
L'invention est illustrée par la
La
L'invention sera mieux comprise à la lumière des exemples suivants qui illustrent l'invention à titre non limitatif.The invention will be better understood in light of the following examples which illustrate the invention by way of non-limiting example.
Les exemples suivants ont été réalisés en mélangeant à chaque fois 4 kg de sable siliceux SIFRACO LA 32 aux autres composants dans les proportions indiquées pour chaque mélange granulaire.The following examples were carried out by mixing each time 4 kg of SIFRACO LA 32 siliceous sand with the other components in the proportions indicated for each granular mixture.
Pour chaque exemple, un prémélange a été réalisé comprenant principalement la résine polycondensée (composant b)) et éventuellement une résine choisie dans le groupe formé par les tanins, les polyphénols naturels, et les lignines (composant e)), et un second prémélange a été réalisé comprenant l'agent durcisseur (composant c)) et éventuellement un composé capteur de formaldéhyde (composant d)). De l'eau était généralement présente dans ces deux prémélanges. Ensuite, le mélange granulaire était effectué par malaxage du sable siliceux, du premier prémélange et du second prémélange. Ce mélange granulaire a été effectué dans un malaxeur à bol vibrant avec un temps de mélange de 60 secondes. Le mélange granulaire a ensuite été insufflé dans une boîte munie d'un système de chauffage et d'une amenée d'air chaud (à 100-120°C), sous une pression de 1,5 bar (0,15 MPa), pendant une durée de 60 secondes, contenant deux éprouvettes de mesure de caractéristiques mécaniques normalisées de section carrée 5 cm2, sur une machine ROPER.For each example, a premix was made comprising mainly the polycondensed resin (component b) and optionally a resin selected from the group consisting of tannins, natural polyphenols, and lignins (component e)), and a second premix a was performed comprising the curing agent (component c)) and optionally a formaldehyde sensor compound (component d)). Water was generally present in these two premixes. Then, the granular mixture was made by mixing the siliceous sand, the first premix and the second premix. This granular mixture was carried out in a vibratory bowl mixer with a mixing time of 60 seconds. The granular mixture was then blown into a box equipped with a heating system and a supply of hot air (at 100-120 ° C) under a pressure of 1.5 bar (0.15 MPa), for a period of 60 seconds, containing two test pieces of standardized mechanical characteristics of square section 5 cm 2 , on a ROPER machine.
Le durcissement s'est effectué selon les données indiquées pour chaque mélange granulaire.Curing was performed according to the data indicated for each granular mixture.
La mesure du formaldéhyde au malaxage a été effectuée par l'appareillage Pompe DRAGER modèle Accuro munie des tubes de dosage DRAGER « formaldéhyde » (0,2/a). La gamme de mesures est de 0,2 à 5 ppm. Les mesures ont été effectuées au-dessus du bol vibrant du malaxeur.The measurement of formaldehyde during mixing was carried out using the DRAGER model Accuro pump equipment equipped with DRAGER "formaldehyde" dosing tubes (0.2 / a). The range of measurements is 0.2 to 5 ppm. The measurements were made above the vibrating bowl of the mixer.
La mesure du formaldéhyde au déboîtage a été effectuée par l'appareillage Pompe DRAGER modèle Accuro munie des tubes de dosage DRAGER « formaldéhyde » (0,2/a ou 2/a), selon la concentration à mesurer dans une enceinte de 10 litres dans laquelle circulait un flux d'azote de 0,5 L/min. Une éprouvette était placée dans l'enceinte dès sa sortie de boîte. Le tube de dosage était utilisé pour mesurer le formaldéhyde dans l'air de l'enceinte durant 180 secondes. Les résultats sont donnés tels quels pour le tube 0,2/a (n = 20 coups de pompe), et sont multipliés par 4 pour le tube 2/a (n = 5 coups de pompe).The formaldehyde removal measurement was carried out using the DRAGER model Accuro pump equipment fitted with DRAGER "formaldehyde" dosing tubes (0.2 / a or 2 / a), depending on the concentration to be measured in a 10 liter chamber in which circulated a flow of nitrogen of 0.5 L / min. A test tube was placed in the enclosure as soon as it came out of the box. The assay tube was used to measure formaldehyde in the enclosure air for 180 seconds. The results are given as such for the tube 0.2 / a (n = 20 strokes), and are multiplied by 4 for the tube 2 / a (n = 5 strokes).
Tous les taux d'incorporation sont des pourcentages en poids.All incorporation rates are percentages by weight.
Les mesures de flexion ont été effectuées selon les recommandations techniques n°481 et 487 de décembre 1999 du B.N.I.F. édités et disponibles auprès du Centre Technique des Industries de la Fonderie situé à Sèvres en France. Les résultats sont exprimés en daN/cm2.The bending measurements were carried out according to the technical recommendations n ° 481 and 487 of December 1999 of the BNIF published and available from the Technical Center of the Foundry Industries located in Sèvres in France. The results are expressed in daN / cm 2 .
On considère que des résistances à la flexion d'environ 10 daN/cm2 à chaud dès la sortie de la boîte sont suffisantes pour permettre la manipulation des corps formés, et que des résistances d'environ 30 daN/cm2 à froid, soit une heure après la sortie de la boîte, sont souvent satisfaisantes pour permettre la coulée du métal.It is considered that flexural strengths of about 10 daN / cm 2 when hot from the outlet of the box are sufficient to allow the handling of the bodies formed, and that resistances of about 30 daN / cm 2 when cold, either an hour after leaving the box, are often satisfactory to allow the casting of the metal.
Les résistances à la flexion ont été mesurées aussi bien à chaud qu'à froid, après un temps de cuisson de 15 secondes, de 30 secondes, de 60 secondes et de 120 secondes en boîte.The flexural strengths were measured both hot and cold after a cooking time of 15 seconds, 30 seconds, 60 seconds and 120 seconds in a can.
La détection en fin de déboîtage (ou extraction) d'une teneur en formaldéhyde (libre) de plus de 20 fois inférieure au procédé boîte chaude classique est considérée comme rendant le corps formé propre à une utilisation industrielle.The detection at the end of dislocation (or extraction) of a content of formaldehyde (free) more than 20 times lower than the conventional hot box process is considered to make the shaped body suitable for industrial use.
L'extrait sec exprimé en % poids est le résiduel produit après chauffage d'un gramme de produit à 135°C pendant une heure.The dry extract expressed in% by weight is the residue produced after heating one gram of product at 135 ° C. for one hour.
Les éprouvettes obtenues sont des corps formés solides que l'on peut assimiler à des noyaux.The test pieces obtained are solid formed bodies that can be assimilated to nuclei.
La vitesse de désintégration du corps granulaire à 450°C a été mesurée dans les conditions suivantes :
- Des corps moulés de forme parallélépipédique de section carrée 5 cm2 ont été confectionnés. Les corps moulés ont ensuite été laissés 24 heures au repos.
- Molded bodies of parallelepipedal shape of square section 5 cm 2 were made. The molded bodies were then left for 24 hours at rest.
On a ensuite confectionné, dans ces corps moulés, des cubes ajustés à 23,5 g (± 0,5 g) par cube, en omettant d'utiliser les extrémités des corps moulés.These cubes were then made into cubes adjusted to 23.5 g (± 0.5 g) per cube, omitting to use the ends of the moldings.
Les cubes ont été placés séparément dans des creusets fermés par un couvercle. Les creusets ont été repérés.The cubes were placed separately in crucibles closed by a lid. The crucibles were spotted.
Les creusets ont ensuite été placés dans un four à moufle régulé à 450°C, un chronomètre ayant été déclenché à la fermeture du four.The crucibles were then placed in a muffle furnace regulated at 450 ° C, a timer having been triggered when the oven was closed.
Les creusets ont été sortis du four à intervalles réguliers (par exemple 5-10-20-30-40 minutes ...) puis laissés à refroidir jusqu'à température ambiante.The crucibles were taken out of the oven at regular intervals (eg 5-10-20-30-40 minutes ...) and allowed to cool to room temperature.
Le contenu de chaque creuset a ensuite été placé sur un tamis de maille 1 mm, et soumis à la vibration d'un tamiseur de laboratoire de marque Retsch et de modèle VS1000 pendant 30 secondes.The contents of each crucible were then placed on a 1 mm mesh screen, and vibrated by a Retsch brand VS1000 laboratory sieve for 30 seconds.
La partie passante a été récupérée, pesée et la masse obtenue a été transformée en pourcentage.The pass-through portion was recovered, weighed and the resulting mass converted to percent.
Cette mesure, qui est représentative de la tenue à chaud de la résine polycondensée, est donnée sur la courbe ci-jointe (
On estime qu'un pourcentage de corps formé passant à travers le tamis, dans ces conditions d'essais, inférieur à 50%, au bout de vingt minutes, permet la coulée de pièces en fonte.It is estimated that a percentage of formed body passing through the sieve, under these test conditions, less than 50%, after twenty minutes, allows the casting of cast iron parts.
- Résine : Résine urée-formol, produit commercial Cleantech 11 R26, synthétisée en milieu acide avec un rapport molaire formaldéhyde/urée de 2,37 (utilisée à 2,0% par rapport au sable)Resin: Urea-formaldehyde resin, Cleantech 11 R26 commercial product, synthesized in an acidic medium with a formaldehyde / urea molar ratio of 2.37 (used at 2.0% relative to sand)
- Catalyseur: Produit commercial Cleantech 14D38 de la société Hüttenes Albertus France contenant 3% de sulfate d'hydroxylamine, 15% de carbohydrazide et 82% d'eau (utilisé à 0,4% par rapport au sable)Catalyst: Cleantech 14D38 commercial product from Hüttenes Albertus France containing 3% hydroxylamine sulfate, 15% carbohydrazide and 82% water (used at 0.4% relative to sand)
- Température Boîte : 130°CTemperature box: 130 ° C
- Température d'air chaud : 100-120°CHot air temperature: 100-120 ° C
- Résistance flexion à chaud en sortie de boîte : respectivement à 30, 60 et 120 secondes : 18, 32 et 55 daN/cm2 Hot bending resistance at the box outlet: at 30, 60 and 120 seconds respectively: 18, 32 and 55 daN / cm 2
- Résistance flexion à froid, respectivement à 30, 60 et 120 secondes : 72, 80 et 72 daN/cm2 Cold bending resistance, respectively 30, 60 and 120 seconds: 72, 80 and 72 daN / cm 2
Les résistances à la flexion à chaud et à froid sont suffisantes pour permettre, respectivement, la manipulation des corps formés et la coulée du métal.
- Formaldéhyde au malaxage : inférieur à 0,2 ppm (non détectable)
- Formaldéhyde au déboîtage : valeur comparative 0,2
- Formaldehyde with mixing: less than 0.2 ppm (not detectable)
- Formaldehyde on release: comparative value 0.2
Les émissions de formaldéhyde au malaxage et au déboîtage sont extrêmement faibles (au déboîtage environ 600 fois plus faibles que le procédé boîte chaude représenté par l'exemple 3).
% passant (P) à 20 minutes : 79% (voir Courbe A de la
% passing (P) at 20 minutes: 79% (see Curve A of the
La tenue thermique, exprimée par ce pourcentage, est incompatible avec la coulée de pièces de fonderie en fonte.The thermal resistance, expressed by this percentage, is incompatible with the casting of cast iron casting parts.
- Résine : Résine urée-mélamine/formol référencée FUM274 synthétisée avec un rapport molaire formaldéhyde/urée de 2,95 et un rapport molaire formaldéhyde/mélamine de 3,45 (utilisée à 2% par rapport au sable)Resin: Resin urea-melamine / formalin referenced FUM274 synthesized with a formaldehyde / urea molar ratio of 2.95 and a formaldehyde / melamine molar ratio of 3.45 (used at 2% relative to sand)
- Catalyseur: référencé UFAC 12/268 contenant (20%) de sulfate d'hydroxylamine et (80%) d'eau (utilisé à 0,4% par rapport au sable)Catalyst: referenced UFAC 12/268 containing (20%) hydroxylamine sulfate and (80%) water (used at 0.4% relative to sand)
- Température Boîte : 120°CBox temperature: 120 ° C
- Température d'air chaud : 100-120°CHot air temperature: 100-120 ° C
- Résistance flexion à chaud en sortie de boîte : respectivement à 30, 60 et 120 secondes : 17, 24 et 44 daN/cm2 Hot bending resistance at the box outlet: at 30, 60 and 120 seconds respectively: 17, 24 and 44 daN / cm 2
- Résistance flexion à froid, respectivement à 30, 60 et 120 secondes : 72, 70 et 53 daN/cm2 Cold bending strength at 30, 60 and 120 seconds respectively: 72, 70 and 53 daN / cm 2
- Formaldéhyde au malaxage : 1 ppmFormaldehyde with mixing: 1 ppm
Les résistances à la flexion à chaud et à froid sont suffisantes pour permettre, respectivement, la manipulation des corps formés et la coulée du métal.
Formaldéhyde au déboîtage : valeur comparative 80The hot and cold bending resistances are sufficient to allow, respectively, the manipulation of the formed bodies and the casting of the metal.
Formaldehyde in Deboxage:
Les émissions de formaldéhyde au malaxage et au déboîtage sont élevées et posent problème.
% passant (P) à 20 minutes : 37% (voir courbe C de la
% passing (P) at 20 minutes: 37% (see curve C of the
La tenue thermique, exprimée par ce pourcentage, est suffisante pour la coulée de pièces de fonderie en fonte.The thermal resistance, expressed by this percentage, is sufficient for the casting of cast iron casting parts.
Résine: Résine urée-phénol/formol, produit commercial Résital 12B62 de la société Hüttenes Albertus France.Resin: Urea-phenol / formaldehyde resin, commercial product Resital 12B62 from Hüttenes Albertus France.
Cette résine est caractéristique du procédé « boîte chaude », et a été utilisée à 2% par rapport au sable.This resin is characteristic of the "hot box" process, and was used at 2% compared to sand.
Catalyseur : Produit commercial Harter AT3B de la société Hüttenes Albertus France (lignosulfonate de magnésium en solution à 50%), d'urée et de nitrate d'ammonium.Catalyst: Commercial product Harter AT3B from Hüttenes Albertus France (50% magnesium lignosulfonate solution), urea and ammonium nitrate.
Ce catalyseur a été utilisé à 0,5% par rapport au sable.This catalyst was used at 0.5% with respect to the sand.
Cette résine est caractéristique du procédé « boîte chaude » utilisé en fonderie de fonte.
Température Boîte : 220°CThis resin is characteristic of the "hot box" process used in cast iron foundries.
Box temperature: 220 ° C
Résistance flexion à chaud en sortie de boîte : respectivement à 30, 60 et 120 secondes : 34, 51 et 61 daN/cm2
Résistance flexion à froid, respectivement à 30, 60 et 120 secondes : 70, 70 et 59 daN/cm2 Hot bending resistance at the box outlet: at 30, 60 and 120 seconds respectively: 34, 51 and 61 daN / cm 2
Cold bending strength at 30, 60 and 120 seconds respectively: 70, 70 and 59 daN / cm 2
Les résistances à la flexion à chaud et à froid sont suffisantes pour permettre, respectivement, la manipulation des corps formés et la coulée du métal.
- Formaldéhyde au malaxage : 1 ppm
- Formaldéhyde au déboîtage : valeur comparative 120
- Formaldehyde with mixing: 1 ppm
- Formaldehyde at the disposal: comparative value 120
Les émissions de formaldéhyde au malaxage et au déboîtage sont incompatibles avec l'évolution des normes hygiène et sécurité.Formaldehyde emissions during mixing and disintegration are incompatible with changes in hygiene and safety standards.
Résine : Résine urée-formol comportant de la vanilline, qui a été synthétisée en milieu acide avec un rapport molaire formaldéhyde/urée de 2,37, et à laquelle il a été ajouté de la vanilline dans un rapport molaire urée/vanilline de 4,5.Resin: Urea-formaldehyde resin comprising vanillin, which has been synthesized in an acidic medium with a formaldehyde / urea mole ratio of 2.37, and to which vanillin has been added in a molar ratio of urea to vanillin of 4, 5.
Le taux de vanilline par rapport à la résine est de 11,3% en poids.The vanillin content with respect to the resin is 11.3% by weight.
Cette résine a été utilisée à 2% par rapport au sable.
Catalyseur : Catalyseur constitué de 1,4% d'hydroxylamine en solution à 50%, de 1,7% d'acide p-toluène sulfonique en solution à 65%, de 15,1% de carbohydrazide, de 2,2% de sulfate d'hydroxylamine et de 79,7% d'eau.This resin was used at 2% relative to sand.
Catalyst: Catalyst consisting of 1.4% hydroxylamine in 50% solution, 1.7% p-toluenesulphonic acid in 65% solution, 15.1% carbohydrazide, 2.2% hydroxylamine sulfate and 79.7% water.
Ce catalyseur a été utilisé à 0,4% par rapport au sable.
- Température Boîte : 120°C
- Température d'air chaud : 100-120°C
- Box temperature: 120 ° C
- Hot air temperature: 100-120 ° C
Résistance flexion à chaud en sortie de boîte : respectivement à 30, 60 et 120 secondes : 15, 30 et 45 daN/cm2
Résistance flexion à froid, respectivement à 30, 60 et 120 secondes : 55, 60 et 65 daN/cm2 Hot bending resistance at the box outlet: at 30, 60 and 120 seconds respectively: 15, 30 and 45 daN / cm 2
Cold bending strength at 30, 60 and 120 seconds respectively: 55, 60 and 65 daN / cm 2
Les résistances à la flexion à chaud et à froid sont suffisantes pour permettre, respectivement, la manipulation des corps formés et la coulée du métal.
- Formaldéhyde au malaxage : inférieur à 0,2 ppm (non détectable)
- Formaldéhyde au déboîtage : valeur comparative 2,5
- Formaldehyde with mixing: less than 0.2 ppm (not detectable)
- Formaldehyde in the process of deboning: comparative value 2.5
Les émissions de formaldéhyde au malaxage et au déboîtage sont faibles (au déboîtage environ 50 fois plus faibles que le procédé boîte chaude représenté par l'exemple 3).
% passant (P) à 20 minutes : 43% (voir Courbe B de la
% passing (P) at 20 minutes: 43% (see Curve B of the
La tenue thermique, exprimée par ce pourcentage, est considérée comme suffisante pour la coulée de pièces de fonderie en fonte.The thermal resistance, expressed by this percentage, is considered sufficient for the casting of cast iron casting parts.
Résine : Résine urée-mélamine/formol , qui a été synthétisée avec un rapport molaire formaldéhyde/urée de 2,95 et à laquelle on a ajouté de la mélamine dans un rapport molaire formaldéhyde/mélamine de 3,45 puis dans laquelle on a ajouté 3% de tanin modifié Fintan 737B, produit commercial de la société Indunor (tanin condensé modifié issu du Schinopsis lorentzii ou Quebracho colorado en poudre).Resin: Urea-melamine / formaldehyde resin, which was synthesized with a formaldehyde / urea molar ratio of 2.95 and to which was added melamine in a formaldehyde / melamine molar ratio of 3.45 then in which was added 3% modified tannin Fintan 737B, commercial product of the company Indunor (modified condensed tannin from Schinopsis lorentzii or Quebracho colorado powder).
Cette résine a été utilisée à 2,2% par rapport au sable.
Catalyseur: Catalyseur contenant 14% de sulfate d'hydroxylamine, 20% de carbohydrazide et 66% d'eau.This resin was used at 2.2% relative to the sand.
Catalyst: Catalyst containing 14% hydroxylamine sulfate, 20% carbohydrazide and 66% water.
Ce catalyseur a été utilisé à 0,3% par rapport au sable.
- Température Boîte : 130°C
- Température d'air chaud : 100-120°C
- Temperature box: 130 ° C
- Hot air temperature: 100-120 ° C
Résistance flexion à chaud en sortie de boîte : respectivement à 30, 60 et 120 secondes : 15, 24 et 42 daN/cm2
Résistance flexion à froid, respectivement à 30, 60 et 120 secondes : 75, 84 et 95 daN/cm2 Hot bending resistance at the box outlet: at 30, 60 and 120 seconds respectively: 15, 24 and 42 daN / cm 2
Bending resistance at 30, 60 and 120 seconds respectively: 75, 84 and 95 daN / cm 2
Les résistances à la flexion à chaud et à froid sont suffisantes pour permettre, respectivement, la manipulation des corps formés et la coulée du métal.
- Formaldéhyde au malaxage : inférieur à 0,2 ppm (non détectable)
- Formaldéhyde au déboîtage : valeur comparative 2,5
- Formaldehyde with mixing: less than 0.2 ppm (not detectable)
- Formaldehyde in the process of deboning: comparative value 2.5
Les émissions de formaldéhyde au malaxage et au déboîtage sont faibles (au déboîtage environ 50 fois plus faibles que le procédé boîte chaude représenté par l'exemple 3).
% passant (P) à 20 minutes : 40% (voir Courbe D de la
% passing (P) at 20 minutes: 40% (see Curve D of the
La tenue thermique, exprimée par ce pourcentage, est considérée comme suffisante pour la coulée de pièces de fonderie en fonte.The thermal resistance, expressed by this percentage, is considered sufficient for the casting of cast iron casting parts.
Résine : Résine urée/formol modifiée tanin, qui a été synthétisée avec un rapport molaire formaldéhyde/urée de 2,37, et dans laquelle on a ajouté 25% de tanin modifié Fintan 737C, produit commercial de la société Indunor (tanin condensé stabilisé issu du Schinopsis lorentzii ou Quebracho colorado en solution à 45%).Resin: Tannin-modified urea / formaldehyde resin, which was synthesized with a formaldehyde / urea molar ratio of 2.37, and in which 25% of modified tannin Fintan 737C, a commercial product of Indunor (stabilized condensed tannin derived from Schinopsis lorentzii or Quebracho colorado in 45% solution).
Cette résine a été utilisée à 2% par rapport au sable.
Catalyseur: Catalyseur contenant 14% de sulfate d'hydroxylamine, 20% de carbohydrazide et 66% d'eau.This resin was used at 2% relative to sand.
Catalyst: Catalyst containing 14% hydroxylamine sulfate, 20% carbohydrazide and 66% water.
Ce catalyseur a été utilisé à 0,3% par rapport au sable.
- Température Boîte : 130°C
- Température d'air chaud : 100-120°C
- Résistance flexion à chaud en sortie de boîte: respectivement à 15, 30 et 60 secondes : 6, 13 et 21 daN/cm2
- Résistance flexion à froid, respectivement à 15, 30 et 60 secondes : 31, 40 et 45 daN/cm2
- Temperature box: 130 ° C
- Hot air temperature: 100-120 ° C
- Hot bending resistance at the box outlet: at 15, 30 and 60 seconds respectively: 6, 13 and 21 daN / cm 2
- Bending resistance at 15, 30 and 60 seconds respectively: 31, 40 and 45 daN / cm 2
Les résistances à la flexion à chaud et à froid sont suffisantes pour permettre, respectivement, la manipulation des corps formés et la coulée du métal.
- Formaldéhyde au malaxage : inférieur à 0,2 ppm (non détectable)
- Formaldéhyde au déboîtage : valeur comparative 2,5
- Formaldehyde with mixing: less than 0.2 ppm (not detectable)
- Formaldehyde in the process of deboning: comparative value 2.5
Les émissions de formaldéhyde au malaxage et au déboîtage sont faibles (au déboîtage environ 50 fois plus faibles que le procédé boîte chaude représenté par l'exemple 3).
% passant (P) à 20 minutes : 50% (voir Courbe E sur la
% passing (P) at 20 minutes: 50% (see Curve E on the
La tenue thermique exprimée par ce pourcentage est considérée comme suffisante pour la coulée de pièces de fonderie en fonte.The thermal resistance expressed by this percentage is considered sufficient for the casting of cast iron casting parts.
Claims (13)
- Method for producing a foundry body, preferably a mould and/or core for a foundry piece, said method comprising at least the following successive steps:- preparing a granular mixture, comprising, in % weight with respect to the total weight of the mixture:a- at least 90%, preferably 96 to 99% by weight of grains, said grains being mainly composed of at least one mineral oxide, and at least 80% of said grains having a size from 10 to 3000 µm,b- 0.3 to 3%, preferably 0.6 to 1.5% by weight of at least one resin polycondensed with formaldehyde and/or its derivatives, the percentage being calculated in dry resin solids,c- 0.001 to 3%, preferably 0.005 to 1% by weight of at least one curing agent, the percentage being calculated in dry curing agent solids,d- 0.003 to 1%, preferably 0.01 to 0.15%, by weight of at least one formaldehyde scavenger compound, andf- 0.2 to 3%, preferably 0.7 to 2%, by weight of water;- placing said granular mixture in contact with at least one surface of a forming tool, and- blowing at least one gas stream into the granular mixture at a temperature of 50°C to 380°C, for a duration comprised from 1 to 300 seconds, in order to ensure at least partial curing of said mixture,Said method being characterized in that the polycondensed resin (component b-) of said mixture is modified:• Either by the presence of a component e- in the mixture, at a content from 0.003% to 1.5%, preferably from 0.15% to 1%, by weight with respect to the total weight of the mixture, of at least one resin chosen from the group consisting of tannins, natural polyphenols and lignins,• Or by the presence during its synthesis of a compound comprising at least one phenolic and/or polyphenolic unit, at a content from 1 to 30% by weight with respect to the total weight of the polycondensed resin.
- Method according to claim 1, such that the formaldehyde scavenger (component d-) is a compound of the hydrazide family, preferably chosen from the group consisting of the mono- and dihydrazides, even more preferably adipic acid dihydrazide, succinic acid dihydrazide or carbohydrazide, particularly preferably carbohydrazide.
- Method according to any one of the claims 1 or 2, such that the resin chosen from the group consisting of tannins, natural polyphenols and lignins (component e)) is a resin of the tannin type, preferably a resin of the condensed tannin type.
- Method according to any one of claims 1 to 3, such that the forming tool is heated to a temperature comprised within a range from 40 to 180°C, preferably from 50 to 150°C.
- Method according to any one of claims 1 to 4, such that said gas is chosen from the group consisting of air, an inert gas and a gas contributing to the acidification of the reaction medium.
- Method according to any one of claims 1 to 5, comprising an additional step, during which a stream of at least one gas is circulated within the at least partially cured granular mixture, at a temperature comprised within a range from 5°C to 45°C, for a duration comprised within a range from 1 to 300 seconds, the gas being preferably chosen from the group consisting of air, dinitrogen and carbon dioxide.
- Method according to any one of claims 1 to 6, in which the resin polycondensed with formaldehyde and/or its derivatives is a composition of at least one resin having undergone a chemical reaction between a first element chosen from urea and its derivatives, melamine, benzoguanamine, glycoluril, phenol and/or its derivatives, and furfuryl alcohol and/or its derivatives, and a second element chosen from formaldehyde and/or its derivatives.
- Method according to any one of claims 1 to 7, such that the phenolic and/or polyphenolic unit is present in a compound chosen from the group consisting of the vanillin (4-hydroxy-3-methoxybenzaldehyde) and phloroglucinol (benzene-1,3,5-triol).
- Method according to any one of claims 1 to 8, in which the resin chosen from the group consisting of tannins, natural polyphenols and lignins is chosen from the group consisting of tannins, preferably condensed and/or modified in order to render them soluble in water, such as extracts of the Quebracho tree, polyphenols, such as for example those extracted from araucaria angustifolia (Paraná pine) or from pinus palustris (longleaf pine), and the lignins, modified or not.
- Method according to any one of claims 1 to 9, in which the curing agent is chosen from the group consisting of the following compounds:- naturally acid salts such as ammonium salts, in particular persulphates, nitrates, bisulphates, sulphates and chlorides;- salts generating an acid by reaction with an aldehyde, such as hydroxylamine salts, in particular hydroxylamine sulphates, hydrochlorides, phosphates, sulphonates and nitrates.- sublimable acids, in particular oxalic acid and benzoic acid; and, optionally,- organic acids compatible with the method with the regard to their reactivity and their toxicity, such as for example lactic acid and citric acid.the curing agent being preferably chosen from the group consisting of hydroxylamine salts, and even more preferably, the curing agent is hydroxylamine sulphate.
- Method for the production of a cast metal, or metal alloy, foundry piece, which comprises pouring a liquid metal or metal alloy into at least one mould and/or core, characterized in that said mould and/or core is a solid body obtained by the method according to one of claims 1 to 10.
- Method according to claim 11, such that said metal, or metal alloy, is chosen from the group consisting of aluminium, ferrous alloys chosen from the group consisting of steels and cast irons, non-ferrous metals, non-ferrous alloys, and preferably, said metal or metal alloy is chosen from the group consisting of the cast irons.
- Cast metal part obtained by a production method according to one of claims 11 or 12.
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PL13774731T PL2892670T3 (en) | 2012-09-10 | 2013-09-10 | Method for obtaining a foundry body from a granular mixture including a modified polycondensed resin and a formaldehyde sensor |
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FR1258481A FR2995234B1 (en) | 2012-09-10 | 2012-09-10 | PROCESS FOR OBTAINING A FOUNDRY BODY FROM A GRANULAR MIXTURE COMPRISING A POLYCONDENSED RESIN CONTAINING AROMATIC PATTERNS AND A FORMALDEHYDE SENSOR |
PCT/FR2013/052077 WO2014037681A2 (en) | 2012-09-10 | 2013-09-10 | Method for obtaining a foundry body from a granular mixture including a modified polycondensed resin and a formaldehyde sensor |
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EP (1) | EP2892670B1 (en) |
CN (1) | CN104619437B (en) |
BR (1) | BR112015004908B1 (en) |
EA (1) | EA028270B1 (en) |
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MX2017013161A (en) * | 2015-04-14 | 2018-02-21 | Huettenes Albertus France | Phenolic resin composition for use in the polyurethane cold-box and/or no-bake process and corresponding two-component binder systems, uses, and processes. |
JP6895804B2 (en) * | 2017-05-29 | 2021-06-30 | 花王株式会社 | Hardener composition for molding |
DE102018118291A1 (en) * | 2018-07-27 | 2020-01-30 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Sizing composition to reduce formaldehyde emissions |
CN112142938A (en) * | 2019-06-28 | 2020-12-29 | 江苏华岗材料科技发展有限公司 | Preparation method of energy-saving and environment-friendly furan resin casting adhesive |
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JPS6478652A (en) | 1987-09-21 | 1989-03-24 | Hitachi Chemical Co Ltd | Resin bonder for shell mold |
AU2002953568A0 (en) | 2002-12-24 | 2003-01-16 | Borden Chemical Australia Pty Ltd | Novel chemical composition, method of making same, and products made therefrom |
US7211137B2 (en) | 2004-10-15 | 2007-05-01 | Ashland Licensing And Intellectual Property Llc | Binder composition comprising condensed tannin and furfuryl alcohol and its uses |
CN101607297B (en) | 2009-07-22 | 2010-12-08 | 福州大学 | Preparation method of modified phenolic resin binder for casting |
FR2948307B1 (en) | 2009-07-24 | 2014-07-25 | Huettenes Albertus France | PROCESS FOR OBTAINING A BODY FORMED FROM A GRANULAR MIXTURE |
KR101421191B1 (en) * | 2009-12-25 | 2014-07-22 | 가오 가부시키가이샤 | Binder composition for the formation of self-curing molds |
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EA201590537A1 (en) | 2015-06-30 |
MX347364B (en) | 2017-04-25 |
PL2892670T3 (en) | 2017-04-28 |
FR2995234A1 (en) | 2014-03-14 |
FR2995234B1 (en) | 2014-12-19 |
CN104619437A (en) | 2015-05-13 |
MX2015003016A (en) | 2015-11-06 |
EP2892670A2 (en) | 2015-07-15 |
BR112015004908B1 (en) | 2019-05-14 |
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