EP3859021B1 - Alliage métallique et procédé de coulée à cire perdue correspondant - Google Patents

Alliage métallique et procédé de coulée à cire perdue correspondant Download PDF

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Publication number
EP3859021B1
EP3859021B1 EP21152386.5A EP21152386A EP3859021B1 EP 3859021 B1 EP3859021 B1 EP 3859021B1 EP 21152386 A EP21152386 A EP 21152386A EP 3859021 B1 EP3859021 B1 EP 3859021B1
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EP
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Prior art keywords
equal
less
weight percentage
metal alloy
alloy
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EP21152386.5A
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German (de)
English (en)
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EP3859021A1 (fr
Inventor
Carlo Faletti
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Metal Sil Car Snc Di S Faletti & C
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Metal Sil Car Snc Di S Faletti & C
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00—Special casting characterised by the nature of the product
    • B22D25/02—Special casting characterised by the nature of the product by its peculiarity of shape; of works of art
    • B22D25/026—Casting jewelry articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C7/00—Patterns; Manufacture thereof so far as not provided for in other classes
    • B22C7/02—Lost patterns
    • 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
    • B22C9/04—Use of lost patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D13/00—Centrifugal casting; Casting by using centrifugal force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D13/00—Centrifugal casting; Casting by using centrifugal force
    • B22D13/06—Centrifugal casting; Casting by using centrifugal force of solid or hollow bodies in moulds rotating around an axis arranged outside the mould
    • B22D13/063—Centrifugal casting; Casting by using centrifugal force of solid or hollow bodies in moulds rotating around an axis arranged outside the mould for dentistry or jewellery
    • 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
    • B22D21/025—Casting heavy metals with high melting point, i.e. 1000 - 1600 degrees C, e.g. Co 1490 degrees C, Ni 1450 degrees C, Mn 1240 degrees C, Cu 1083 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/05—Alloys based on copper with manganese as the next major constituent

Definitions

  • the present invention relates to a copper-based metal alloy and a lost-wax casting process for the production of objects (for example glasses parts) made of this metal alloy.
  • the lost-wax casting process is widely used for the production of small objects made of metal alloys.
  • objects can for example be parts or components (e.g., frames, hinges, oval lenses, nose pads, temples, etc.) of wearable accessories such as costume jewellery or glasses.
  • the lost-wax casting process can involve the making of a mould (e.g., in silicone or steel) for moulding (typically in series) wax models (e.g., beeswax or silicone wax, or similar material) of the objects which are to be made.
  • a mould e.g., in silicone or steel
  • wax models e.g., beeswax or silicone wax, or similar material
  • the wax models are joined together in a "tree-like" structure that will allow the flowing of the melted alloy.
  • a plaster mould is made around the wax model (or the tree-like structure) which is placed in oven (e.g., at a temperature of about 600°C) for allowing the melting/evaporation and the consequent spill of the wax through appropriate channels.
  • the molten metal alloy is casted into the mould, which fills all the interstices of the mould, possibly also thanks to the action of a depression (e.g., in case of vacuum lost-wax casting) or of a centrifugal force (e.g., in case of centrifugal lost-wax casting).
  • the plaster mould is completely removed (e.g., through water bath operations and preferably pickling operations for removing the plaster residues from the finished object).
  • the finished objects e.g., separating them from the tree-like structure and/or from the channels), which can undergo further surface treatments and/or heat treatments.
  • Copper-based metal alloys are commonly used. Copper is in fact a common, cheap, non-toxic, recyclable metal and it has advantageous technological properties (for example a high castability and drawability).
  • copper-based metal alloys containing beryllium and/or cobalt are typically used for the making of objects by lost wax casting.
  • These alloys in addition to showing a colour and a gloss appreciated in the wearable accessories market, have characteristics suitable for their treatment (e.g., melting, casting, welding and tools working). Furthermore, these alloys have excellent corrosion resistance.
  • Al-Mn-Cu based alloys are known in the art as for example in EP 0568094 for spectacle frames applications or in cast forms including further alloying elements as in EP 3118338 or US 6406566 .
  • the known alloys require, after the lost-wax casting, a heat treatment (e.g., tempering, which includes a solubilization and an aging, and/or hardening), for improving their hardness and the fatigue resistance.
  • a heat treatment e.g., tempering, which includes a solubilization and an aging, and/or hardening
  • the Applicant has found that the copper-based metal alloys notoriously used for the lost-wax casting have some drawbacks and/or can be improved in some aspects.
  • the alloys containing beryllium and/or cobalt have serious toxicity and/or carcinogenicity problems, in particular during the processing cycle for the production of the alloy and/or the subsequent lost-wax casting for the making of the objects destined to the market.
  • Common processes such as melting, casting, welding, high temperature heat treatments, cutting, polishing and processing by electrochemical methods are subject to the emission of vapours and fumes, which if inhaled can cause serious diseases of the respiratory apparatus.
  • the objects notoriously made by lost-wax casting with the aforesaid copper-based alloys containing beryllium and/or cobalt after the lost-wax casting process typically require a heat treatment which by heating and cooling cycles, leads the alloy to assume a crystalline structure which gives the desired mechanical properties.
  • the need to carry out these heat treatments entails an increase in the complexity of the production process and/or of the production times and/or of the production costs of the object to be destined to the market.
  • the Applicant has therefore faced the problem of making, or selecting, a metal alloy which has physical qualities and/or mechanical properties suitable for the making of objects by lost-wax casting, for example for eyewear and costume jewellery, and at the same time entailing little or no risks for the health and hygiene of the man and/or of the environment.
  • the Applicant has faced the problem of making, or selecting, a copper-based metal alloy, free from beryllium and/or cobalt, which has mechanical properties suitable for making objects by lost-wax casting even without heat treatment after the lost-wax casting process, for limiting the complexity of the production process and/or saving in terms of both production times and production costs.
  • the invention relates to a metal alloy containing:
  • said lost-wax casting process comprises:
  • said filling said mould is made with a pressure gradient and/or with a centrifugal force.
  • said filling said mould is made at a casting temperature of said metal alloy, greater (e.g., greater than 50-150°C) than a melting temperature of said metal alloy.
  • a casting temperature of said metal alloy greater (e.g., greater than 50-150°C) than a melting temperature of said metal alloy.
  • it is provided making a wax model of said objects, making said mould around said model and removing said wax from said mould.
  • the invention relates to a production process of objects comprising the lost-wax casting process according to the present invention.
  • said objects are parts of wearable accessories, for example glasses parts or costume jewellery.
  • Exemplarily said objects do not undergo heat treatments for enhancing their hardness.
  • the aforesaid features of the alloy allow obtaining a metal alloy easily castable, tough, elastic, weldable (for example by TIG welding and flame and/or induction soldering) and easily workable: this makes the alloy particularly suitable for producing for example objects by lost-wax casting, in particular parts of wearable accessories.
  • the metals that make up the alloy have, to current knowledge, limited or no toxicity, and also entail a reduced release of fumes during the casting, helping to make their processing healthier.
  • This entails that no special machinery and/or safety devices are required for the processing of described and claimed the metal alloy, with consequent increase of the production process simplicity and/or reduction of the production times and costs with respect to the known copper-based alloys containing beryllium and/or cobalt.
  • the aforesaid features allow obtaining alloys having mechanical properties (e.g., tensile strength, yield stress, breaking strength) comparable to the aforesaid copper-based alloys notoriously used for the lost-wax casting, even without undergoing heat treatments at the end of the manufacturing process, with consequent savings of manufacturing times and of production costs.
  • mechanical properties e.g., tensile strength, yield stress, breaking strength
  • the Applicant has verified that the main physical and mechanical properties of the described and claimed metal alloy are comparable, if not even superior, to the aforesaid copper-based alloys notoriously used for the lost-wax casting, which are subjected to heat treatments (e.g., tempering and/or hardening), consequently making the heat treatment unnecessary, and thus simplifying the production process of objects made with the described and claimed alloys.
  • heat treatments e.g., tempering and/or hardening
  • the alloys of the present invention maintain their high mechanical properties even after surface treatments and/or manufacturing processes (e.g., welding) which can subject the alloy to high temperatures.
  • the alloys of the present invention since they do not require heat treatments for obtaining the desired mechanical properties, can undergo high-temperature surface treatments and/or high-temperature manufacturing processes without undergoing a loss of mechanical properties due to remelting.
  • the high-temperature processing can entail, in the points subjected to processing, a localized loss of the mechanical properties gained after heat treatment, since the remelting of the material cancels out the effects of the heat treatment.
  • the Applicant considers advantageous the composition of the alloy according to the aforesaid features for making parts of wearable accessories, since it contains low-density materials, such as aluminum, in a percentage such as to make the objects comfortable to be worn.
  • the aforesaid features finally allow obtaining metal alloys having aesthetic properties, such as for example colour and/or gloss and/or brilliance (e.g., after polishing and/or brushing), such as to be particularly attractive to the market for the production of wearable accessories, such as eyewear and costume jewellery.
  • the present invention in one or more of the aforesaid aspects can have one or more of the following preferred features.
  • said weight percentage of copper (Cu) is greater than or equal to 62,0%, more preferably greater than or equal to 65,0%, even more preferably greater than or equal to 68,0%. In this way the embrittlement of the alloy is kept limited.
  • said weight percentage of copper (Cu) is less than or equal to 77,0%, more preferably less than or equal to 75,0%, even more preferably less than or equal to 73,0%. In this way the malleability of the alloy is kept limited.
  • said weight percentage of aluminium (Al) is greater than or equal to 8,0%, more preferably greater than or equal to 8,4%, even more preferably greater than or equal to 8,8%, and/or less than or equal to 9,8%, more preferably less than or equal to 9,5%, even more preferably less than or equal to 9,2%.
  • the Applicant has found that for weight percentages of aluminum greater than or equal to 8,0% (and less than or equal to 10,0%), it is obtained a hardness comparable to that of the aforesaid copper-based metal alloys notoriously used for the lost-wax casting, even without any heat treatment, allowing obtaining alloys having both good malleability (for alloys with low content of aluminum within the above-described ranges) and alloys with good toughness (for alloys with high content of aluminum within the above-described ranges). Furthermore, the Applicant has found that by increasing the weight percentage of aluminum, within the above-described ranges, the hardness of the alloy is increased, regardless of possible heat treatment.
  • the preferred above-described ranges of content of aluminum therefore represent for the Applicant an optimal selection with respect to the hardness of the resulting alloy, for the purpose of the lost-wax casting for wearable accessories.
  • Aluminum also creates a passivating layer on the surface of objects made of the alloy, making them resistant to oxidation and to atmospheric agents. In addition, aluminum helps making the alloy lighter.
  • the Applicant has observed that when the alloy is subjected to remelting it can happen that a certain weight percentage of aluminum (e.g., around 0,3-0,4% of the overall weight of the alloy) is lost (e.g., by oxidation). For example, it can happen that by subjecting to lost-wax casting an alloy initially having a weight percentage of aluminum of 7,8%, the percentage of aluminum in the finished product drops to 7,4%.
  • a certain weight percentage of aluminum e.g., around 0,3-0,4% of the overall weight of the alloy
  • said weight percentage of manganese (Mn) is greater than or equal to 13,0%, more preferably greater than or equal to 14,0%, even more preferably greater than or equal to 14,4%, and/or less than or equal to 17,0%, more preferably less than or equal to 16,0%, even more preferably less than or equal to 15,0%.
  • Manganese in the above-described ranges, is soluble in the alloy, it improves the grain fineness of the alloy (e.g., it contributes to the formation of the crystalline structure) contributing to give the desired mechanical properties to the alloy, it improves the fluidity of the alloy in the molten state and it acts as deoxidizer in the molten alloy.
  • the Applicant has found that by increasing the weight percentage of manganese (within the above-described preferred ranges), a progressive increase of the deoxidation degree (e.g., absence of oxygen and hydrogen) in the molten alloy is obtained, with consequent decrease of the occurrence of the oxidation phenomenon of the molten alloy.
  • said weight percentage of iron (Fe) is greater than or equal to 3,0%, more preferably greater than or equal to 3,5%, even more preferably greater than or equal to 3,8%, and/or less than or equal to 5,0%, more preferably less than or equal to 4,5%, even more preferably less than or equal to 4,2%.
  • Iron in the above-described ranges, gives the alloy high mechanical strength and good workability (given its high ductility), it is a low-cost material and moreover it is a refiner of the crystalline structure, helping ensuring the desired mechanical properties to the alloy.
  • the Applicant has found that by increasing the weight percentage of iron (within the above-described preferred ranges), a progressive increase in the refinement degree of the alloy is obtained (e.g., progressive increase in the crystallinity percentage of the resulting alloy) with a consequent increase in the mechanical properties of the alloy.
  • said weight percentage of silver (Ag) is greater than or equal to 0,6%, more preferably greater than or equal to 0,7%, even more preferably greater than or equal to 0,8%, and/or less than or equal to 1,7%, more preferably less than or equal to 1,5%, even more preferably less than or equal to 1,3%.
  • Silver in the above-described ranges, gives the alloy a white-like colour and, possibly following polishing and/or brushing of the surface, excellent gloss and/or brilliance properties which makes it particularly attractive for applications such as the eyewear and the costume jewellery.
  • impurity element any element not belonging to the group: copper, aluminum, manganese, iron and silver.
  • the alloy of the present invention ideally contains all and only the elements of this group in the aforesaid weight percentages. However, it is possible that inside the alloy there are one or more elements which constitute unavoidable or tolerable impurities, for example due to the intrinsic impurity of the raw materials used for the making of the alloy and/or due to impurities deriving from the use of tools or machinery for the production and/or the treatment of the metal alloy.
  • substantially absent or “alloy substantially not containing” referred to an element or to a system of elements, it is meant that said element or system of elements is absent or at most present in traces, for example in weight percentage lower than 0,01%, typically lower than 0,005%.
  • the Applicants consider zinc and tin.
  • said overall weight percentage of zinc (Zn) and tin (Sn) is less than or equal to 1,0%, more preferably less than or equal to 0,5%.
  • tin and zinc are substantially absent.
  • the possible presence of tin and zinc in quantities such that the overall weight percentage remains less than or equal to 2% does not substantially change the physical and/or mechanical properties of the alloy.
  • the alloy can contain further impurity elements, for example one or more of the following elements: silicon (Si), nickel (Ni) and lead (Pb).
  • said overall weight percentage of further impurity elements is less than or equal to 0,2%, more preferably less than or equal to 0,1%, even more preferably less than or equal to 0,08%.
  • said metal alloy contains a weight percentage of nickel (included in said overall weight percentage of further impurity elements) less than or equal to 0,05%, more preferably less than or equal to 0,03%.
  • nickel is substantially absent. The very low or null content of nickel in the alloy eliminates toxicity and/or allergy problems from the objects made with the alloy.
  • said metal alloy does not substantially contain beryllium and/or cobalt (e.g., a weight percentage of one or both beryllium and cobalt is less than 0,01%).
  • the Applicant has made some samples of the alloy according to the present invention, as shown in table 1, wherein the measured weight percentages of the elements are shown.
  • the casting temperature i.e., the optimal temperature for casting the alloy under gravity
  • the hardness is equal to 300 Vickers (hardness value obtained without heat treatments on the samples)
  • the linear shrinkage i.e., the percentage decrease in the linear length of the sample following cooling
  • the specific weight is equal to 7,17 g/cm 3
  • the elastic modulus (E) is equal to about 90-100 GPa.
  • Table 4 shows the measured values of yield stress (Rp), breaking stress (Rm) (both expressed in MPa (N/mm 2 )) and elongation percentage (A) for a tensile test performed on a sample (having area equal to 11,4 mm 2 and length equal to 25 mm) of the alloy according to the aforesaid example 5.
  • Rp yield stress
  • Rm breaking stress
  • A elongation percentage
  • the alloys object of the present invention have low or null emission of fumes during casting, few residues in the melting crucible (index of low stickiness and good fluidity), excellent weldability (with TIG technology and flame and/or induction soldering), excellent tools workability, as well as not being subjected to loss of mechanical properties following remelting due to high temperature processing (e.g., welding). Moreover, these alloys have a white-like colour and an excellent gloss following polishing and/or brushing.
  • the described and claimed alloys can be subjected to electrochemical processes (e.g., galvanization) with the aim of making a passivating layer with function of both protection (e.g., antioxidant) from external agents and providing the appropriate aesthetic characteristics (e.g., colouring), resulting to be furtherly attractive for the making of objects for wearable accessories.
  • electrochemical processes e.g., galvanization
  • protection e.g., antioxidant
  • aesthetic characteristics e.g., colouring
  • the described and claimed alloys are particularly suitable for their use in lost-wax casting processes, and show advantages in terms of health and safety for the man and/or the environment (e.g., absence of beryllium and cobalt which are carcinogenic and/or mutagenic materials, and absence of nickel which is allergenic), in terms of process simplicity (e.g., no heat treatments are required), and in terms of aesthetic characteristics (given by the silver content) with respect to copper-based alloys notoriously used for the lost-wax casting.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Claims (10)

  1. Alliage métallique, contenant :
    - un pourcentage en poids d'aluminium supérieur ou égal à 7,5 % et inférieur ou égal à 10,0 % ;
    - un pourcentage en poids de manganèse supérieur ou égal à 12,0 % et inférieur ou égal à 18,0 % ;
    - un pourcentage en poids de fer supérieur ou égal à 2,5 % et inférieur ou égal à 6,0 % ;
    - un pourcentage en poids d'argent supérieur à 0,4 % et inférieur ou égal à 2,0 % ;
    - éventuellement un pourcentage en poids total de zinc et d'étain supérieur ou égal à 0 % et inférieur ou égal à 2,0 % ;
    - éventuellement un pourcentage en poids total d'autres éléments-impuretés supérieur ou égal à 0 % et inférieur à 0,4 % ;
    - un pourcentage en poids de cuivre tel que la somme desdits pourcentages en poids d'aluminium, de manganèse, de fer, d'argent, de zinc, d'étain, d'autres éléments-impuretés et de cuivre est égale à 100 %.
  2. Alliage métallique selon la revendication 1, dans lequel ledit pourcentage en poids de cuivre est supérieur ou égal à 62,0 %, de préférence supérieur ou égal à 68,0 %, et/ou inférieur ou égal à 77,0 %, de préférence inférieur ou égal à 73,0 %.
  3. Alliage métallique selon l'une quelconque des revendications précédentes, dans lequel ledit pourcentage en poids d'aluminium est supérieur ou égal à 8,0 %, de préférence supérieur ou égal à 8,8 %, et/ou inférieur ou égal à 9,8 %, de préférence inférieur ou égal à 9,2 %.
  4. Alliage métallique selon l'une quelconque des revendications précédentes, dans lequel ledit pourcentage en poids de manganèse est supérieur ou égal à 13,0 %, de préférence supérieur ou égal à 14,4 %, et/ou inférieur ou égal à 17,0 %, de préférence inférieur ou égal à 15,0 %.
  5. Alliage métallique selon l'une quelconque des revendications précédentes, dans lequel ledit pourcentage en poids de fer est supérieur ou égal à 3,0 %, de préférence supérieur ou égal à 3,8 %, et/ou inférieur ou égal à 5,0 %, de préférence inférieur ou égal à 4,2 %.
  6. Alliage métallique selon l'une quelconque des revendications précédentes, dans lequel ledit pourcentage en poids d'argent est supérieur ou égal à 0,6 %, de préférence supérieur ou égal à 0,8 %, et/ou inférieur ou égal à 1,7 %, de préférence inférieur ou égal à 1,3 %.
  7. Alliage métallique selon l'une quelconque des revendications précédentes, dans lequel ledit pourcentage en poids total de zinc et d'étain est inférieur ou égal à 1,0 %, dans lequel ledit pourcentage en poids total d'autres éléments-impuretés est inférieur ou égal à 0,2 %, de préférence inférieur ou égal à 0,08 %, dans lequel ledit alliage métallique contient un pourcentage en poids de nickel inférieur ou égal à 0,05 %, et dans lequel un pourcentage en poids de cobalt et/ou de béryllium est inférieur à 0,01 %.
  8. Procédé de moulage à la cire perdue pour la production d'objets dans l'alliage métallique selon l'une quelconque des revendications précédentes.
  9. Procédé de moulage à la cire perdue selon la revendication 8, comprenant :
    - réaliser un modèle en cire desdits objets, réaliser un moule autour dudit modèle et retirer ladite cire dudit moule ;
    - faire fondre ledit alliage métallique ;
    - remplir ledit moule avec ledit alliage métallique fondu ;
    - solidifier ledit alliage métallique à l'intérieur dudit moule ;
    - retirer ledit moule dudit alliage métallique solidifié ;
    dans lequel ledit remplissage dudit moule est effectué avec un gradient de pression et/ou avec une force centrifuge, et dans lequel ledit remplissage dudit moule est effectué à une température de moulage dudit alliage métallique, supérieure à une température de fusion dudit alliage métallique.
  10. Procédé de production d'objets comprenant le procédé de moulage à la cire perdue selon les revendications 8 ou 9, dans lequel lesdits objets sont des pièces d'accessoires portables, par exemple des pièces de lunettes ou de bijouterie fantaisie.
EP21152386.5A 2020-01-30 2021-01-19 Alliage métallique et procédé de coulée à cire perdue correspondant Active EP3859021B1 (fr)

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IT102020000001843A IT202000001843A1 (it) 2020-01-30 2020-01-30 Lega metallica e relativo processo di microfusione a cera persa

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EP3859021B1 true EP3859021B1 (fr) 2022-11-09

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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4214304A1 (de) * 1992-04-30 1993-11-04 Deutsche Nickel Ag Nickelfreie buntmetallegierung und deren verwendung
JP3300684B2 (ja) * 1999-07-08 2002-07-08 清仁 石田 形状記憶特性及び超弾性を有する銅系合金、それからなる部材ならびにそれらの製造方法
WO2015137283A1 (fr) * 2014-03-14 2015-09-17 古河電気工業株式会社 MATÉRIAU EN ALLIAGE À BASE DE Cu-Al-Mn, SON PROCÉDÉ DE PRODUCTION ET MATÉRIAU SOUS FORME DE BARRE OU SOUS FORME DE TÔLE L'UTILISANT
IT201700005383A1 (it) 2017-01-19 2018-07-19 Metal Sil Car Snc Di S Faletti & C Lega metallica

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