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EP2161349B1 - Procede de production d'alliage blanc a base de cuivre pour produire des articles naturellement antibacteriens - Google Patents

Procede de production d'alliage blanc a base de cuivre pour produire des articles naturellement antibacteriens Download PDF

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Publication number
EP2161349B1
EP2161349B1 EP09008026.8A EP09008026A EP2161349B1 EP 2161349 B1 EP2161349 B1 EP 2161349B1 EP 09008026 A EP09008026 A EP 09008026A EP 2161349 B1 EP2161349 B1 EP 2161349B1
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EP
European Patent Office
Prior art keywords
cold
copper
alloy
subjecting
semifinished article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP09008026.8A
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German (de)
English (en)
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EP2161349A1 (fr
Inventor
Niccolò Ammannati
Elena Martellucci
Aldo Giusti
Armando Sbrana
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KME Italy SpA
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KME Italy SpA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • 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 method for producing articles made of a copper-based white alloy, wherein these articles are naturally antibacterial and simultaneously have an excellent mechanical resistance, an easy machinability, a high cleaning ease and an appearance similar to that of stainless steel.
  • copper and brasses have aesthetical and technological features which are generally considered inappropriate to validly replace stainless steel, for instance in the manufacturing of articles such as sanitaryware, sinks, tables, working surfaces for canteens or laboratories, basins for sanitary use, lockers, both because the mechanical features are typically much poorer than those of stainless steel, and because they are not white, but are instead of different colours such as red, pink and yellow.
  • the use of copper and alloys thereof in the health field has been for the time being limited to components intended to remain hidden, for instance those of hydraulic or conditioning systems, such as finned heat exchangers.
  • manganese may have a whitening effect on copper similar to that of nickel
  • the only known white alloys which do not contain nickel and are not brasses are the so-called “manganins", used for manufacturing electrical resistors due to the low conductivity manganese imparts alloyed copper, already from a few percentage points.
  • the examined alloys have a Cu-Mn-combination of 70:30.
  • the examples comprise Zn and Al.
  • CA 964 408 A1 discloses a method comprising casting a plate based on a Cu-alloy and comprising 30% Mn. A hot rolling from three inches to 0.35 inch is performed followed by cold rolling from 0.35 to 0.1 inch. It follows an annealing procedure for 1 h at 600 - 750°C for recrystallization.
  • DE 1 224 937 B refers to the use of copper alloys.
  • the disclosed copper alloys may be used for bearings according to their friction properties.
  • the alloy contains up to 8% aluminum, up to 5% Ni and up to 45% Zn. Further the alloy contains Tellur, Silicium and up to 12% Mangan.
  • the alloy may be subject of hot forming or cold forming and annealing between 200 and 700°C for recrystallization. This document does not deal with articles that have antibacterial properties.
  • WO 00/68447 A discloses a copper alloy with a golden visual appearance.
  • the material has a transverse electrical conductivities substantially similar to that of copper alloy C713 and when clad to a copper alloy C110 core, a transverse electrical conductivities substantially similar to both sides of a Susan-B.-Anthony-US-Dollar coin.
  • the copper base alloy is a copper-manganese-zink-nickel alloy consisting for example by weight of 10-15% Zn, 7-12% Mn, 2-6% Ni or 10-14% Zn, 5-10% Mn, 2-6% Ni, optionally controlled contents of Cr, Al, Fe, P, the balance being Cu with inevitable impurities.
  • planchet is stamped from the clad material
  • the planchet is annealed prior to coining.
  • the suitable annealing profile is 700°C for 15-20 minutes in an atmosphere of 96% by volume, of nitrogen and 4%, by volume, of hydrogen or other combustible gas mixtures.
  • the copper alloys were hot rolled to a thickness of 0.5 inch, milled to remove oxides and then cold rolled to 0.03 inch and buffed to provide a constant surface finish.
  • a copper alloy treated by this method has a golden visual appearance.
  • the invention relates to the method of claim 1 for producing articles, these articles being in particular intended to be employed in the health and/or food field, these articles being provided with intrinsic antibacterial properties.
  • the manganese, and possible other alloying elements, except for impurities are present in an amount such as to determine machinability, colour and surface properties of the alloy similar to those of stainless steel and simultaneously intrinsic antibacterial properties of the articles on respective exposed surfaces thereof.
  • the employed alloy does not contain aluminium, except as an impurity and neither zinc nor other alloying elements, but exclusively manganese and copper.
  • Tin in case it is required, may also be contained as further alloying element, but again in very low percentages, preferably below 2% so as not to produce in use the segregation of precipitates or low-melting phases which impart fragility to the alloy.
  • said alloy exclusively contains, except for impurities, copper and manganese, copper being prevailing.
  • the content of manganese ranges, in any case, in varying percentages between 15% and up to 40% by weight and preferably in an amount such as to obtain a crystalline structure of the alloy, exclusively in alpha phase, at ambient temperature.
  • the optimal nominal composition of the alloy according to the use of the invention is 80% copper and 20% manganese.
  • composition of the alloy according to the use of the invention is in any case such as to display on the surface antibacterial properties directed at least against microorganisms selected from the group consisting of: E.coli, MSRA, Listeria monocytogenes.
  • the method of the invention comprises the steps of:
  • the alloy contains manganese in a varying weight percentage between 15% and 40% and does not contain aluminium, and preferably neither zinc, except as impurities.
  • the first and second predetermined percentages of sectional reduction are on the order of 90% and the step of complete re-crystallization annealing of the cold semifinished article is performed at a temperature ranging between 550°C and 750°C and for about 4 hours, if performed in a static furnace or for a total time of about 45 minutes, if performed in a tunnel type furnace.
  • a step of abrasive brushing is performed so as to remove a surface layer of the cold annealed semifinished article having a thickness of about 4 microns.
  • the antibacterial properties of copper alloys experimentally tested on many different bacterial strains are probably due to the surface migration, and therefore on the exposed surfaces of articles made with these alloys, of copper atoms, a migration that is interrupted by the presence of aluminium in the alloy.
  • the presence of aluminium in the alloy, unless the latter is present only as an impurity (the presence of impurities is in any case inevitable) must be avoided.
  • Plate P88501 was then used, due to its better quality (chemical composition identical to the nominal composition - 80% copper and 20% manganese).
  • the plate was subjected to a hot rolling process bringing it to 740°C for 3.5 hours and was subsequently rolled thus obtaining in subsequent steps a reduction in the section of about 90%; the thickness was in particular reduced from 115 mm to 10 mm in 8 steps, thus reaching a final temperature of about 660-670°; the hot-rolled product was cooled down to about 350°C before forcedly cooling down to ambient temperature with water.
  • the rolled product was then examined and analysed to detect the depth and nature of the surface layers oxidised and depleted of alloying elements (manganese).
  • Table 2 Thickness of the oxidising layers measured on both sides of the longitudinal section of Cu80Mn20 hot-rolled plate
  • Top - edge 1 Mean MAX. m MIN. m ST.DEV. m Side A 25.48 73.71 3.98 18.65 Side B 24.28 47.81 10.76 9.09
  • Top - edge 2 Mean m MAX. m MIN. m ST.DEV.
  • the depth of the detected layers of oxidation and depletion of Mn were relatively high and discontinuous, but such that said layers could easily and totally be removed by the normal milling/scalping operations which are generally performed after hot-rolling.
  • the hot-rolled product after the milling/scalping operation and subsequent removal of the oxidised layers and with depletion of manganese, was subjected to a cold-rolling operation, again obtaining a reduction in the section of about 90% (from 10 to 0.7 mm of thickness) in subsequent steps, with the consequent work hardening and increase of hardness.
  • the cold-rolled product was then subjected to a heat annealing treatment in a static furnace in a reducing atmosphere at 600°C for 4 hours for the re-crystallization. This treatment has been selected on the basis of a series of laboratory tests at different temperatures, in order to identify the optimal treatment, as shown in table 4.
  • Table 4 Structure and size of the grain of Cu80Mn20 samples after one hour of heat treatment at increasing temperatures.
  • Mean size of the grain (mm) Heat treatment 1 mm thickness 0.5 mm thickness 400 °C / 1 hour Fibrous structure Fibrous structure 450 °C / 1 hour Fibrous structure Fibrous structure 500 °C / 1 hour Re-crystallization start Re-crystallization start 550 °C / 1 hour 0.005 0.0075 600°C / 1 hour 0.0075 0.0075 650 °C / 1 hour 0.010 0.015
  • the depletion involves a layer which is no more than 4-5 microns, which may easily be removed with a common operation of abrasive brushing after the heat treatment.
  • the tested CuMn20 alloy is suitable to replace the stainless steel in any application, such as the manufacture of furniture, tools, work surfaces, etc., having a considerable hardness and high mechanical resistance, well beyond those of brasses.
  • the antimicrobial properties of three different copper alloys were compared, and specifically the CuMn20 alloy (alloy 3) according to the invention, previously prepared according to the previous examples, a CuSn6Zn6 alloy (alloy 2) and a CuZn10 alloy (alloy 1), with two different reference materials and specifically DHP copper AISI 304 steel (stainless steel).
  • sample specimens were incubated at 37°C.
  • the test was repeated 6 times, varying the time of contact in incubation.
  • Each sample specimen was tested for the following times: 0, 5, 10, 20, 40 and 80 minutes.
  • the sample specimen was recovered and treated with an aqueous solution to remove the pathogens; the solution was then diluted and incorporated in agar and a microscopical count was finally carried out on the survived microbial cells.
  • the antimicrobial activity of the previously prepared and machined alloy, CuMn20 is substantially very similar to that of copper DHP against all of the tested pathogenic microorganisms, while stainless steel is substantially devoid thereof.
  • the antimicrobial activity of the CuMn20 alloy is also comparable (or better), with the content of copper being the same, with respect to that of the other tested alloys, which however have a mechanical resistance and hardness that make them unsuitable to replace steel and, especially, do not have a colour comparable to that of steel, while the CuMn20 alloy according to the invention has a white metal colour comparable to that of steel.
  • the double-hole extrusion of the ingots was performed so as to obtain wires with a diameter of 26 mm, with a 4000 ton press in a range of extrusion temperatures from 770 to 800 °C, spraying the outputted wires with water coming from appropriate sprayers to limit oxidation of the alloy and/or the depletion of Mn.
  • the power absorbed by the press expressed in tons, varies from 2000 to 2300 due to the high mechanical features of the Cu80Mn20 alloy. From the metallographic point of view, the best results both as regards the mean diameter of the grain and as regards the homogeneity thereof, were obtained with an extrusion temperature equivalent to 780°C.
  • the wires were subjected to a final step of cold drawing to a 2mm- or 1.80mm-diameter, so as to obtain a work hardening of 7.4% or, respectively, of 25% and therefore give rise, with the same alloy, to a final wire material in a medium-hard or hard physical state.
  • the possible brushing ensured the absence of surface layers of oxide or of layers depleted of Mn.
  • Billets of Cu80Mn20 alloy were extruded under water to tubes having a 100mm-diameter, 11mm-thickness wall, so as to limit the formation of surface oxides and/or layers depleted of Mn.
  • the extrusion of the billet in the form of a tube was performed in a range of extrusion temperatures in the range between 790 and 805°C.
  • the power absorbed by the press expressed in bars, was about 290, which is an acceptable value considering the high mechanical features of the Cu80Mn20 alloy.
  • a cold plastic deformation processing was performed using a pilgrim mill set at 70 hits/minute with a feed of 11.11 mm until tubes having a 45mm-diameter by a 2.25-wall thickness were obtained and later the semifinished products obtained thereby were subjected to a single operation of rectilinear cold drawing to a 35mm-diameter by 1.90 mm-thickness and a following annealing at 650°C for 4 hours in a reducing atmosphere.

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Heat Treatment Of Steel (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Adornments (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)

Claims (4)

  1. Procédé de fabrication d'articles, ces articles étant de préférence destinés à être utilisés dans le domaine de la santé et/ou de l'alimentation, ces articles étant dotés de propriétés antibactériennes intrinsèques, le procédé étant caractérisé en ce qu'il comprend les étapes de :
    - couler une plaque ou un barreau cylindrique constitué d'un alliage à base de cuivre contenant du manganèse en tant qu'élément d'alliage principal, en une quantité telle que l'alliage soit de couleur blanche et pour lui conférer une structure cristalline en phase alpha à température ambiante, dans lequel ledit alliage contient du manganèse dans un pourcentage de poids variant entre 15% et 40%, éventuellement jusqu'à 2%, d'étain, et ne contient pas d'aluminium, ni de zinc comme impuretés, le reste étant du cuivre ;
    - soumettre la plaque ou le barreau à une série de traitements d'usinage par déformation plastique à chaud en séquence, de préférence par laminage ou étirage ou extrusion, pour obtenir un premier pourcentage prédéterminé de réduction de section ;
    - soumettre l'article semi-fini chaud à une série de traitements d'usinage par déformation plastique à froid en séquence, de préférence par laminage ou étirage, pour obtenir un second pourcentage prédéterminé de réduction de section ;
    - soumettre l'article semi-fini froid ainsi obtenu à un ou plusieurs traitements de recuit thermique de recristallisation complète, dans une atmosphère réductrice ;
    - soumettre l'article semi-fini chaud et/ou froid à au moins une étape d'enlèvement d'une couche superficielle de celui-ci avec une faible teneur en manganèse ;
    - soumettre l'article semi-fini recuit froid à une étape de brossage abrasif, dans lequel ladite étape de brossage abrasif est effectuée de manière à enlever la couche de surface de l'article semi-fini recuit froid ayant une épaisseur égale à 4 microns ; et
    - obtenir un article désiré avec l'article semi-fini recuit froid.
  2. Procédé selon la revendication 1, caractérisé en ce que lesdits premier et second pourcentages prédéterminés de réduction de section sont de l'ordre de 90%.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que ladite étape de recuit complet de recristallisation de l'article semi-fini froid est effectuée à une température comprise entre 550°C et 750°C, soit dans un four statique soit dans un four de type tunnel, et dans une atmosphère réductrice.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'article semi-fini chaud est soumis à une étape de fraisage en surface pour éliminer les couches oxydées à faible teneur en manganèse.
EP09008026.8A 2008-09-01 2009-06-19 Procede de production d'alliage blanc a base de cuivre pour produire des articles naturellement antibacteriens Active EP2161349B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
ITTO2008A000649A IT1392421B1 (it) 2008-09-01 2008-09-01 Uso di una lega bianca a base rame per la produzione di manufatti naturalmente antibatterici e metodo per la produzione degli stessi

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EP2161349A1 EP2161349A1 (fr) 2010-03-10
EP2161349B1 true EP2161349B1 (fr) 2018-10-17

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EP (1) EP2161349B1 (fr)
ES (1) ES2695752T3 (fr)
IT (1) IT1392421B1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1224937B (de) * 1963-06-07 1966-09-15 Kurt Dies Dr Ing Verwendung von Kupferlegierungen fuer auf Gleitung, Reibung und Verschleiss beanspruchte Gegenstaende und Verfahren zur Herstellung derselben
US3725052A (en) * 1969-09-13 1973-04-03 Foundation Res Inst Electric A Non-magnetic resilient manganese-copper alloy having a substantially temperature-free elastic modulus
GB1382202A (en) * 1971-03-03 1975-01-29 Olin Corp Cuprous composite article
JPS6072695A (ja) * 1983-09-28 1985-04-24 Maruyasu Kogyo Kk ステンレス鋼用ろう付け合金
JPH08206876A (ja) * 1995-02-02 1996-08-13 Mazda Motor Corp ろう付方法およびそのろう材
JP3396658B2 (ja) * 1999-05-05 2003-04-14 オリン コーポレイション 金色外観の銅合金
US6863746B2 (en) 2001-08-02 2005-03-08 Keith Weinstein White gold compositions without nickel and palladium
JP3915889B2 (ja) 2001-10-26 2007-05-16 Ｙｋｋ株式会社 ニッケルフリー白色系銅合金及びニッケルフリー白色系銅合金の製造方法
EP1880776A1 (fr) * 2006-07-19 2008-01-23 Europa Metalli S.p.A. Procédé pour la fabrication de tubes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
ITTO20080649A1 (it) 2010-03-02
ES2695752T3 (es) 2019-01-10
IT1392421B1 (it) 2012-03-02
EP2161349A1 (fr) 2010-03-10

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