EP3024956B1 - Grain-refined copper casting alloy with iron and boron - Google Patents
Grain-refined copper casting alloy with iron and boron Download PDFInfo
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- EP3024956B1 EP3024956B1 EP14735475.7A EP14735475A EP3024956B1 EP 3024956 B1 EP3024956 B1 EP 3024956B1 EP 14735475 A EP14735475 A EP 14735475A EP 3024956 B1 EP3024956 B1 EP 3024956B1
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- iron
- content
- boron
- weight
- copper
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 102
- 229910052796 boron Inorganic materials 0.000 title claims description 52
- 229910052742 iron Inorganic materials 0.000 title claims description 52
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims description 48
- 229910045601 alloy Inorganic materials 0.000 title claims description 46
- 239000000956 alloy Substances 0.000 title claims description 46
- 238000005266 casting Methods 0.000 title claims description 30
- 239000010949 copper Substances 0.000 title claims description 20
- 229910052802 copper Inorganic materials 0.000 title claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 59
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 238000007670 refining Methods 0.000 description 20
- 229910000676 Si alloy Inorganic materials 0.000 description 14
- QBOMBCGAEZXOSM-UHFFFAOYSA-N [Si].[Zn].[Cu] Chemical compound [Si].[Zn].[Cu] QBOMBCGAEZXOSM-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 241001275902 Parabramis pekinensis Species 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- GFAWQOJYGFJWNJ-UHFFFAOYSA-N [Bi].[Zn].[Cu] Chemical compound [Bi].[Zn].[Cu] GFAWQOJYGFJWNJ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
Classifications
-
- 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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
Definitions
- the invention relates to a copper-zinc casting alloy.
- the invention relates to a copper-zinc-silicon alloy in which boron and iron and optionally nickel are added.
- molded parts made of copper alloys are produced as castings.
- molded parts are fittings, elbows, T-pieces for media-carrying piping systems, components for pumps and valves as well as structural parts in mechanical and plant engineering and in vehicle construction.
- silicon-containing brasses are used as material for this purpose.
- a material In order to ensure the mechanical stability of the molded part, a material is required, which already has a homogeneous structure in the cast state. Inhomogeneities in the structure must be taken into account by costly safety margins or they can lead to failure of the component. With wrought materials, the homogeneity of the structure is achieved by forming. In order to achieve a homogeneous structure without forming steps, the material must already have a fine-grained structure in the cast state. After casting, the molding is in many cases by machining, grinding or polishing, such as sealing surfaces, reworked. For this purpose, the material must be free from voids and hard particles. Furthermore, a coarse dendritic microstructure has a negative effect on the corrosion resistance of the material.
- the material In the production of castings, the material is usually melted and poured twice: the first time the alloy is melted, the alloy composition is roughly adjusted. The alloy is poured into ingots. For the production of the castings, the ingots are melted down and the alloy is cast into moldings. A change in the alloy composition during this second reflow and pouring operation is undesirable but unavoidable due to the burning of some elements, such as Zn, Zr or P. For the quality of the product, the casting condition after the second casting is crucial.
- boron as a grain refining agent for copper alloys is known. So will in DE 10 2005 024 037 A1 proposed to add 0.00001 to 0.5% boron to a copper-zinc-silicon alloy. Boron-fines of small amounts of boron are detected by alloys containing approximately 76% copper, 21% zinc and 3% silicon.
- the publication CN 103114220 A discloses a Cu-Zn-Si alloy containing 0.11-0.2% Fe and 0.001-0.01% B, Ag and / or Ti.
- the invention has for its object to provide improved copper-zinc casting alloys.
- a grain refining of the cast structure should be able to be achieved largely independently of the zinc or copper content.
- grain refining agents for copper contents greater than 80% by weight are particularly desirable.
- the invention relates to the copper-zinc casting alloy according to claim 1.
- the others refer back Claims relate to advantageous embodiments and further developments of the invention.
- the invention is based on the consideration that by the simultaneous addition of boron and iron to a silicon-containing copper-zinc alloy, a grain refining of the cast structure occurs when boron content and iron content are in a certain ratio. Iron can be partially replaced by nickel. The ratio of boron content and the sum of iron and nickel content is at least 0.025 and at most 0.12. The respective element contents are defined as parts by weight of the total alloy. Are boron content and the sum of iron and nickel content in the relation to each other, iron borides or nickel borides or iron-nickel Mischboride can form. These borides lead to the formation of a fine grain in the cast structure of the material.
- the alloy may contain tin.
- Tin improves the corrosion resistance of the material. With tin contents greater than 2.0% by weight, unwanted tin blends may occur due to the interaction of all alloy constituents.
- the alloy may contain phosphorus.
- phosphorus serves to deoxidize the melt. Furthermore, it can favorably influence the formation of the initial cast structure and the corrosion properties. Phosphorus increases the fluidity of the melt and reduces the susceptibility of the material to stress corrosion cracking.
- the lead content of the alloy according to the invention is limited to a maximum of 0.25 wt .-%.
- the lead content of the alloy may preferably be at most 0.1% by weight.
- the alloy may contain small amounts of antimony and / or arsenic. These two elements reduce the tendency of the material for Entzinkung.
- the ratio of boron content and the sum of iron and nickel content may be at least 0.05 and at most 0.075.
- the boron content may be at least 0.005% by weight, more preferably at least 0.01% by weight and at most 0.025% by weight.
- Boron contents of at least 0.005 wt .-%, preferably at least 0.01 wt .-%, in conjunction with iron and optionally nickel borides can form particularly rapidly. With a boron content greater than 0.025 wt .-% can lead to the formation of undesirable large borides.
- the iron content may be at least 0.1% by weight and at most 0.5% by weight.
- This preferred selection of iron content is stoichiometrically particularly favorable conditions for the formation of borides in suitable frequency and size.
- this preferred iron content is combined with a boron content of not less than 0.01% by weight and not more than 0.025% by weight. -% is already present at the first casting the alloy a fine-grained structure.
- the nickel content may amount to at most 0.3 wt .-%.
- nickel can at least partially replace the iron.
- the sum of iron and nickel content at least 0.1 wt .-% and at most 0.5 wt .-% amount.
- the copper content of the alloy may be more than 80% by weight, preferably at least 81% by weight. Copper contents of more than 80% by weight make the alloy particularly corrosion-resistant and therefore suitable for use in fluid-carrying piping systems, such as drinking water pipes.
- the silicon content in this copper content is typically at least 3 wt .-% and at most 4 wt .-%.
- the zinc content is then below 16 wt .-%, and is preferably at least 8 wt .-% and at most 15 wt .-%.
- the ratio of boron content of the alloy [in% by weight] and iron content of the alloy [in% by weight] is at least 0.025 and at most 0.12.
- the copper-zinc-silicon alloy may have the following composition [in% by weight]: Cu 70.0 to 97.0%, Si 2.0 to 4.5%, B From 0.002 to 0.03%, Fe 0.01 to 1.0%, optionally up to 2.0% Sn, optionally up to 0.2% P, optionally up to 0.25% Pb, optionally still up to 0.15% As or Sb, Rest Zn as well as unavoidable impurities.
- grain refining of the cast structure may occur in a copper-zinc-silicon alloy.
- the boron content is preferably at least 0.005% by weight and at most 0.025% by weight.
- the iron content is preferably at least 0.1% by weight and at most 0.5% by weight.
- the aspect of using boron and iron to refine copper-zinc-silicon alloys includes all of the above-described preferred embodiments of a silicon-containing copper-zinc casting alloy according to the present invention.
- the copper-zinc-silicon alloy may have the following composition [in% by weight]: Cu 70.0 to 97.0%, Si 2.0 to 4.5%, B From 0.002 to 0.03%, Fe 0.01 to 1.0%, Ni 0.01 to 0.4% optionally up to 2.0% Sn, optionally up to 0.2% P, optionally up to 0.25% Pb, optionally still up to 0.15% As or Sb, Rest Zn as well as unavoidable impurities.
- grain refining of the cast structure may occur in a copper-zinc-silicon alloy.
- the boron content is preferably at least 0.005% by weight and at most 0.025% by weight.
- the iron content is preferably at least 0.1% by weight and at most 0.5% by weight.
- the nickel content is preferably at least 0.05% by weight and at most 0.3% by weight.
- the aspect of using boron, iron and nickel for grain refining of copper-zinc-silicon alloys includes all of the above-described preferred embodiments of a silicon-containing copper-zinc casting alloy according to the present invention.
- Table 1 shows the composition in% by weight of 18 trial alloys, with samples 1, 2, 3, 4, 11 and 18 not belonging to the invention.
- the penultimate column of the table gives the ratio of boron content and the sum of iron and nickel content.
- the alloys were melted and poured off.
- the individual casts were melted down again and poured off a second time.
- the samples were characterized metallographically.
- the last column of the table indicates whether the structure after the second casting was coarse or fine grained.
- Samples 1 to 3 contain no boron.
- the cast structure is always coarse-grained.
- Sample 4 and sample 11 contain small amounts of boron. Again, the structure is coarse-grained.
- Samples 5 to 10 contain both boron (0.01 to 0.02 wt%) and iron (0.1 to 0.3 wt%). Sample 8 additionally contains 0.4% by weight of tin. For samples 5 to 10, a fine-grained cast structure is always observed after the second casting. The quotient of boron content and iron content in these samples is between 0.03 and 0.11. The addition of tin has no influence on the formation of the fine-grained casting structure.
- the samples 5, 7, 8 and 15, in contrast to the other samples after the first casting have a fine-grained structure.
- These samples are characterized in that the quotient of boron content and the sum of iron and nickel content is between 0.05 and 0.065. If one chooses the alloy composition so that said quotient is exactly in this window, then the formation of iron borides or nickel borides or iron-nickel Mischboriden is particularly favored. Iron borides with the stoichiometric formula Fe 3 B would correspond exactly to this weight ratio of boron and iron.
- sample 18 On the basis of sample 18, the influence of manganese on the cast structure was examined in the form of a random sample. Sample 18 contains no boron but about 0.08 wt% manganese. The manganese-containing sample always shows a coarse-grained cast structure.
Description
Die Erfindung betrifft eine Kupfer-Zink-Gusslegierung. Insbesondere betrifft die Erfindung eine Kupfer-Zink-Silicium-Legierung, bei welcher Bor und Eisen sowie optional Nickel zugegeben sind.The invention relates to a copper-zinc casting alloy. In particular, the invention relates to a copper-zinc-silicon alloy in which boron and iron and optionally nickel are added.
Es ist bekannt, dass Formteile aus Kupferlegierungen als Gussteile hergestellt werden. Beispiele für solche Formteile sind Armaturen, Bögen, T-Stücke für medienführende Leitungssysteme, Komponenten für Pumpen und Ventile sowie Konstruktionsteile im Maschinen- und Anlagenbau und im Fahrzeugbau. Unter anderem werden hierfür siliciumhaltige Messinge als Werkstoff verwendet.It is known that molded parts made of copper alloys are produced as castings. Examples of such molded parts are fittings, elbows, T-pieces for media-carrying piping systems, components for pumps and valves as well as structural parts in mechanical and plant engineering and in vehicle construction. Among other things, silicon-containing brasses are used as material for this purpose.
Um die mechanische Stabilität des Formteils zu gewährleisten, ist ein Werkstoff erforderlich, der bereits im Gusszustand ein homogenes Gefüge aufweist. Inhomogenitäten im Gefüge müssen durch kostspielige Sicherheitszuschläge berücksichtigt werden oder sie können zum Versagen des Bauteils führen. Bei Knetwerkstoffen wird die Homogenität des Gefüges durch Umformung erzielt. Um ein homogenes Gefüge ohne Umformschritte zu erreichen, muss der Werkstoff bereits im Gusszustand ein feinkörniges Gefüge aufweisen. Nach dem Gießen wird das Formteil in viele Fällen durch Zerspanen, Schleifen oder Polieren, beispielsweise von Dichtflächen, nachbearbeitet. Hierfür muss der Werkstoff frei von Lunkern und Hartpartikeln sein. Ferner wirkt sich ein grobes dendritisches Gefüge negativ auf die Korrosionsbeständigkeit des Werkstoffs aus.In order to ensure the mechanical stability of the molded part, a material is required, which already has a homogeneous structure in the cast state. Inhomogeneities in the structure must be taken into account by costly safety margins or they can lead to failure of the component. With wrought materials, the homogeneity of the structure is achieved by forming. In order to achieve a homogeneous structure without forming steps, the material must already have a fine-grained structure in the cast state. After casting, the molding is in many cases by machining, grinding or polishing, such as sealing surfaces, reworked. For this purpose, the material must be free from voids and hard particles. Furthermore, a coarse dendritic microstructure has a negative effect on the corrosion resistance of the material.
Bei der Herstellung von Gussteilen wird der Werkstoff üblicherweise zweimal aufgeschmolzen und abgegossen: Beim ersten Aufschmelzen wird die Legierungszusammensetzung grob eingestellt. Die Legierung wird zu Gussblöcken gegossen. Zur Herstellung der Gussteile werden die Gussblöcke eingeschmolzen und die Legierung zu Formteilen vergossen. Eine Änderung der Legierungszusammensetzung während dieses zweiten Aufschmelz- und Abgussvorgangs ist unerwünscht, aber aufgrund des Abbrands mancher Elemente, wie Zn, Zr oder P, unvermeidlich. Für die Qualität des Produkts ist der Gusszustand nach dem zweiten Abguss entscheidend.In the production of castings, the material is usually melted and poured twice: the first time the alloy is melted, the alloy composition is roughly adjusted. The alloy is poured into ingots. For the production of the castings, the ingots are melted down and the alloy is cast into moldings. A change in the alloy composition during this second reflow and pouring operation is undesirable but unavoidable due to the burning of some elements, such as Zn, Zr or P. For the quality of the product, the casting condition after the second casting is crucial.
Es ist bekannt, dass bei Kupferlegierungen durch die Zugabe von bestimmten Elementen ein feinkörniges Gussgefüge eingestellt werden kann. In
In
Bor als Kornfeinungsmittel für Kupferlegierungen zu verwenden, ist bekannt. So wird in
Der Druckschrift ,Kornfeinung von Kupferlegierungen' von
Die Druckschrift
In der
Der Fachmann erhält aus dem Stand der Technik nur unbefriedigende Hinweise, wie bei Kupfer-Zink-Silicium-Legierung ein feinkörniges Gussgefüge eingestellt werden kann. Zirkon ist aufgrund seines Abbrands nur sehr schwierig einsetzbar. Bor bewirkt eine Kornfeinung für Zinkgehalte von ungefähr 21 Gew.-%, nicht jedoch für Zinkgehalte von ungefähr 16 Gew.-%. Deshalb wäre ein Kornfeinungsmittel wünschenswert, das weitgehend unabhängig vom Zinkgehalt seine Wirkung entfaltet. Insbesondere soll es für Kupfergehalte größer 80 Gew.-% eine Kornfeinung bewirken.The expert receives from the prior art only unsatisfactory evidence, as in copper-zinc-silicon alloy, a fine-grained cast structure can be adjusted. Zircon is very difficult to use due to its burnup. Boron causes grain refining for zinc contents of about 21% by weight, but not for zinc contents of about 16% by weight. It would therefore be desirable to have a grain refining agent that exerts its effect largely independently of the zinc content. In particular, it should bring about grain refining for copper contents greater than 80% by weight.
Der Erfindung liegt die Aufgabe zugrunde, verbesserte Kupfer-Zink-Gusslegierungen anzugeben. Insbesondere soll eine Kornfeinung des Gussgefüges weitgehend unabhängig vom Zink- beziehungsweise Kupfergehalt erreicht werden können. Mangels Alternativen sind Kornfeinungsmittel für Kupfergehalte größer 80 Gew.-% besonders erstrebenswert.The invention has for its object to provide improved copper-zinc casting alloys. In particular, a grain refining of the cast structure should be able to be achieved largely independently of the zinc or copper content. In the absence of alternatives, grain refining agents for copper contents greater than 80% by weight are particularly desirable.
Die Erfindung betrifft die Kupfer-Zink-Gusslegierung gemäß Anspruch 1. Die weiteren rückbezogenen Ansprüche betreffen vorteilhafte Aus- und Weiterbildungen der Erfindung.The invention relates to the copper-zinc casting alloy according to claim 1. The others refer back Claims relate to advantageous embodiments and further developments of the invention.
Die Erfindung geht dabei von der Überlegung aus, dass durch die gleichzeitige Zugabe von Bor und Eisen zu einer siliciumhaltigen Kupfer-Zink-Legierung eine Kornfeinung des Gussgefüges eintritt, wenn Borgehalt und Eisengehalt in einem bestimmten Verhältnis zueinander stehen. Eisen kann dabei teilweise durch Nickel ersetzt werden. Das Verhältnis aus Borgehalt und der Summe aus Eisen- und Nickelgehalt beträgt mindestens 0,025 und höchstens 0,12. Die jeweiligen Elementgehalte sind dabei als Gewichtsanteile an der Gesamtlegierung definiert. Stehen Borgehalt und die Summe aus Eisen- und Nickelgehalt in der genannten Relation zu einander, können sich Eisenboride beziehungsweise Nickelboride oder Eisen-Nickel-Mischboride bilden. Diese Boride führen zur Ausbildung eines feinen Korns im Gussgefüge des Werkstoffs.The invention is based on the consideration that by the simultaneous addition of boron and iron to a silicon-containing copper-zinc alloy, a grain refining of the cast structure occurs when boron content and iron content are in a certain ratio. Iron can be partially replaced by nickel. The ratio of boron content and the sum of iron and nickel content is at least 0.025 and at most 0.12. The respective element contents are defined as parts by weight of the total alloy. Are boron content and the sum of iron and nickel content in the relation to each other, iron borides or nickel borides or iron-nickel Mischboride can form. These borides lead to the formation of a fine grain in the cast structure of the material.
Diese Erkenntnis ist um so überraschender, als der Fachmann dem Stand der Technik, insbesondere der
Wahlweise kann die Legierung Zinn enthalten. Zinn verbessert die Korrosionsbeständigkeit des Werkstoffs. Bei Zinngehalten größer 2,0 Gew.-% kann es aufgrund des Zusammenwirkens aller Legierungsbestandteile zu unerwünschten Zinnentmischungen kommen.Optionally, the alloy may contain tin. Tin improves the corrosion resistance of the material. With tin contents greater than 2.0% by weight, unwanted tin blends may occur due to the interaction of all alloy constituents.
Wahlweise kann die Legierung Phosphor enthalten. In kleinen Mengen dient Phosphor der Desoxidation der Schmelze. Ferner kann er die Ausbildung des anfänglichen Gussgefüges und die Korrosionseigenschaften günstig beeinflussen. Phosphor erhöht das Fließvermögen der Schmelze und vermindert die Anfälligkeit des Werkstoffs gegen Spannungsrisskorrosion.Optionally, the alloy may contain phosphorus. In small amounts, phosphorus serves to deoxidize the melt. Furthermore, it can favorably influence the formation of the initial cast structure and the corrosion properties. Phosphorus increases the fluidity of the melt and reduces the susceptibility of the material to stress corrosion cracking.
Blei macht die Legierungen leichter zerspanbar. Um den gesetzlichen Vorschriften für den Einsatz von Kupferlegierungen in Trinkwasseranwendungen zu genügen, wird der Bleigehalt der erfindungsgemäßen Legierung auf maximal 0,25 Gew.-% eingeschränkt. Bevorzugt kann der Bleigehalt der Legierung höchstens 0,1 Gew.-% betragen.Lead makes the alloys easier to machine. To comply with the legal requirements for the use of copper alloys in drinking water applications, the lead content of the alloy according to the invention is limited to a maximum of 0.25 wt .-%. The lead content of the alloy may preferably be at most 0.1% by weight.
Wahlweise kann die Legierung in geringen Mengen Antimon und/oder Arsen enthalten. Diese beiden Elemente verringern die Neigung des Werkstoffs zur Entzinkung.Optionally, the alloy may contain small amounts of antimony and / or arsenic. These two elements reduce the tendency of the material for Entzinkung.
In bevorzugter Ausgestaltung der Erfindung kann das Verhältnis aus Borgehalt und der Summe aus Eisen- und Nickelgehalt mindestens 0,05 und höchstens 0,075 betragen. Überraschenderweise hat sich gezeigt, dass sich bei Wahl der Legierungszusammensetzung gemäß dieser Spezifikation bereits nach dem ersten Abguss ein feinkörniges Gefüge einstellt. Auch nach dem zweiten Abguss ist das Gefüge immer feinkörnig. Diese vorteilhafte Auswahl der Legierungszusammensetzung gewährleistet also besonders zuverlässig die Ausbildung eines feinkörnigen Gussgefüges und aus der Feinkörnigkeit der Gussblöcke lässt sich bereits eine Aussage über die Qualität der Formteile ableiten. Diese bevorzugte Auswahl des Borgehalts und der Summe aus Eisen- und Nickelgehalt stellt stöchiometrisch besonders günstige Bedingungen für die Ausbildung von Boriden dar.In a preferred embodiment of the invention, the ratio of boron content and the sum of iron and nickel content may be at least 0.05 and at most 0.075. Surprisingly, it has been found that, when the alloy composition according to this specification is selected, a fine-grained microstructure already ensues after the first casting. Even after the second casting, the microstructure is always fine-grained. This advantageous selection of the alloy composition thus ensures particularly reliable the formation of a fine-grained cast structure and from the fine grain of the cast blocks can already derive a statement about the quality of the molded parts. This preferred selection of the boron content and the sum of iron and nickel content represents stoichiometrically particularly favorable conditions for the formation of borides.
In bevorzugter Ausgestaltung der Erfindung kann der Borgehalt mindestens 0,005 Gew.-%, besonders bevorzugt mindestens 0,01 Gew.-% und höchstens 0,025 Gew.-% betragen. Bei Borgehalten von mindestens 0,005 Gew.-%, bevorzugt mindestens 0,01 Gew.-%, können sich in Verbindung mit Eisen und gegebenenfalls Nickel Boride besonders rasch ausbilden. Bei einem Borgehalt größer als 0,025 Gew.-% kann es zur Bildung von unerwünschten großen Boriden kommen.In a preferred embodiment of the invention, the boron content may be at least 0.005% by weight, more preferably at least 0.01% by weight and at most 0.025% by weight. Boron contents of at least 0.005 wt .-%, preferably at least 0.01 wt .-%, in conjunction with iron and optionally nickel borides can form particularly rapidly. With a boron content greater than 0.025 wt .-% can lead to the formation of undesirable large borides.
Vorteilhafterweise kann der Eisengehalt mindestens 0,1 Gew.-% und höchstens 0,5 Gew.-% betragen. Diese bevorzugte Auswahl des Eisengehalts stellt stöchiometrisch besonders günstige Bedingungen für die Ausbildung von Boriden in geeigneter Häufigkeit und Größe dar. Insbesondere bei Kombination dieses bevorzugten Eisengehalts mit einem Borgehalt, der nicht weniger als 0,01 Gew.-% und nicht mehr als 0,025 Gew.-% beträgt, stellt sich bereits beim ersten Abguss der Legierung ein feinkörniges Gefüge ein.Advantageously, the iron content may be at least 0.1% by weight and at most 0.5% by weight. This preferred selection of iron content is stoichiometrically particularly favorable conditions for the formation of borides in suitable frequency and size. In particular, when this preferred iron content is combined with a boron content of not less than 0.01% by weight and not more than 0.025% by weight. -% is already present at the first casting the alloy a fine-grained structure.
In bevorzugter Ausgestaltung der Erfindung kann der Nickelgehalt höchstens 0,3 Gew.-% betragen. Hinsichtlich der Bildung der Boride kann Nickel das Eisen zumindest teilweise ersetzen. In besonders bevorzugter Ausgestaltung kann die Summe aus Eisen- und Nickelgehalt mindestens 0,1 Gew.-% und höchstens 0,5 Gew.-% betragen. Ferner kann es vorteilhaft sein, den Eisengehalt der Legierung größer als den Nickelgehalt zu wählen. Durch den Eisenanteil wird die Bildung von Boriden initiiert und somit der Kornfeinungseffekt eingeleitet.In a preferred embodiment of the invention, the nickel content may amount to at most 0.3 wt .-%. With regard to the formation of borides, nickel can at least partially replace the iron. In a particularly preferred embodiment, the sum of iron and nickel content at least 0.1 wt .-% and at most 0.5 wt .-% amount. Furthermore, it may be advantageous to choose the iron content of the alloy greater than the nickel content. The iron content initiates the formation of borides and thus initiates the grain refining effect.
Vorteilhafterweise kann der Kupfergehalt der Legierung mehr als 80 Gew-%, bevorzugt mindestens 81 Gew.-% betragen. Kupfergehalte größer 80 Gew-% machen die Legierung besonders korrosionsbeständig und damit geeignet für den Einsatz in fluidführenden Leitungssystemen, wie beispielsweise Trinkwasserleitungen. Der Siliciumgehalt beträgt bei diesem Kupfergehalt typischerweise mindestens 3 Gew.-% und höchstens 4 Gew.-%. Der Zinkgehalt liegt dann unter 16 Gew.-%, und beträgt bevorzugt mindestens 8 Gew.-% und höchstens 15 Gew.-%.Advantageously, the copper content of the alloy may be more than 80% by weight, preferably at least 81% by weight. Copper contents of more than 80% by weight make the alloy particularly corrosion-resistant and therefore suitable for use in fluid-carrying piping systems, such as drinking water pipes. The silicon content in this copper content is typically at least 3 wt .-% and at most 4 wt .-%. The zinc content is then below 16 wt .-%, and is preferably at least 8 wt .-% and at most 15 wt .-%.
Bor und Eisen in Kombination sind als Kornfeinungsmittel in Kupfer-Zink-Silicium-Legierungen geeignet. Dabei beträgt das Verhältnis aus Borgehalt der Legierung [in Gew.-%] und Eisengehalt der Legierung [in Gew.-%] mindestens 0,025 und höchstens 0,12. Die Kupfer-Zink-Silicium-Legierung kann dabei folgende Zusammensetzung [in Gew.-%] aufweisen:
wahlweise noch bis 0,2 % P,
wahlweise noch bis 0,25 % Pb,
wahlweise jeweils noch bis zu 0,15 % As oder Sb,
Rest Zn sowie unvermeidbare Verunreinigungen.Boron and iron in combination are suitable as grain refining agents in copper-zinc-silicon alloys. The ratio of boron content of the alloy [in% by weight] and iron content of the alloy [in% by weight] is at least 0.025 and at most 0.12. The copper-zinc-silicon alloy may have the following composition [in% by weight]:
optionally up to 0.2% P,
optionally up to 0.25% Pb,
optionally still up to 0.15% As or Sb,
Rest Zn as well as unavoidable impurities.
Durch die Zugabe von Bor und Eisen im oben genannten Verhältnis der Gehalte kann bei einer Kupfer-Zink-Silicium-Legierung eine Kornfeinung des Gussgefüges eintreten. Bevorzugt beträgt der Borgehalt dabei mindestens 0,005 Gew.-% und höchstens 0,025 Gew.-%. Bevorzugt beträgt der Eisengehalt dabei mindestens 0,1 Gew.-% und höchstens 0,5 Gew.-%.By the addition of boron and iron in the above ratio of the contents, grain refining of the cast structure may occur in a copper-zinc-silicon alloy. The boron content is preferably at least 0.005% by weight and at most 0.025% by weight. The iron content is preferably at least 0.1% by weight and at most 0.5% by weight.
Der Aspekt der Verwendung von Bor und Eisen zur Kornfeinung von Kupfer-Zink-Silicium-Legierungen schließt alle vorstehend beschriebenen, bevorzugten Ausführungsformen einer erfindungsgemäßen siliciumhaltigen Kupfer-Zink-Gusslegierung ein.The aspect of using boron and iron to refine copper-zinc-silicon alloys includes all of the above-described preferred embodiments of a silicon-containing copper-zinc casting alloy according to the present invention.
Bor, Eisen und Nickel in Kombination sind als Kornfeinungsmittel in Kupfer-Zink-Silicium-Legierungen geeignet. Dabei beträgt das Verhältnis aus Borgehalt der Legierung [in Gew.-%] und der Summe aus Eisen- und Nickelgehalt der Legierung [in Gew.-%] mindestens 0,025 und höchstens 0,12. Die Kupfer-Zink-Silicium-Legierung kann dabei folgende Zusammensetzung [in Gew.-%] aufweisen:
wahlweise noch bis 0,2 % P,
wahlweise noch bis 0,25 % Pb,
wahlweise jeweils noch bis zu 0,15 % As oder Sb,
Rest Zn sowie unvermeidbare Verunreinigungen.Boron, iron and nickel in combination are suitable as grain refining agents in copper-zinc-silicon alloys. The ratio of boron content of the alloy [in wt .-%] and the sum of iron and nickel content of the alloy [in wt .-%] is at least 0.025 and at most 0.12. The copper-zinc-silicon alloy may have the following composition [in% by weight]:
optionally up to 0.2% P,
optionally up to 0.25% Pb,
optionally still up to 0.15% As or Sb,
Rest Zn as well as unavoidable impurities.
Durch die Zugabe von Bor, Eisen und Nickel im oben genannten Verhältnis der Gehalte kann bei einer Kupfer-Zink-Silicium-Legierung eine Kornfeinung des Gussgefüges eintreten. Bevorzugt beträgt der Borgehalt dabei mindestens 0,005 Gew.-% und höchstens 0,025 Gew.-%. Bevorzugt beträgt der Eisengehalt dabei mindestens 0,1 Gew.-% und höchstens 0,5 Gew.-%. Bevorzugt beträgt der Nickelgehalt dabei mindestens 0,05 Gew.-% und höchstens 0,3 Gew.-%.By the addition of boron, iron and nickel in the above ratio of the contents, grain refining of the cast structure may occur in a copper-zinc-silicon alloy. The boron content is preferably at least 0.005% by weight and at most 0.025% by weight. The iron content is preferably at least 0.1% by weight and at most 0.5% by weight. The nickel content is preferably at least 0.05% by weight and at most 0.3% by weight.
Der Aspekt der Verwendung von Bor, Eisen und Nickel zur Kornfeinung von Kupfer-Zink-Silicium-Legierungen schließt alle vorstehend beschriebenen, bevorzugten Ausführungsformen einer erfindungsgemäßen siliciumhaltigen Kupfer-Zink-Gusslegierung ein.The aspect of using boron, iron and nickel for grain refining of copper-zinc-silicon alloys includes all of the above-described preferred embodiments of a silicon-containing copper-zinc casting alloy according to the present invention.
Die Erfindung wird anhand der in Tabelle 1 aufgeführten Ausführungsbeispiele näher erläutert.The invention will be explained in more detail with reference to the embodiments shown in Table 1.
Tabelle 1 zeigt von 18 Versuchslegierungen die Zusammensetzung in Gew.-%, wobei Proben 1, 2, 3, 4, 11 und 18 nicht zur Erfindung gehören. In der vorletzten Spalte der Tabelle ist das Verhältnis aus Borgehalt und der Summe aus Eisen- und Nickelgehalt angegeben. Die Legierungen wurden erschmolzen und abgegossen. Die einzelnen Abgüsse wurden wieder eingeschmolzen und ein zweites Mal abgegossen. Die Proben wurden metallographisch charakterisiert. In der letzten Spalte der Tabelle ist angegeben, ob das Gefüge nach dem zweiten Abguss grobkörnig oder feinkörnig war.Table 1 shows the composition in% by weight of 18 trial alloys, with samples 1, 2, 3, 4, 11 and 18 not belonging to the invention. The penultimate column of the table gives the ratio of boron content and the sum of iron and nickel content. The alloys were melted and poured off. The individual casts were melted down again and poured off a second time. The samples were characterized metallographically. The last column of the table indicates whether the structure after the second casting was coarse or fine grained.
Proben 1 bis 3 enthalten kein Bor. Das Gussgefüge ist immer grobkörnig. Probe 4 und Probe 11 enthalten geringe Mengen an Bor. Auch hier ist das Gefüge grobkörnig.Samples 1 to 3 contain no boron. The cast structure is always coarse-grained. Sample 4 and sample 11 contain small amounts of boron. Again, the structure is coarse-grained.
Proben 5 bis 10 enthalten sowohl Bor (0,01 bis 0,02 Gew.-%) als auch Eisen (0,1 bis 0,3 Gew.-%). Probe 8 enthält zusätzlich 0,4 Gew.-% Zinn. Für die Proben 5 bis 10 ist nach dem zweiten Abguss immer ein feinkörniges Gussgefüge zu beobachten. Der Quotient aus Borgehalt und Eisengehalt liegt bei diesen Proben zwischen 0,03 und 0,11. Die Zugabe von Zinn hat keinen Einfluss auf die Bildung des feinkörnigen Gussgefüges.
Bei den Proben 12 bis 17 ist ein Teil des Eisens durch Nickel ersetzt. Der Borgehalt variiert von 0,005 bis 0,013 Gew.-%. Der Eisengehalt liegt zwischen 0,1 und 0,2 Gew.-%, der Nickelgehalt zwischen 0,08 und 0,18 Gew.-%. Ferner variiert der Zinngehalt von 0,1 bis 0,2 Gew.-%. Mit Ausnahme von Probe 13 zeigen alle Proben nach dem zweiten Abguss ein feinkörniges Gefüge. Bei diesen Proben liegt der Quotient aus Borgehalt und der Summe aus Eisen- und Nickelgehalt zwischen 0,025 und 0,06. Bei Probe 13 liegt dieser Quotient bei 0,016. Die Probe 13 enthält in der Summe zu viel Eisen und Nickel bezogen auf den Borgehalt von 0,006 Gew.-%. Der Zinngehalt hat keinen Einfluss auf die Bildung des feinen Gussgefüges.In Samples 12 to 17, part of the iron is replaced by nickel. The boron content varies from 0.005 to 0.013% by weight. The iron content is between 0.1 and 0.2 wt .-%, the nickel content between 0.08 and 0.18 wt .-%. Further, the tin content varies from 0.1 to 0.2 wt%. With the exception of sample 13, all samples after the second casting show a fine-grained texture. For these samples, the quotient of boron content and the sum of iron and nickel content is between 0.025 and 0.06. For sample 13, this quotient is 0.016. The sample 13 contains in total too much iron and nickel based on the boron content of 0.006 wt .-%. The tin content has no influence on the formation of the fine cast structure.
Es ist hervorzuheben, dass die Proben 5, 7, 8 und 15 im Unterschied zu den anderen Proben bereits nach dem ersten Abguss ein feinkörniges Gefüge aufweisen. Diese Proben sind dadurch gekennzeichnet, dass der Quotient aus Borgehalt und der Summe aus Eisen- und Nickelgehalt zwischen 0,05 und 0,065 liegt. Wählt man die Legierungszusammensetzung so, dass der genannte Quotient genau in diesem Fenster liegt, dann ist die Bildung von Eisenboriden beziehungsweise Nickelboriden oder Eisen-Nickel-Mischboriden besonders begünstigt. Eisenboride mit der stöchiometrischen Formel Fe3B würden genau diesem Gewichtsverhältnis aus Bor und Eisen entsprechen.It should be emphasized that the samples 5, 7, 8 and 15, in contrast to the other samples after the first casting have a fine-grained structure. These samples are characterized in that the quotient of boron content and the sum of iron and nickel content is between 0.05 and 0.065. If one chooses the alloy composition so that said quotient is exactly in this window, then the formation of iron borides or nickel borides or iron-nickel Mischboriden is particularly favored. Iron borides with the stoichiometric formula Fe 3 B would correspond exactly to this weight ratio of boron and iron.
Anhand von Probe 18 wurde in Form einer Stichprobe der Einfluss von Mangan auf das Gussgefüge untersucht. Probe 18 enthält kein Bor, dafür ungefähr 0,08 Gew.-% Mangan. Die manganhaltige Probe zeigt immer ein grobkörniges Gussgefüge.On the basis of sample 18, the influence of manganese on the cast structure was examined in the form of a random sample. Sample 18 contains no boron but about 0.08 wt% manganese. The manganese-containing sample always shows a coarse-grained cast structure.
Claims (8)
- Copper/zinc casting alloy with the following composition [in% by weight]:
Cu from 70 to 97.0%, Si from 2.0 to 4.5%, B from 0.002 to 0.03%, Fe from 0.01 to 1.0%,
optionally further up to 0.4% Ni,
optionally further up to 0.2% P,
optionally further up to 0.25% Pb,
optionally further up to 0.15% As or Sb,
balance Zn and inevitable impurities,
characterised in that
the ratio of boron content and the sum of iron and nickel content is at least 0.025 and a maximum of 0.12. - Copper/zinc casting alloy according to claim 1, characterised in that
the ratio of boron content and the sum of iron and nickel content is at least 0.05 and a maximum of 0.075. - Copper/zinc casting alloy according to claim 1 or 2, characterised in that
the boron content is at least 0.005% by weight and a maximum of 0.025% by weight. - Copper/zinc casting alloy according to claim 3, characterised in that
the boron content is at least 0.01% by weight and a maximum of 0.025% by weight. - Copper/zinc casting alloy according to any one of claims 1 to 4, characterised in that
the iron content is at least 0.1% by weight and a maximum of 0.5% by weight. - Copper/zinc casting alloy according to any one of claims 1 to 5, characterised in that
the nickel content is a maximum of 0.3% by weight. - Copper/zinc casting alloy according to any one of claims 1 to 6, characterised in that
the iron content is greater than the nickel content. - Copper/zinc casting alloy according to any one of claims 1 to 7, characterised in that
the copper content is at least 81% by weight.
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CN103114220A (en) | 2013-02-01 | 2013-05-22 | 路达(厦门)工业有限公司 | Excellent-thermoformability lead-free free-cutting corrosion-resistant brass alloy |
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GB2234986A (en) | 1989-08-18 | 1991-02-20 | London Scandinavian Metall | Grain refining of copper-based alloys |
JPH03115538A (en) * | 1989-09-29 | 1991-05-16 | Tsuneaki Mikawa | Oxide dispersion strengthened special copper alloy |
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US5893953A (en) * | 1997-09-16 | 1999-04-13 | Waterbury Rolling Mills, Inc. | Copper alloy and process for obtaining same |
US20070039817A1 (en) * | 2003-08-21 | 2007-02-22 | Daniels Brian J | Copper-containing pvd targets and methods for their manufacture |
JP3964930B2 (en) | 2004-08-10 | 2007-08-22 | 三宝伸銅工業株式会社 | Copper-base alloy castings with refined crystal grains |
DE102005024037A1 (en) | 2004-10-11 | 2006-04-13 | Diehl Metall Stiftung & Co.Kg | Copper-based alloy used e.g. in the production of electro-technical components contains copper, silicon, boron and phosphorus and/or arsenic and a balance of zinc |
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US20070253858A1 (en) * | 2006-04-28 | 2007-11-01 | Maher Ababneh | Copper multicomponent alloy and its use |
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CN103114220A (en) | 2013-02-01 | 2013-05-22 | 路达(厦门)工业有限公司 | Excellent-thermoformability lead-free free-cutting corrosion-resistant brass alloy |
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