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EP4569148A1 - Matériau de coulée fait d'un alliage de cuivre-zinc, procédé de fabrication d'un produit coulé et pièce coulée - Google Patents

Matériau de coulée fait d'un alliage de cuivre-zinc, procédé de fabrication d'un produit coulé et pièce coulée

Info

Publication number
EP4569148A1
EP4569148A1 EP23764232.7A EP23764232A EP4569148A1 EP 4569148 A1 EP4569148 A1 EP 4569148A1 EP 23764232 A EP23764232 A EP 23764232A EP 4569148 A1 EP4569148 A1 EP 4569148A1
Authority
EP
European Patent Office
Prior art keywords
phase
weight
proportion
copper
cast
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.)
Pending
Application number
EP23764232.7A
Other languages
German (de)
English (en)
Inventor
HOLLY (geb. Obert), Susanne
Andrea KÄUFLER
Dalibor KRSTIC
Tony Robert Noll
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wieland Werke AG
Original Assignee
Wieland Werke AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wieland Werke AG filed Critical Wieland Werke AG
Publication of EP4569148A1 publication Critical patent/EP4569148A1/fr
Pending legal-status Critical Current

Links

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
    • 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

Definitions

  • Casting material made from a copper-zinc alloy, process for producing a cast product and casting
  • the invention relates to a casting material made of a copper-zinc alloy, a method for producing a cast product and a casting.
  • Copper-zinc casting materials also called “casting alloys” consisting of a and ß phases with approximately 1% by weight of lead, such as CuZn39Pb1AI-B (CB757S), are excellent for casting, very easy to machine and also easy to polish .
  • Lead-containing copper-zinc casting alloys are used in a variety of applications in the sanitary sector, especially for taps and fittings in the drinking water sector.
  • lead in copper-zinc alloys is based on the fact that lead is present as elementary particles in the structure and these particles act as chip breakers.
  • lead is present as a liquid phase due to the strong local deformation in the workpiece and the resulting local increase in temperature. Since the lead cannot absorb stress in its liquid state, this leads to a stress concentration on the load-transferring, weakened matrix and thus to easier chip breakage.
  • lead is incorporated into the tribological layer between the material and the tool during machining, resulting in effective lubrication and thus a reduction in friction and wear.
  • CONFIRMATION COPY Lead causes significant grain refinement in copper-zinc alloys. This is particularly beneficial for the polishability of cast material. In addition, lead has a low price.
  • copper-zinc alloys are known from the document EP 2 194 150 B1 which contain 0.1 to 1.5% by weight of Si, 0.03 to 0.4% by weight of Al, 0.01 to 0 .36% by weight of P, 0.05 to 0.5% by weight of Sn and 0.001 to 0.05% by weight of rare earths.
  • the alloys are easy to machine due to the formation of an a, ß and possibly y structure.
  • the Al content causes Al phosphides to form, which are undesirable.
  • the y-phase and Al phosphides improve chip formation, but worsen the tool life.
  • the proportion of rare earths probably leads to embrittlement of the structure.
  • the alloys are used for castings and hot-pressed parts.
  • the invention is based on the object of providing a casting material made of a copper-zinc alloy which has excellent machinability, good mechanical properties, a small grain size and thus good polishability, a low tendency to voids and the lowest possible content of ecologically questionable alloy components having. Furthermore, the invention is based on the object of specifying a method for producing a cast product and a cast part.
  • the invention is represented by the features of claim 1 with regard to a casting material made of a copper-zinc alloy and by the features of claim 7 with regard to a manufacturing process.
  • the further related claims relate to advantageous developments and further developments of the invention.
  • the invention relates to a casting material made of a copper-zinc alloy with the following composition in% by weight:
  • AI optional up to 0.05%
  • Pb optionally up to 0.25%, preferably up to 0.10%
  • the alloy has a structure of a-phase, ß-phase and phosphide particles.
  • the phosphide particles preferably contain or are copper- and/or zinc-containing phosphides.
  • the proportion of the ß-phase in the sum of a-phase and ß-phase is at least 20% by volume, preferably at least 40% by volume, and at most 70% by volume, preferably at most 60% by volume. Silicon is present in both the a phase and the ß phase.
  • the invention is based on the idea of reducing the proportion of Pb in the copper-zinc alloy as much as possible without impairing the machinability of the material.
  • Si and P are specifically added to the alloy and the volume fraction of the ß-phase is adjusted so that, on the one hand, favorable machining properties result and, on the other hand, the cast structure of the original base matrix made of ß-phase is refined.
  • the casting process is chosen so that the desired properties result.
  • a small ß grain size is advantageous for good polishability. Therefore, the ß phase must be fine-grained in the cast state. Surprisingly, it has been shown that with increasing P content, a significant grain refinement of the cast structure of the original base matrix from ß-phase occurs. In order to achieve sufficient grain refinement of the cast structure, the addition of at least 0.20% by weight of P is necessary. This is similar to the effect of 1 to 3 wt% Pb on grain refinement of ⁇ - ⁇ brass. During the primary crystallization of the ß-crystallites, the residual melt enriches with P and thereby leads to a subdivision and thus to a grain refinement of the ß-phase. During solidification, a eutectic consisting of phosphide and ß-phase is formed. In addition to the grain refinement of the base matrix from the ß phase, a grain refinement of the ⁇ crystals is observed.
  • phosphide particles are present in both the a-phase and the ß-phase in the cast material.
  • the alloy preferably contains at least 0.22% by weight of P.
  • coarse phosphides form in the cast state by individual ones Phosphides coagulate and form long network-like shapes. These coarse phosphides wet the grain boundaries and reduce ductility.
  • the material needs high strength corresponding to high hardness.
  • coarse undesirable phosphides can also occur at P contents of less than 0.38% by weight if the cooling rate when casting the alloy is too slow, such as when casting into a permanent mold.
  • the necessary high cooling rates are achieved, for example, when casting small 25 x 55 x 160 mm blocks into a steel mold. In this way it is achieved that with a P content of 0.20 to 0.38% by weight, the phosphide particles are already globular and finely distributed in the structure in the cast state. These act as separation points during machining and promote chip breakage.
  • the cooling rate during solidification must be at least 20 °C per minute (°C/min), preferably at least 30 °C per minute, and at most 60 °C in a temperature range of 550 °C to 350 °C C per minute, preferably at most 50 °C per minute.
  • the distribution of the phosphides and the grain size of the ß-phase are therefore determined not only by the chemical composition of the alloy, but also by the conditions during casting.
  • the characteristics of the phosphides in the cast state are like a fingerprint that the special process management leaves on the product.
  • the distribution of phosphides in the as-cast state can be characterized as follows: In an area of 21000 pm 2 there are 20 to 300 phosphide particles with an equivalent diameter of 0.5 to 1 pm, 30 to 120 phosphide particles with an equivalent diameter of 1 to 2 pm and 20 to 100 phosphide particles with an equivalent diameter of 2 to 5 pm are present. Below the equivalent diameter of a phosphide particle is the diameter of a to the phosphide particle of the same area. The majority of phosphide particles with an equivalent diameter of at least 0.5 pm have an equivalent diameter of at most 2 pm. If the cooling conditions are observed, the alloy is also suitable for continuous casting and mold casting, for example in the form of sand casting or chill casting.
  • Brittle structural components are advantageous for the machinability of the material, as they act as separation points during machining and thus promote chip breakage.
  • the ß phase is brittle and promotes machinability.
  • An increase in the proportion of ß-phase can be achieved by increasing the Zn content and/or by alloying silicon, because silicon stabilizes the ß-phase.
  • the ductility of the a-phase is reduced. This is achieved by alloying and incorporating silicon into the a-phase as well as finely distributed phosphides in the a-phase. Therefore, the Si content in the alloy must be at least 0.15% by weight.
  • the phosphide particles described above represent particles that act as separation points during machining and promote chip breakage.
  • a P content of at least 0.20% by weight not only improves machinability, but in particular refines the grain.
  • a small, optional proportion of Pb has an advantageous effect on machinability.
  • the machinability of the material is therefore determined by the combined selection of the parameters ß-phase, Si and P and an optionally present small proportion of Pb.
  • the proportion of the ß-phase in the sum of the a-phase and ß-phase is at least 20% by volume, preferably at least 35% by volume, particularly preferably at least 40% by volume. -%.
  • a high proportion of the ß-phase has a negative effect on ductility. Therefore, the proportion of the ß phase is at most 70% by volume, preferably at most 60% by volume.
  • the Si content of the alloy is 0.15 to 1.2% by weight
  • the P content is 0.20 to 0.38% by weight.
  • up to 0.25% by weight of Pb preferably up to a maximum of 0.10% by weight of Pb, can be added.
  • the proportion of the ß phase and the proportions of Si and P are selected so that the alloy meets the condition
  • the Cu content of the alloy is 58.0 to 66.0% by weight. If the Cu content is less than 58.0% by weight, the ductility of the alloy is too low. If the Cu content is more than 66.0% by weight, the zinc content in the alloy is too low to achieve good machinability.
  • the composition of the alloy can preferably be chosen so that the Si/P ratio is at least 0.6, particularly preferably at least 0.9.
  • the composition of the alloy can be selected such that the sum of Si and P is at least 0.58% by weight, particularly preferably at least 0.64% by weight. Both measures mentioned above contribute both independently and in combination to fulfilling the relationship described above and thus to achieving favorable cutting properties.
  • the optional elements Sn and AI support the formation of the ß-phase. If the Sn content is more than 0.5% by weight, further tin-containing phases can form, which can have a negative effect on the properties of the alloy.
  • the proportion of tin should preferably be at most 0.3% by weight, particularly preferably at most 0.2% by weight.
  • aluminum forms aluminum phosphides with phosphorus. However, these are undesirable, which is why the Al content should not exceed 0.05% by weight.
  • the proportion of iron may be at most 0.3% by weight, preferably at most 0.1% by weight.
  • Nickel supports the formation of the a-phase. Furthermore, nickel forms phosphides, which have no beneficial influence on machinability. Therefore, the proportion of nickel may be at most 0.3% by weight, preferably at most 0.1% by weight.
  • the element Bi is present as an impurity in secondary raw materials such as scrap. It can improve the machinability of the alloy. In amounts up to a maximum of 0.1% by weight, Bi has no negative influence on the alloy. Therefore, up to 0.1% by weight of Bi in the alloy is tolerated.
  • the proportion of Bi is preferably less than 0.015% by weight.
  • Te, Se and In can have a beneficial effect on the machinability of the alloy. In amounts up to a maximum of 0.1% by weight, they have no negative influence on the alloy. Therefore, up to 0.1% by weight of Te, Se and In are tolerated in the alloy. An optional proportion of up to 0.01% by weight boron contributes to grain refinement.
  • the rest of the alloy composition consists of zinc and unavoidable impurities.
  • the proportion of these impurities is a maximum of 0.2% by weight.
  • the proportions of Mn and Mg should preferably be at most 0.1% by weight, particularly preferably at most 0.05% by weight, because these elements can form phosphides that compete with those containing copper and/or zinc Phosphides can occur.
  • the Pb content in the alloy can be at least 0.02% by weight. Even such a small proportion of Pb improves the cutting properties.
  • the ratio of the proportions by weight of P and the sum of Fe and Ni can be more than 2.0, i.e. P/(Fe+Ni) > 2.0. This ensures that predominantly the copper and/or zinc-containing phosphides which are favorable for the cutting properties are formed. The formation of iron phosphides or nickel phosphides is suppressed.
  • the P content can be at least 0.26% by weight and at most 0.33% by weight. If the P content is at least 0.26% by weight, a sufficient number of phosphide particles are formed to produce a particularly fine grain and a very good to achieve machinability.
  • the Si content can be at least 0.50% by weight and at most 1.0% by weight.
  • a cast material made of a copper-zinc alloy with a Si content in this range is characterized by excellent machining properties.
  • a further aspect of the invention relates to a method for producing a cast product, the method comprising the following steps: a) melting a copper-zinc alloy with a composition as described above, b) casting a cast product with subsequent cooling of the cast product, in one Temperature range from 550 to 350 °C, the cooling rate is at least 20 °C per minute and at most 60 °C per minute.
  • a cast product can be produced from a cast material described above from a copper-zinc alloy.
  • Cu cathodes, Zn ingots, brass scraps, Cu-P master alloys and Cu-Si master alloys can be used to melt the alloy. Melting is preferably carried out in an induction furnace. The melt is then poured into a cast product. The cast product is cooled, with the cooling rate being at least 20 °C per minute, preferably at least 30 °C per minute, and at most 60 °C per minute, preferably at most 50 °C per minute, in a temperature range of 550 °C to 350 °C .
  • the defined cooling sets a favorable ratio of the volume fractions of the a-phase and the ß-phase to one another and a favorable particle distribution of copper- and/or zinc-containing phosphides in the cast material of the cast product.
  • a further aspect of the invention relates to a casting made from a casting material described above.
  • a casting refers to a product whose material has not been formed after casting and cooling.
  • the production of a casting is based on a cast product which is melted and cast using the process described above.
  • the cast product is machined to shape it. Furthermore, at least part of the surface can be polished.
  • the casting can be fully or partially coated.
  • the cast part is therefore produced by machining and optional further processing steps from a cast material or cast product described above.
  • Such a casting can be, for example, a connector, a T-piece, part of a valve, a faucet or a water meter.
  • Samples No. 1 to No. 12 were melted in an induction furnace and then cast into small blocks in molds. The cooling rate during solidification was 36 °C per minute (°C/min) in the temperature range from 550 °C to 350 °C.
  • the composition of the samples is documented in Table 1.
  • Sample No. 5 represents the lead-containing reference alloy CuZn39Pb1AI-B.
  • Cross slices were removed from the cast blocks and the microstructure was examined using a light microscope.
  • the specified volume proportions of the a-phase and the ß-phase are normalized to the sum of the a-phase and ß-phase.
  • the hardness HV was determined.
  • the electrical conductivity was determined using an eddy current method using a probe.
  • the grain size of the ß-grains was determined based on EN ISO 2624.
  • line cuts were made in the width direction of the transverse slices (referred to as “vertical”) and the number of cut ß-grains along the line cuts was determined.
  • the average line cut length in the width direction corresponds to the average ß-grain diameter in the width direction.
  • line cuts were made in the thickness direction of the transverse slices (referred to as “horizontal”) and the number of cut ⁇ -grains along these line cuts was determined.
  • the average line cut length in the thickness direction corresponds to the average ß-grain diameter in the thickness direction.
  • the light microscopic images of the unetched samples were used to quantitatively determine the size distribution of the phosphide particles.
  • Image sections measuring 167 pm x 126 pm (corresponding to an area of 21,000 pm 2 ) were selected and evaluated at 1000x magnification using the ImageJ software. In this way it was possible to detect individual particles and determine their equivalent diameter and area. Based on their equivalent diameter, the phosphide particles were divided into the categories 0.5 to 1 pm, 1 to 2 pm, 2 to 5 pm and - if available - larger than 5 pm.
  • the machinability was determined using a planing test. An indexable insert with a contour that promotes chip breakage was used. The depth of cut was 125 pm and the planing speed - I4
  • the chip shape was assigned a chip shape number according to the following list:
  • the chip shape number 1.0 corresponds to the reference alloy CuZn39Pb1AI-B, which
  • Samples No. 1 to No. 4 are samples according to the invention.
  • Samples No. 5 to No. 12 are comparison samples and are marked with (*).
  • f 92, 7249-0, 473254 [Beta]-80, 6378 [Si]-142.65 [P]+279.309-[Si] [P], where f is approximate the measured bending moment is quantified in Nm and where [Beta] denotes the proportion of the ß-phase in % by volume, [Si] denotes the proportion of silicon in % by weight and [P] denotes the proportion of phosphorus in % by weight.
  • Samples No. 1 to No. 4 are samples according to the invention.
  • the volume fraction of the ß phase is at least 38% and at most 57%.
  • the ß grain size is a maximum of 645 pm in the width direction (“vertical”) and a maximum of 781 pm in the thickness direction (“horizontal”).
  • the ratio of ß grain size in the thickness direction to ß grain size in the width direction is a maximum of 1.21.
  • the grains therefore have a topology without a preferred direction and are rated as globular.
  • the hardness is at least 110 HV10.
  • the measured bending moment is a maximum of 36.5 Nm.
  • the shape of the chips corresponds to the chip shape number 1.25 for all samples. The shape of the chips is therefore very favorable.
  • Samples No. 5 to No. 12 are comparative samples.
  • Reference sample No. 5 contains 1.1% by weight of lead and is characterized by a very small grain size, a very low bending moment and a good chip shape.
  • Samples No. 6 and No. 7 contain only very small amounts of silicon and phosphorus in addition to copper and zinc. In both samples, the ß grain size is very large, the bending moment measured during machining is high and the chip shape is poor.
  • Samples No. 8 to No. 11 each contain approximately 0.55 wt% silicon. Samples No. 8 and No. 10 contain no or very little phosphorus, while Samples No. 9 and No. 11 contain phosphorus in an amount of 0.126% by weight and 0.067% by weight, respectively.
  • the zinc content is slightly more than 1% by weight higher than the zinc content of samples No. 8 and No. 9.
  • the larger zinc content leads to a larger volume fraction ß phase.
  • the comparison of samples No. 8 and No. 10 with samples No. 6 and No. 7 shows that by alloying approximately 0.55% by weight of silicon, the bending moment acting during machining is reduced due to the hardening of the a-phase and the ß phase is significantly reduced.
  • the ß-grain size is smaller in samples No. 8 to No. 11 than in samples No. 6 and No. 7.
  • the ß-grain size tends to decrease with increasing P content.
  • Samples No. 8 to No. 11 have a beta grain size larger than the beta grain size of Samples No. 1 to No. 4.
  • the horizontal ß-grain size is larger than the vertical ß-grain size by more than a factor of 1.25, usually even by more than a factor of 2.5, while in samples no. 1 to No. 4 the horizontal ß-grain size is at most a factor of 1.25 larger than the vertical ß-grain size.
  • sample no. 12 Due to the phosphorus content of 0.276% by weight, sample no. 12 shows a globular ß-grain with a vertical ß-grain size of 605 pm and a horizontal ß-grain size of 856 pm. However, sample No. 12 has a volume fraction of the ⁇ phase of only 22% and a low Si content of 0.277 wt%, which increases the bending moment acting during machining and the condition
  • the samples No. 1 to No. 4 are characterized by grains with a topology without a preferred direction, i.e. globular grains, and with a ß-grain size of a maximum of 800 pm, while in the samples No. 8 to No. 11 the ß- Grain size is generally larger.
  • the ß grain size in the thickness direction (“horizontal”) is significantly larger than in the width direction (“vertical”). Therefore, the grain formation in samples No. 8, No. 10 and No. 11, as in samples No. 6 and No. 7, is described as stalky and rated as unfavorable. The reason for the favorable topology and size of the grains in samples No. 1 to No.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Conductive Materials (AREA)
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Abstract

L'invention concerne un matériau de coulée fait d'un alliage de cuivre-zinc ayant la composition suivante en % en poids : Cu : 58,0 à 66,0 %, Si : 0,15 à 1,2 %, P: 0,20 à 0,38 %, Sn : facultativement jusqu'à 0,5 %, Al : facultativement jusqu'à 0,05 %, Fe : facultativement jusqu'à 0,3 %, Ni : facultativement jusqu'à 0,3 %, Pb : facultativement jusqu'à 0,25 %, Bi : facultativement jusqu'à 0,1 %, Te, Se, In, chacun facultativement jusqu'à 0,1 %, B : facultativement jusqu'à 0,01 %, le reste étant Zn et les impuretés inévitables, la proportion d'impuretés inévitables étant inférieure à 0,2 % en poids. L'alliage a une structure de phase α, de phase β et des particules de phosphure. La proportion de phase β dans la somme de la phase α et de la phase β est d'au moins 20 % en volume et d'au maximum 70 % en volume. Le silicium est présent à la fois dans la phase α et dans la phase β. Dans une surface de 21000 µm2, il y a 20 à 300 particules de phosphure ayant un diamètre équivalent de 0,5 à 1 µm, 30 à 120 particules de phosphure ayant un diamètre équivalent de 1 à 2 µm, et 20 à 100 particules de phosphure ayant un diamètre équivalent de 2 à 5 µm. La proportion de phase β et les proportions de Si et de P sont choisies de telle sorte que la condition 92, 7249-0, 473254 [Bêta] -80,6378 [Si] -142,65 [P] +279, 309 [Si] [P] < 40 est satisfaite, [Bêta] représentant la proportion de phase β en % en volume, [Si] représentant la proportion de silicium en % en poids et [P] représentant la proportion de phosphore en % en poids.
EP23764232.7A 2022-08-11 2023-08-02 Matériau de coulée fait d'un alliage de cuivre-zinc, procédé de fabrication d'un produit coulé et pièce coulée Pending EP4569148A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102022002928.6A DE102022002928B4 (de) 2022-08-11 2022-08-11 Knetwerkstoff aus einer Kupfer-Zink- Legierung, Halbzeug aus einemKnetwerkstoff und Verfahren zur Herstellung von solchem Halbzeug
PCT/EP2023/000052 WO2024032925A1 (fr) 2022-08-11 2023-08-02 Matériau de coulée fait d'un alliage de cuivre-zinc, procédé de fabrication d'un produit coulé et pièce coulée

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EP4569148A1 true EP4569148A1 (fr) 2025-06-18

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EP23751540.8A Pending EP4569146A1 (fr) 2022-08-11 2023-07-20 Alliage de cuivre-zinc corroyé, produit semi-fini formé d'un alliage de cuivre-zinc corroyé et procédé de production d'un produit semi-fini de ce type
EP23764232.7A Pending EP4569148A1 (fr) 2022-08-11 2023-08-02 Matériau de coulée fait d'un alliage de cuivre-zinc, procédé de fabrication d'un produit coulé et pièce coulée

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EP23751540.8A Pending EP4569146A1 (fr) 2022-08-11 2023-07-20 Alliage de cuivre-zinc corroyé, produit semi-fini formé d'un alliage de cuivre-zinc corroyé et procédé de production d'un produit semi-fini de ce type

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EP (2) EP4569146A1 (fr)
JP (2) JP2025527197A (fr)
KR (1) KR20250047661A (fr)
CN (2) CN119630824A (fr)
CA (2) CA3261021A1 (fr)
DE (1) DE102022002928B4 (fr)
MX (2) MX2024015900A (fr)
TW (1) TW202407110A (fr)
WO (2) WO2024032923A1 (fr)

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EP4569146A1 (fr) 2025-06-18
CN119630824A (zh) 2025-03-14
JP2025527197A (ja) 2025-08-20
CA3261007A1 (fr) 2025-04-07
WO2024032925A1 (fr) 2024-02-15
DE102022002928A1 (de) 2024-02-22
CA3261021A1 (fr) 2025-04-07
DE102022002928B4 (de) 2024-04-25
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CN119585454A (zh) 2025-03-07
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TW202407110A (zh) 2024-02-16
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