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EP3649266B1 - Alliage de zinc corroyé contenant du titane - Google Patents

Alliage de zinc corroyé contenant du titane Download PDF

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Publication number
EP3649266B1
EP3649266B1 EP18742945.1A EP18742945A EP3649266B1 EP 3649266 B1 EP3649266 B1 EP 3649266B1 EP 18742945 A EP18742945 A EP 18742945A EP 3649266 B1 EP3649266 B1 EP 3649266B1
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EP
European Patent Office
Prior art keywords
weight
content
zinc
alloy according
wrought alloy
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.)
Active
Application number
EP18742945.1A
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German (de)
English (en)
Other versions
EP3649266A1 (fr
Inventor
Jan HÜTTIG
Armin Melzer
Frank Prenger
Didier Rollez
Markus VAN WESEL
Joanna VON KRIES
Jürgen Wisniewski
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.)
Grillo Werke AG
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Grillo Werke AG
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Publication date
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Priority to PL18742945T priority Critical patent/PL3649266T3/pl
Publication of EP3649266A1 publication Critical patent/EP3649266A1/fr
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Publication of EP3649266B1 publication Critical patent/EP3649266B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon

Definitions

  • the present invention relates to a zinc wrought alloy with improved machinability as compared to known wrought alloys, as well as semifinished products, forgings, turned parts, locks, screw connections, locking cylinders, sleeves, fittings, pressed parts, pneumatic parts, hydraulic parts, mountings, valves and ball valves that comprise a zinc wrought alloy according to the invention.
  • machinability i.e., the property of a material to be processable by machining
  • lead such as free-machining brass, CuZn39Pb3.
  • EP 2675971 A “Accessory consisting of a lock accessory” may be mentioned. It discloses a zinc alloy with an Al content of from 13 to 25%, a Cu content of from 0.2 to 3.5%, and an Mg content of less than 0.1%, which is employed for lock accessories.
  • EP 2 385 148 A - "Zinc alloy with high creep resistance” relates to a zinc-aluminum alloy with an Al content of 10 to ⁇ 25%, a Cu content of 0.05 to 3%, an Mg content of from 0.001 to 0.1%, an Mn content of 0.05% to 1.0% and an Si content of from 0.05 to 1%.
  • the disclosed alloy has a high creeping resistance and is suitable for the furnace brazing and normal brazing of heat exchangers.
  • US 3,734,785 - "Zinc forging alloy” claims a zinc-based alloy with an Al content of 9 to 22%, a Cu content of 0.5 to 1.5%, and an Mg content of 0.01 to 0.03%, which is particularly suitable for hot formability.
  • EP 0 679 198 A "Method for producing Zn-Al-Cu alloy articles by centrifugal or die casting” describes a zinc alloy with an Al content of 6.0 to 8.0%, a Cu content of 3.2 to 4.3%, for preparing articles by centrifugal casting in a rubber mold, or pressure die-casting in a metal mold.
  • ZAMAK® zinc pressure die-casting alloys
  • ZAMAK® zinc pressure die-casting alloys
  • the object of the present invention is achieved by a zinc wrought alloy having an Al content of from 5% by weight to 18% by weight, a Cu content of from 0.1% by weight to 4% by weight, an Mg content of from 0.001% by weight to 0.05% by weight, a Ti content of from 0.01% by weight to 1% by weight, wherein Zn is the balance to 100%, and wherein the alloy may contain impurities at a proportion of 0.07% by weight or less.
  • Titanium is an extremely effective alloy element, strongly affecting the microstructure already in the ppm range because of its lattice structure. With it, a better machinability can be achieved. At the same time, the mechanical properties of the alloy are not adversely affected. Further, the zinc alloy according to the invention has very good hot formability properties.
  • the machining index could be brought into the reference range of free-machining brass (CuZn39Pb3) by alloying with titanium, but without having to alloy with lead.
  • CuZn39Pb3 free-machining brass
  • processing may be dry or wet. Alloying with lead is not necessary.
  • lead is not alloyed.
  • Preferred is a Pb content in the alloy according to the invention of ⁇ 0.003% by weight, especially ⁇ 0.003% by weight, which is present in the alloy as an impurity of zinc, in particular, but not as an additional alloy component.
  • the microstructure fineness of grain
  • the proportion of titanium (Ti) in the alloy according to the invention is preferably from 0.01% to 1% by weight, especially from 0.03% to 1% by weight, specifically from 0.05% to 1% by weight, preferably from 0.06% to 1% by weight. It has been found that these proportions of titanium are sufficient to achieve the improved properties. Larger amounts are not necessary and also can be introduced only with difficulty without adversely affecting the microstructure of the alloy. Particularly preferred is a Ti content of from 0.05% to 1% by weight.
  • the alloy according to the invention may also comprise impurities resulting from the fact that these components (Zn, Al, Cu, Mg, Ti) are derived from recycling.
  • these components are not critical.
  • Common impurities are Cd, Pb, Sn and/or Fe.
  • these impurities are contained only in very small amounts, so that they do not affect the properties of the alloy according to the invention.
  • the content of all stated impurities is below the mentioned values.
  • the content of all impurities is 0.07% by weight or less.
  • the alloys according to the invention are suitable for surface treatments (for example, electroplating, PVD, CVD, passivation, painting, cathodic dip painting/coating, powder coating).
  • a zinc wrought alloy with a content of aluminum (Al) of from 5 % by weight to 18 % by weight, especially from 8% to 18% by weight, preferably from 10% to 16% by weight, more preferably from 5 % to 9% by weight, preferably from 10% to 12% by weight, more preferably from 14% to 16% by weight, especially from 16% to 18% by weight.
  • Al aluminum
  • These ranges are preferred because all alloys are supereutectic therein, and there is a first beta phase in the crystal structure. This beta phase is preferred because it recrystallizes at room temperature very slowly (> 10 years), so that the properties of the alloy are retained.
  • a zinc wrought alloy with a content of copper (Cu) of from 0.1% to 2.5% by weight, especially from 0.5 to 1.5% by weight. This range is preferred to achieve the maximum mechanical strength, and to avoid the risk of forming of a brittle epsilon phase in the crystal structure.
  • a zinc wrought alloy with a content of magnesium (Mg) of from 0.003 % by weight to 0.05 % by weight, especially from 0.003% to 0.03% by weight. This range serves as a precaution to prevent intercrystalline corrosion by the residual traces of impurities.
  • the titanium content of at most 1% in the zinc alloy is limited by the solubility of titanium.
  • the zinc wrought alloy according to the invention may further contain silicon as an impurity. If it contains silicon, the content of silicon in the alloy is within a range of from 0.005% by weight to 0.02% by weight, in particular. The silicon content is determined by the selection of Al, because silicon is an impurity in aluminum.
  • an alloy having an Al content of from 10% to 12% by weight, a Cu content of from 0.5% by weight to 1.5% by weight, an Mg content of from 0.003% by weight to 0.05% by weight, a Ti content of from 0.05% to 1% by weight, with zinc as the balance to reach 100% by weight has particularly good properties with respect to machinability. At the same time, mechanical properties, such as strength or hardness, are not adversely affected. Therefore, such an alloy is preferred.
  • Particularly preferred according to the invention is a zinc wrought alloy with an Al content of from 14% to 16% by weight, a Cu content of from 0.5% by weight to 1.5% by weight, an Mg content of from 0.003% by weight to 0.05% by weight, a Ti content of from 0.05% to 1% by weight, with zinc as the balance to reach 100% by weight.
  • Corresponding alloys have good properties with respect to machinability and in addition have a good processability.
  • mechanical properties of the alloy such as strength or hardness, are not adversely affected.
  • the present invention further relates to the use of the titanium-containing zinc wrought alloy according to the invention for preparing semifinished products and articles with improved machining properties.
  • a semifinished product or article obtainable by processing the zinc wrought alloy according to the invention.
  • This semifinished product may be, in particular, a billet, an extruded section, a drawn section, a wire, a strip, a powder, or a pressure die-cast alloy.
  • the article may be a forging, turned part, lock, screw connection, locking cylinder, sleeve, fitting, pressed part, pneumatic part, hydraulic part, mounting, valve or ball valve.
  • the semifinished product according to the invention can be prepared, for example, by casting the zinc wrought alloy according to the invention into a mold.
  • a section can be prepared therefrom by reshaping by means of extrusion.
  • the zinc wrought alloy according to the invention can be processed by different reshaping methods. Such reshaping methods include, in particular, rolling, forging, drawing.
  • the articles according to the invention are excellently suitable for being subjected to machining methods.
  • the zinc wrought alloy according to the invention and the articles prepared therefrom exhibit an improved machinability as compared to conventional ZnAI/ZnAICu/ZnAICuMg alloys.
  • the requirement for the invention is to enhance the processability of zinc wrought alloys. This object was achieved by alloying with titanium. There may be mentioned, in particular, the machining properties that were significantly improved thereby, so that a machining index within the reference range of free-machining brass (CuZn39Pb3) can be achieved. In the experiments, it is found that the titanium content leads to ideal chip shapes. Surprisingly, increased cutting speeds could be achieved additionally, which significantly enhances productivity.
  • the prepared products made of the titanium-containing zinc wrought alloy according to the invention are more cost-effective than comparably lead-free brass materials. This results from a lower density and an excellent processability caused by the optimum composition of zinc, aluminum, copper, magnesium and titanium.
  • the zinc wrought alloy according to the invention was compared with the following materials: Table 1: Comparative material (comparative experiments) Properties Unit Zinc alloy Aluminum content % by weight 13-25 Copper content % by weight 0.2-3.5 Magnesium content % by weight ⁇ 0.1 Lead content % by weight ⁇ 0.004 Zinc content % by weight balance Tensile strength MPa 412 Yield strength MPa 374 Brinell hardness HB (2.5/62.5) 128 Creep tendency (A f RT 100.1 ) % 0.05
  • a zinc wrought alloy as described in EP 2 675 971 was used as a comparative material (information in column “zinc alloy” in Table 1).
  • the qualification of the zinc wrought alloy according to the invention is based on four methods delimited from one another, which are set forth in the following. They are the basis of the determination of the claimed composition boundaries. If one of the compositions showed defects, this led to exclusion.
  • the billet was heated at 250 °C in an oven. Thereafter, the billet was extruded into a round section. Further, the extruded round rod was drawn to a final dimension of 26 mm. The testing requirements were considered to be met if no signs of surface cracks or blisters have formed.
  • a section of the drawn round rod having a diameter of 26 mm was lathe-turned into a specimen for tensile testing as shown in Figure 1 . It was clamped into the tensile testing machine and exposed to a uniaxial load until the specimen broke. Meanwhile, the force, width and length were continuously measured electronically, whereby the stress-strain curve ( Figure 2 ) could be determined.
  • a section of the drawn round rod was clamped into a turning machine.
  • a turned part having rotational symmetry with five recessed grooves having widths of 3 mm and depths of 3 mm was prepared therefrom. The testing requirements were considered to be met if the chip shape corresponds to industrial custom.
  • Photographs of the chip shapes and the specimens that were processed are shown in Figure 4 . At a medium cutting speed, all the specimens showed a good machinability. Both spiral chips and conical helical chips were produced.
  • Table 7 shows the results of the mechanical properties of the specimens (results of methods 2 and 3).
  • Table 7 Mechanical properties of the specimens with different titanium contents (methods 2 and 3)
  • Properties Unit Specimen 3a Specimen 3 Specimen 3b Specimen 3c Tensile strength MPa 401 411 409 410 Yield strength (R p0.2 ) MPa 365 372 370 369 Brinell hardness HB (2.5/62.5) 129 132 133 131 Creep tendency (A f RT 100.1 ) % 0.03 0.05 0.04 0.04
  • the titanium content in different amounts does not show any negative impact on the mechanical properties.
  • the alloy 3 according to the invention was compared with the comparative material from EP 2 657 971 .
  • the zinc alloy according to the invention achieved chip shapes that are better for turning processing as compared to those obtained with the comparative zinc alloy as described in EP 2 675 971 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Forging (AREA)

Claims (15)

  1. Alliage de corroyage de zinc, ayant une teneur en Al de 5 % en poids à 18 % en poids, une teneur en Cu de 0,1 % en poids à 4 % en poids, une teneur en Mg de 0,001 % en poids à 0,05 % en poids, une teneur en Ti de 0,01 % en poids à 1 % en poids, dans lequel Zn est le complément jusqu'à 100 % en poids, et dans lequel ledit alliage peut contenir des impuretés en une teneur de 0,07 % en poids ou moins.
  2. Alliage de corroyage de zinc selon la revendication 1, caractérisé en ce qu'on n'ajoute pas de plomb dans l'alliage.
  3. Alliage de corroyage de zinc selon la revendication 1 ou 2, caractérisé en ce que la teneur en Al est de 8 % à 16 % en poids, de préférence de 10 % à 14 % en poids, de préférence de 10 % à 12 % en poids, ou de 14 % à 16 % en poids.
  4. Alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la teneur en Ti est de 0,03 % à 1 % en poids, de préférence de 0,05 % à 1 % en poids, notamment de 0,06 % à 1 % en poids.
  5. Alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la teneur en Cu est de 0,1 % à 2,5 % en poids, notamment de 0,5 % à 1,5 % en poids.
  6. Alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la teneur en Mg est de 0,003 % à 0,05 % en poids, notamment de 0,003 % à 0,03 % en poids.
  7. Alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'il contient du silicium comme impureté, notamment avec une teneur de 0,005 % à 0,02 % en poids.
  8. Alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 7, ayant une teneur en Al de 5 % à 9 % en poids, une teneur en Cu de 0,5 % à 2,5 % en poids ou de 0,5 % à 1,5 % en poids, une teneur en magnésium de 0,003 % à 0,05 % en poids, une teneur en titane de 0,05 % à 1 % en poids, dans lequel Zn est le complément jusqu'à 100 %.
  9. Alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 7, ayant une teneur en Al de 10 % à 12 % en poids, une teneur en Cu de 0,5 % à 2,5 % en poids ou de 0,5 % à 1,5 % en poids, une teneur en Mg de 0,003 % à 0,05 % en poids, une teneur en Ti de 0,05 à 1 % en poids, dans lequel Zn est le complément jusqu'à 100 %.
  10. Alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 7, ayant une teneur en Al de 14 % à 16 % en poids, une teneur en Cu de 0,5 % à 2,5 % en poids ou de 0,5 % à 1,5 % en poids, une teneur en Mg de 0,003 % à 0,05 % en poids, une teneur en Ti de 0,05 à 1 % en poids, dans lequel Zn est le complément jusqu'à 100 %.
  11. Alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 7, ayant une teneur en Al de 16 % à 18 % en poids, une teneur en Cu de 0,5 % à 2,5 % en poids ou de 0,5 % à 1,5 % en poids, une teneur en magnésium de 0,001 % à 0,05 % en poids, une teneur en titane de 0,05 à 1 % en poids, dans lequel Zn est le complément jusqu'à 100 %.
  12. Utilisation de l'alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 11 pour préparer des produits et/ou articles semi-finis.
  13. Utilisation selon la revendication 12, dans lequel ledit produit semi-fini est un boulon, un profilé extrudé, un profilé pultrudé, un fil, une bande, une poudre, ou un alliage moulé sous pression,
    et/ou
    dans lequel ledit article est une pièce forgée, une pièce tournée, une fermeture, un raccord vissé, un cylindre de fermeture, un manchon, un raccord, une pièce moulée, une pièce pneumatique, une pièce hydraulique, une garniture, une vanne, ou une vanne à boule.
  14. Produits semi-finis, pièces forgées, pièces tournées, fermetures, raccords vissés, cylindres de fermeture, manchons, raccords, pièces moulées, pièces pneumatiques, pièces hydrauliques, garnitures, vannes, et vannes à boule, caractérisés en ce qu'ils comprennent, notamment consistent en, un alliage de corroyage de zinc selon l'une quelconque des revendications 1 à 11.
  15. Procédé pour préparer et/ou former et/ou traiter des produits semi-finis, pièces forgées, pièces tournées, fermetures, raccords vissés, cylindres de fermeture, manchons, raccords, pièces moulées, pièces pneumatiques, pièces hydrauliques, garnitures, vannes, et vannes à boule, caractérisés en ce qu'ils comprennent, notamment consistent en, un alliage de corroyage de zinc selon la revendication 14 par formage à froid ou à chaud.
EP18742945.1A 2017-07-04 2018-07-02 Alliage de zinc corroyé contenant du titane Active EP3649266B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL18742945T PL3649266T3 (pl) 2017-07-04 2018-07-02 Przerabialny plastycznie stop cynku zawierający tytan

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17179643 2017-07-04
PCT/EP2018/067808 WO2019007906A1 (fr) 2017-07-04 2018-07-02 Alliage corroyé de zinc contenant du titane

Publications (2)

Publication Number Publication Date
EP3649266A1 EP3649266A1 (fr) 2020-05-13
EP3649266B1 true EP3649266B1 (fr) 2021-01-27

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US (1) US20210140014A1 (fr)
EP (1) EP3649266B1 (fr)
PL (1) PL3649266T3 (fr)
PT (1) PT3649266T (fr)
WO (1) WO2019007906A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117305655A (zh) * 2023-09-25 2023-12-29 中国航发南方工业有限公司 锌铝铅合金材料及其制备方法与应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA919458A (en) 1969-12-31 1973-01-23 Cominco Ltd. Zinc forging alloy
FR2102861A5 (en) * 1970-08-26 1972-04-07 Nisso Smelting Co Ltd Compression - resistant zinc alloys - contg aluminium, copper, magnes beryllium, titanium optionally silver
US3880679A (en) 1971-07-21 1975-04-29 Noranda Mines Ltd Method of forming zinc-aluminum alloys with good machinability
FR2700343B1 (fr) 1993-01-14 1995-03-17 France Sa Union Miniere Procédé de fabrication d'articles en alliage Zn-Al-Cu par coulée centrifuge ou coulée sous pression.
PT2385148T (pt) 2010-05-03 2017-01-12 Grillo-Werke Ag Liga de zinco com elevada resistência ao deslizamento
ITMI20110218A1 (it) 2011-02-15 2012-08-16 Almar S P A Accessorio costituito da serratura o simile
KR101963809B1 (ko) 2012-04-25 2019-03-29 삼성전자주식회사 이미지 센서 패키지

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Publication number Publication date
WO2019007906A1 (fr) 2019-01-10
US20210140014A1 (en) 2021-05-13
EP3649266A1 (fr) 2020-05-13
PT3649266T (pt) 2021-02-08
PL3649266T3 (pl) 2021-12-27

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