EP3099832A2 - Laiton présentant une meilleure résistance à la dézincification et une meilleure usinabilité - Google Patents

Laiton présentant une meilleure résistance à la dézincification et une meilleure usinabilité

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Publication number
EP3099832A2
EP3099832A2 EP15709371.7A EP15709371A EP3099832A2 EP 3099832 A2 EP3099832 A2 EP 3099832A2 EP 15709371 A EP15709371 A EP 15709371A EP 3099832 A2 EP3099832 A2 EP 3099832A2
Authority
EP
European Patent Office
Prior art keywords
weight
brass alloy
alloy according
brass
balance
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.)
Granted
Application number
EP15709371.7A
Other languages
German (de)
English (en)
Other versions
EP3099832B1 (fr
Inventor
Jan Nilsson
Cato MARTINSEN MERELID
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.)
Nordic Brass Gusum AB
IMI Hydronic Engineering AB
Original Assignee
Nordic Brass Gusum AB
IMI Hydronic Engineering AB
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
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Application filed by Nordic Brass Gusum AB, IMI Hydronic Engineering AB filed Critical Nordic Brass Gusum AB
Publication of EP3099832A2 publication Critical patent/EP3099832A2/fr
Application granted granted Critical
Publication of EP3099832B1 publication Critical patent/EP3099832B1/fr
Revoked legal-status Critical Current
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002—Castings of light metals
    • B22D21/005—Castings of light metals with high melting point, e.g. Be 1280 degrees C, Ti 1725 degrees C
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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

  • the present invention concerns an essentially arsenic-free brass alloy with improved dezincification resistance, protection against intergranular grain boundary corrosion, and machinability.
  • Brass is a material the basic components of which are copper (Cu) and zinc (Zn).
  • alloying materials such as lead (Pb), iron (Fe), aluminium (Al), nickel (Ni), manganese (Mn), silicon (Si), the brass can be given unique properties, and there are many different brass alloys adapted to different types of processing and final products.
  • Pb lead
  • Fe iron
  • Al aluminium
  • Ni nickel
  • Mn manganese
  • Si silicon
  • the brass will consist of different so-called phases, which are microstructure components.
  • the usual phases of brass are the a-phase, which is rich in copper and the ⁇ -phase, which is rich in zinc.
  • brass consists of a mixture of these two phases.
  • a solid solution having a uniform brass composition is formed when up to about 35 % by weight of zinc is added to copper.
  • a further increase of the content of zinc gives a mixture of the original solid solution (the a-phase) and a new solid solution having a higher content of zinc (the ⁇ -phase).
  • Brass containing between 35-45 % by weight of zinc consists of mixtures of these two phases and is called ⁇ - ⁇ -brass or duplex brass, the relationship between the a-phase to the ⁇ -phase depending primarily on the content of zinc.
  • ⁇ -phase in ⁇ - ⁇ -brass gives a decreased cold ductility but a considerably increased susceptibility to hot working by extrusion or punching and casting without thermal cracks, also when lead is present.
  • ⁇ - ⁇ -alloys have better mechanical properties and, since they contain a higher share of zinc, they are in certain cases more inexpensive than a- brass.
  • ⁇ - ⁇ -brass alloys have a higher sensitivity to dezincification.
  • Dezincification is a type of corrosion where zinc selectively is attacked and leaves a porous copper structure.
  • Dezincification resistant brass has a relatively high Cu content, above 60 %, and contains an inhibitor such arsenic (As), antimony (Sb), or phosphorus (P), which makes the a- phase of the brass resistant to dezincification.
  • Brass alloys may in addition to dezincification be subjected to intergranular grain boundary corrosion, which is a form of corrosion taking place along the grain boundaries.
  • intergranular grain boundary corrosion is a form of corrosion taking place along the grain boundaries.
  • the content of zinc is higher at the grain boundaries of brass alloys and intergranular grain boundary corrosion attacks just at the zinc present along the grain boundaries. Thereby, there is also a need of protecting brass alloys against intergranular grain boundary corrosion.
  • the American Academy of Sciences has estimated the lifetime risk of cancer to 1- 3 cases per 1000 individuals at a daily intake of 1 I of drinking water having arsenic contents at the threshold level of 10 pg/l, which exceeds the low-risk level (approx. one case per 100 000 exposed) that could be considered to be an acceptable risk of an individual environmental factor [3]. As with other carcinogenic substances, the risk of health effects decreases at decreased exposure.
  • the threshold for arsenic in drinking water is 10 g/l within the EU.
  • the threshold for arsenic in drinking water in Sweden 10 g/l, is based on the cancer risk [3].
  • Lifetime risk of the genesis of cancer at a daily intake of arsenic corresponding to the threshold in drinking water (10-20 g arsenic per day depending on age, climate and physical activity), has been estimated to 1 -3 per 1 000 individuals (0.1-0.3 %).
  • lead in drinking water has contributed to high exposure. Lead may damage the nervous system already at very low doses [3.4]. The immature nervous system is particularly sensitive.
  • the lead content of blood may be set in relation to the health risk.
  • symptoms as degraded intellectual capacity, delayed development, and behaviour disorders have been possible to be demonstrated in children who have been exposed during the foetal stage and the infant ages.
  • the object of the present invention is to provide an essentially arsenic-free ⁇ - ⁇ - brass alloy.
  • the object is furthermore that the brass alloy has improved dezincification resistance than brass alloys with arsenic or solely arsenic.
  • the object is furthermore to provide a brass alloy having similar or better protection against intergranular grain boundary corrosion than brass alloys with arsenic or solely arsenic.
  • the object is furthermore that the lead content of the brass alloy should be ⁇ 1 .0 % by weight, preferably ⁇ 0.10 % by weight of Pb.
  • the object is furthermore that the content of the ⁇ -phase is ⁇ 5 %, preferably ⁇ 1 %.
  • the invention concerns an essentially arsenic-free ⁇ - ⁇ -brass alloy with improved (i) dezincification resistance, (ii) machinability, and (iii) protection against intergranular grain boundary corrosion.
  • the essentially arsenic-free brass alloy comprises 62-68 % by weight of Cu, 0.02-1 .00 % by weight of Pb, ⁇ 0.02 % by weight of As, and/or 0.01-0.06 % by weight of P and/or 0.01-0.06 % by weight of Sb (antimony), and balance Zn.
  • Said brass alloy is characterized in that it comprises ⁇ 5 % of ⁇ -phase, preferably ⁇ 1 %. Since only the a-phase can be stabilized, it is important to minimize the content of ⁇ -phase to ⁇ 5 % of ⁇ -phase, preferably ⁇ 1 %, with the purpose of counteracting dezincification and
  • the essentially arsenic-free brass alloy comprises 62-68 % by weight of Cu, 0.02-1 .00 % by weight of Pb, ⁇ 0.02 % by weight of As, and/or 0.01-0.06 % by weight of P and/or 0.01-0.06 % by weight of Sb, and balance Zn, the brass alloy being produced by means of a method comprising the steps of:
  • the cast brass alloy being heat-treated at 500 °C to 550 °C for 1-2 h.
  • the essentially arsenic-free brass alloy has been characterized by the method of producing it (product-by-process) in combination with other determinations of the alloy since it is difficult to define the technical features of the alloy in another way, i.e., it is partly thanks to heat treatment that the alloy obtains improved (i) dezincification resistance and (ii) protection against intergranular grain boundary corrosion.
  • the essentially arsenic-free brass alloy comprises 63.0-64.0 % by weight of Cu, 0.02-1 .00 % by weight of Pb, and/or 0.02-0.06 % by weight of P, 0.02-0.06 % by weight of Sb, and balance Zn.
  • the somewhat higher amount of Pb gives a certain improved machinability.
  • the essentially arsenic-free brass alloy comprises 63.0-64.0 % by weight of Cu, 0.80-1 .00 % by weight of Pb, 0.02-0.06 % by weight of P, 0.02-0.06 % by weight of Sb, and balance Zn.
  • the somewhat higher amount of Pb gives a certain improved machinability.
  • the essentially arsenic-free brass alloy comprises also 0.07-0.12 % by weight of Fe and 0-0.05 % by weight or 0.45-0.70 % by weight of Al.
  • the presence of Fe and Al in the brass alloy entails a certain increased hardness, strength, and tensile strength.
  • the essentially arsenic-free brass alloy comprises 63.5 % by weight of Cu, 35.0 % by weight of Zn, 0.9 % by weight of Pb, 0.10 % by weight of Fe, 0.50 % by weight of Al, 0.02-0.06 % by weight of P, 0.02- 0.06 % by weight of Sb. Alloying additives such as Fe and Al improve strength, hardness, and tensile strength. The content of P and Sb of 0.02-0.06 % by weight each gives protection against dezincification and intergranular grain boundary corrosion.
  • the essentially arsenic-free brass alloy comprises 63.5 % by weight of Cu, 35.0 % by weight of Zn, 0.9 % by weight of Pb, 0.10 % by weight of Fe, 0.50 % by weight of Al, 0.03 % by weight of P, and 0.03 % by weight of Sb.
  • the content of P and Sb of 0.03 % by weight each gives better protection against dezincification and intergranular grain boundary corrosion and approx. 10 % lower cutting forces.
  • the essentially arsenic-free brass alloy comprises 0-0.200 % by weight of Ni, 0-0.100 % by weight of Mn, 0-0.02 % by weight of Si, 0-0.002 % by weight of As and/or 0.0004-0.0006 % by weight of B (boron), preferably 0.0005 % by weight of B.
  • Nickel improves corrosion resistance, hardness, and tensile strength without significant effect on ductility, which gives improved properties at elevated temperatures.
  • Mn entails a certain increased hardness, strength, and tensile strength.
  • Si increases the strength, workability, and the resistance to wear.
  • the content of As and B is acceptable contents of inevitable impurities in the alloy.
  • the brass alloy comprises 62-68 % by weight of Cu, 0.02-1 .00 % by weight of Pb, 0.01 % by weight of As, 0.02 % by weight of Sb, and balance Zn.
  • the brass alloy comprises 62-68 % by weight of Cu, 0.02-1 .00 % by weight of Pb, 0.01 % by weight of As, 0.02 % by weight of Sb, 0.015 % by weight of P, and balance Zn.
  • the essentially arsenic-free brass alloy according to the present application is produced by the steps of:
  • the cast brass alloy being heat-treated at 500 °C to 550 °C for 1-2 h.
  • the essentially arsenic-free brass alloy is produced by heat treating at 550 °C for 2 h, which lowers the amount of ⁇ -phase to ⁇ 5 %, preferably ⁇ 1 %, as well as that the alloying additive P lowers the cutting forces to approx. 10 % lower cutting forces.
  • Figure 1 The microstructure of both cast and heat-treated test alloy 10 is illustrated. All pictures are taken using optical light microscopy. The first row is with 200* magnification and the second row is 500* magnification.
  • the present invention concerns an essentially arsenic-free brass alloy with improved (i) dezincification resistance, (ii) machinability, and (iii) protection against intergranular grain boundary corrosion, wherein said brass alloy comprises 62-68 % by weight of Cu, 0.02-1 .00 % by weight of Pb, ⁇ 0.02 % by weight of As, 0.01- 0.06 % by weight of P and/or 0.01-0.06 % by weight of Sb, and balance Zn, and the brass alloy being characterized by it comprising ⁇ 5 % of ⁇ -phase, preferably ⁇ 1 %.
  • the brass alloy according to the present invention may also comprise alloying additives such as Fe, Al, Ni, Mn, and Si with the purpose of improving strength, wear resistance, and/or tensile strength.
  • alloying additives such as Fe, Al, Ni, Mn, and Si with the purpose of improving strength, wear resistance, and/or tensile strength.
  • the presence of Fe, Mn, and Al in the brass alloy entails a certain increased hardness, strength, and tensile strength.
  • Si increases the strength and the resistance to wear of the brass alloy.
  • Nickel improves hardness and tensile strength without significant effect on ductility, which gives improved properties at elevated temperatures.
  • Other elements such as B, Bi, Mg, Cr, and As may also be present in the brass alloy as inevitable impurities.
  • the brass alloy according to the present application comprises ⁇ 0.02 % by weight of As.
  • the brass alloy comprises ⁇ 0.02 % by weight of As, i.e., that As is present as an inevitable impurity.
  • the brass alloy according to the present invention is produced by a method comprising the steps of
  • the cast brass alloy being heat-treated at 500 °C to 550 °C for 1-2 h, the heat treatment preferably taking place at 550 °C for 2 h.
  • a brass alloy comprising ⁇ 5 % of ⁇ -phase, preferably ⁇ 1 % of ⁇ -phase, which gives improved dezincification resistance and protection against intergranular grain boundary corrosion.
  • the present invention indicates furthermore that in the presence of Al or Fe, P does not act as inhibitor against dezincification but instead P results in lower cutting forces, which is an unexpected technical effect (see Example 1 ).
  • Sb and the heat treatment at 550 °C for 2 h promotes that the ⁇ -zones are not continuous, which in turn promotes protection against intergranular grain boundary corrosion
  • the following examples are there to illustrate a preferred embodiment and do not thereby exclude other brass alloys with both a- and ⁇ -phases falling within the scope of protection of the claims according to the present invention.
  • the example also comprises comparative experiments (with the purpose of demonstrating technical effect) between brass alloys containing different combinations of As, Sb, and/or P.
  • Test alloys 1-1 1 which were tested in the present application, were produced by using a base alloy having the prototype name 752 wherein the content of As, Sb, and P is as close to zero as possible.
  • the chemical composition of 752 is given in Table 1 in % by weight wherein "NBG standard value” indicates the chemical composition of the base alloy desired to be achieved while “Min” and “Max” gives the tolerances.
  • the measured composition of the base alloy is also given.
  • Table 1 Minimum, maximum, and standard values for 752 and chemical analysis of the base alloy
  • test alloys were produced in the form of ingots of 2 kg by adding As, Sb, and/or P to the base alloy in a furnace (Leybold) where the alloys were melted in a melting-pot (Morgan crucible), which had been placed in an inductance coil. The alloys were melted in the presence of air by means of ventilation above the furnace and the smelt was then poured into a mould by tipping the melting-pot together with the coil. The dimension of the mould was 40x40 mm (height, 300 mm). Test alloys with different combinations of As, Sb, and/or P tested are given in Table 2.
  • Table 2 The content of As, P, and Sb of the test alloys 1-1 1 indicated in % by weight.
  • the "Analysed” contents indicate the measured % by weight while the “Planned” contents indicate the contents desired to achieve in the test alloys.
  • the chemical composition of the test alloys is presented in Table 3 wherein also inevitable impurities such as B, Bi, Mg, and Cr have been included in the table.
  • Table 3 The chemical composition of the test alloys in % by weight.
  • test alloys 1-1 1 are exposed to corrosion in the form of both cast and heat- treated sample plates. Said heat treatment was made at 550 °C for 2 h, and after removal from the furnace, the samples were quickly quenched in water (with a delay of up to 5 min). As has been indicated previously, the purpose of the heat treatment is to reduce the ⁇ -phase in the test alloys.
  • the heat treatment was made at 550 °C for 2 h since comparative experiments with other temperatures and time intervals (such as 460 °C to 550 °C for 30 min-8 h) indicate that improved dezincification resistance and protection against intergranular grain boundary corrosion are obtained upon heat treatment at 550 °C for 2 h. Moreover, experiments have shown that heat treatment at 550 °C for 2 h also promotes that the ⁇ -zones are not continuous, which in turn promotes protection against IGA.
  • test alloys 1-1 1 were exposed to corrosion in accordance with ISO 6509 "Copper and copper alloys - brass - Determination of dezincification", in 1 % CuCI 2 solution for 24 h at 75 ⁇ 2 °C.
  • Characterizing of structures before corrosion exposure was made in the same way on etched cross-sections. Quantification was made by counting a fraction of the intersection points (mesh-intersection) of the grid which superseded 200 points; i.e., a grid is laid over the picture, then the number of points of a- and ⁇ -phase, respectively, are counted and translated into %.
  • test alloy 1-1 1 The results from the CuC ⁇ exposure of test alloy 1-1 1 are presented in Table 5 where it is seen if corrosion has occurred in the a- and/or ⁇ -phase and how deep ( ⁇ ) the dezincification (AD - dezincification depth) is present.
  • Figure 2 illustrates cross-sections from test plates showing the degree of corrosion attack for representative test alloys.
  • test alloy 7, 9, 10 and 1 1 which all comprise Sb >0.02 % by weight or a combination of As and Sb >0.02 % by weight.
  • Table 5 Dezincification depth (AD) after CuCI 2 exposure and identification of coexistent corrosion mechanisms such as intergranular grain boundary corrosion (IGA) and general. "?” indicates that it was difficult to determine type of corrosion, i.e., it may be a or ⁇ .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Investigating And Analyzing Materials By Characteristic Methods (AREA)
  • Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
  • Contacts (AREA)
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  • Paper (AREA)
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Abstract

La présente invention concerne un alliage de laiton essentiellement exempt d'arsenic présentant une meilleure (i) résistance à la dézincification, (ii) usinabilité et (iii) protection contre la corrosion de joint de grain intergranulaire, ledit alliage de laiton comprenant 62 à 68 % en poids de Cu, 0,02 à 1,00 % en poids de Pb, 0,2 à 0,6 % en poids de P, 0,02 à 0,06 % en poids de Sb, et le reste étant du Zn, et l'alliage de laiton étant caractérisé en ce qu'il comprend < 5 % de phase beta, de préférence < 1 % En outre, l'invention concerne un procédé pour la production dudit alliage de laiton.
EP15709371.7A 2014-01-30 2015-01-30 Laiton présentant une meilleure résistance à la dézincification et une meilleure usinabilité Revoked EP3099832B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE1450094A SE1450094A1 (sv) 2014-01-30 2014-01-30 Arsenikfri mässing med förbättrad avzinkningshärdighet och skärbarhet
PCT/SE2015/050103 WO2015115989A2 (fr) 2014-01-30 2015-01-30 Laiton présentant une meilleure résistance à la dézincification et une meilleure usinabilité

Publications (2)

Publication Number Publication Date
EP3099832A2 true EP3099832A2 (fr) 2016-12-07
EP3099832B1 EP3099832B1 (fr) 2018-11-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP15709371.7A Revoked EP3099832B1 (fr) 2014-01-30 2015-01-30 Laiton présentant une meilleure résistance à la dézincification et une meilleure usinabilité

Country Status (13)

Country Link
US (1) US20160340759A1 (fr)
EP (1) EP3099832B1 (fr)
JP (1) JP6178016B2 (fr)
KR (1) KR101802933B1 (fr)
CN (1) CN106170569A (fr)
AU (1) AU2015211433A1 (fr)
BR (1) BR112016017682A2 (fr)
CA (1) CA2937664A1 (fr)
MX (1) MX2016009812A (fr)
RU (1) RU2016133287A (fr)
SE (1) SE1450094A1 (fr)
SG (1) SG11201605577PA (fr)
WO (1) WO2015115989A2 (fr)

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JP6315868B1 (ja) * 2017-11-28 2018-04-25 日酸Ｔａｎａｋａ株式会社 ガス切断火口
CN109038940A (zh) * 2018-08-08 2018-12-18 东莞市特姆优传动科技有限公司 一种高效大推力太阳能板电动推杆
CN111235427B (zh) * 2020-01-15 2020-12-29 宁波博威合金材料股份有限公司 一种易切削黄铜合金及其制备方法和应用
CN112342428A (zh) * 2020-10-23 2021-02-09 开平大昌铜材有限公司 一种dzr铜及其制备方法
CN114672690B (zh) * 2022-03-16 2023-02-24 宁波金田铜业(集团)股份有限公司 一种易镀色黄铜及其制备方法
CN118064759A (zh) * 2024-04-23 2024-05-24 中铝科学技术研究院有限公司 抗脱锌腐蚀耐蚀黄铜合金、其制备方法及应用

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Also Published As

Publication number Publication date
EP3099832B1 (fr) 2018-11-14
JP2017508073A (ja) 2017-03-23
JP6178016B2 (ja) 2017-08-09
MX2016009812A (es) 2017-02-28
BR112016017682A2 (pt) 2017-08-08
CN106170569A (zh) 2016-11-30
RU2016133287A (ru) 2018-03-05
SE1450094A1 (sv) 2015-07-31
WO2015115989A2 (fr) 2015-08-06
AU2015211433A1 (en) 2016-09-01
SG11201605577PA (en) 2016-08-30
US20160340759A1 (en) 2016-11-24
RU2016133287A3 (fr) 2018-10-15
WO2015115989A3 (fr) 2015-09-24
CA2937664A1 (fr) 2015-08-06
KR20170005402A (ko) 2017-01-13
KR101802933B1 (ko) 2017-11-29

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