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WO1998010106A1 - Alliage de cuivre et procede de fabrication correspondant - Google Patents

Alliage de cuivre et procede de fabrication correspondant Download PDF

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Publication number
WO1998010106A1
WO1998010106A1 PCT/JP1997/003152 JP9703152W WO9810106A1 WO 1998010106 A1 WO1998010106 A1 WO 1998010106A1 JP 9703152 W JP9703152 W JP 9703152W WO 9810106 A1 WO9810106 A1 WO 9810106A1
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WO
WIPO (PCT)
Prior art keywords
parts
brass
equipment
products
cans
Prior art date
Application number
PCT/JP1997/003152
Other languages
English (en)
Japanese (ja)
Inventor
Katsuaki Nakamura
Nobuyuki Ashie
Ryuji Matsubara
Masanao Hamasaki
Original Assignee
Toto Ltd.
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27579509&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1998010106(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Toto Ltd. filed Critical Toto Ltd.
Priority to CA002265812A priority Critical patent/CA2265812A1/fr
Priority to DE69720261T priority patent/DE69720261T2/de
Priority to EP97939214A priority patent/EP0947592B1/fr
Priority to AT97939214T priority patent/ATE235573T1/de
Priority to JP51249198A priority patent/JP3303301B2/ja
Priority to AU41360/97A priority patent/AU4136097A/en
Publication of WO1998010106A1 publication Critical patent/WO1998010106A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent

Definitions

  • the present invention relates to a metal material, a method for manufacturing the same, and a metal product.
  • the present invention mainly relates to a Cu—Zn-based copper alloy, that is, brass and a method for producing the same, but the principle of the present invention is not limited to brass alone.
  • aluminum or stainless steel has been known as a metal material having an elongation of more than 100%. These good elongations are due to grain boundary slippage that relaxes the strain. Since grain boundary sliding works effectively for low-speed external force with a strain rate of about 0.1 Ol Z sec, aluminum / stainless steel has large ductility against such low-speed external force. However, for high-speed external forces with a strain rate exceeding 0.1 / sec, grain boundary sliding does not work effectively, and excessive dislocations occur in the crystal grains, resulting in cracking.
  • the processing force is applied at a temperature below the limit at which the crystal grains do not become coarse, so that there is insufficient energy to increase the recrystallization speed.
  • brass has many uses. The characteristics required of brass vary depending on the application. For example, a brass material for forging is required to have high ductility against the high-speed external force described above. For example, brass used for water contact parts such as valves and faucet fittings is required to have high corrosion resistance to water and high erosion resistance. Furthermore, high strength and good machinability are also required for various applications.
  • the corrosion resistance of brass mainly means the resistance to dezincification corrosion.
  • Dezincification corrosion means that Zri preferentially elutes in water due to the difference in ionization tendency between Cu and Zn, and as a result, the content of Zn decreases over time, resulting in a decrease in strength This is an important issue when brass is applied to water contact parts.
  • Japanese Patent Publication No. 61-58 ⁇ 40 discloses that a Pb, Fe, i, Sb and P are added to a Cu-Zn-Sn-based copper alloy, Is disclosed.
  • Japanese Patent Application Laid-Open No. 6-10884 discloses that a copper alloy of the type 11-21-311 added with Pb, Fe, Xi, Sb and ⁇ is hot-pressed or drawn. It has been disclosed that after removal, heat treatment at 500 to 60 CTC for 30 minutes to 3 hours substantially results in a solid phase.
  • An object of the present invention is to provide a metal material having high ductility against a high-speed external force.
  • Another object of the present invention is to provide brass having high ductility against high-speed external force.
  • Yet another object of the present invention is to provide brass having good corrosion resistance and good machinability.
  • Still another object of the present invention is to provide brass excellent in various properties such as ductility, strength, machinability and corrosion resistance.
  • Still another object of the present invention is to provide a method for producing brass according to the above objects.
  • Still another object of the present invention is to provide a metal product and a brass product excellent in various properties.
  • the metal material according to the first aspect of the present invention has a crystal structure such that the strain of the metal crystal is dispersed when deformed by an external force, and the strain energy due to the deformation is the energy of recrystallization of the metal crystal. It can be a source. Therefore, when a high-speed external force is applied, the strain is generated not locally but in a dispersed manner, and the large strain energy causes recrystallization and dislocations are eliminated. As a result, high ductility to high-speed external force is obtained.
  • the strain energy of a metal crystal deformed by an external force during hot working is defined as SE
  • the thermal energy given to the metal crystal by heating during hot working is defined as TE.
  • the energy required for coarsening the crystal grains without external force A step of performing hot working on the metal material under the following conditions.
  • the metal material when performing hot working, the metal material is not ripened to a high temperature at which the crystal grains become coarse and the ductility is reduced, but the temperature is relatively low.
  • One example of such a condition is to adjust the crystal structure of the metal material used for hot working to a type that causes the strain to be dispersed when subjected to an external force.
  • One type of crystal structure in which the strain is dispersed when subjected to an external force is a mixture of relatively soft and relatively hard crystals, and the crystal grains are sufficiently fine. is there.
  • a soft crystal is deformed when subjected to an external force
  • Such a crystal structure is an alloy containing at least two kinds of metal elements, and a soft crystal phase and a hard crystal phase are precipitated, typically brass, which is an alloy of Cu and ⁇ , Can be realized.
  • Specific examples include ⁇ + +, ⁇ + ⁇ + ⁇ , and h + r-type brass having fine crystal grains (15 111 or less).
  • a third element that contributes to increasing the recrystallization rate (increase the rate at which nuclei for recrystallization are generated) in the soft crystal of the alloy of two metals as described above.
  • a typical example of such a third element is one in which the atomic radii are close to those of the above two metal elements, such as Sn in the case of brass, so as to form a substitutional solid solution in a soft crystal.
  • the brass according to the third aspect of the present invention has a crystal structure of + ⁇ in the recrystallization temperature range. And in the recrystallization temperature range
  • (A2) the average crystal grain size of the ⁇ phase and the three phases is 15 m or less, preferably 10 m or less, and
  • the preferred embodiment of the brass according to the present invention is in the recrystallization temperature range.
  • the strain rate is 1 / sec, giving 1 ⁇ 0% strain and no damage
  • a strain rate of more than 200% at a strain rate of 0.01 Zsec gives no damage, or (4) A strain rate of more than 600% at a strain rate of 0.001 Zsec causes no damage. Absent,
  • the brass of the present invention is roughly classified into four types, which are referred to in the present specification as “H + r type”, “H + + ⁇ type”, “ ⁇ + normal 3 type” and “ ⁇ + enhanced / 3 type”. it can.
  • “He + ⁇ type” brass has an ⁇ + r crystal structure at room temperature, and at room temperature
  • the area ratio of the r phase is 3 to 30%, preferably 5 to 30%
  • the average crystal grain size of the phase is 15 m or less, preferably 10 _m or less, and (B3) the average crystal grain size (minor axis) of the r phase is 8 ⁇ m or less, preferably 5 ⁇ m.
  • Brass of “H + 0 + r type” has a crystal structure of + / 3 + ′ at room temperature, and at room temperature.
  • the average crystal grain size of the phase and the three phases is 15 m or less, preferably 10 m or less, and
  • This type of brass is preferably further provided at room temperature
  • (B5) r phase contains at least 8 wt% of Sn
  • the “ ⁇ + normal / 3 type” brass has a crystal structure of 0 at room temperature, and at room temperature.
  • (B1) i3 phase area ratio is 20% or more, preferably 25% or more;
  • the average crystal grain size of the phase and the three phases is 15 m or less, preferably 10 m or less.
  • This type of brass has excellent machinability and strength.
  • the brass of “Hi + Strength / 3B” has a crystal structure of ⁇ 10 / 3 at room temperature
  • the area ratio of the phase is at least 15%, preferably at least 2%
  • the average crystal grain size of the a phase and the / 3 phase is 15 m or less, preferably 10 m or less, and
  • (B3) / 3 phase contains 1.5 wt% or more of Sn, It satisfies the condition.
  • the brass of this evening is excellent in all of machinability, corrosion resistance and SCC resistance.
  • the preferred embodiment provides a strain rate in the recrystallization temperature range.
  • the cutting resistance index based on a free-cutting brass bar in accordance with Japanese Industrial Standard JISC-3604 is 80 or more.
  • the maximum zinc removal depth direction is parallel to the processing direction, the maximum zinc removal depth is 100 m or less, or When the maximum zinc removal depth is perpendicular to the processing direction, the maximum zinc removal depth is 0 m or less.
  • SPZ zinc aluminum
  • aluminum have poor corrosion resistance in water, and aluminum in particular causes pitting corrosion, and they are sticky and have poor machinability.
  • the apparent Zn content of the raw material composition is 37 to 46 wt%
  • the solidification rate during fabrication is 5 X 10 'to 10 3 KZs ec, preferably 10 2 to 10 S K / sec, and
  • the cooling rate after solidification is 5Ksec or more until it becomes 400 ° C or less.
  • the brass structure produced by this method satisfies the conditions in the brass recrystallization temperature range according to the third aspect of the present invention, and thus has high hot ductility.
  • the production method of the present invention comprises, after the above-mentioned structure, a step of hot-extruding the brass structure at a temperature in the range of 480 to 650 ° (preferably 480 to 600 ° C to form a brass extruded product.
  • the cooling after the hot extrusion is preferably performed at a rate of 0.4 KZsec or more until the temperature becomes 400 ° C. or less. Meets the requirements of brass according to the sides.
  • the method for producing brass according to the fifth aspect of the present invention comprises: a brass material having an apparent Zn content of 37 to 46 wt%;
  • the temperature during extrusion is in the range of 480 to 650 ° C, preferably 480 to 600 ° C, and
  • a brass extruded product satisfying the brass conditions according to the third aspect of the present invention can be obtained.
  • the cooling rate after hot extrusion is preferably at least 0.4 KZsec until the temperature reaches 400 ° C or lower.
  • the method may further include the step of reheating the brass extrudate and forging at a temperature in the range of 480-750 ° C to produce a brass forged product.
  • the forging also satisfies the brass requirements according to the third aspect of the invention.
  • the strain rate of hot forging is preferably 1 / sec or more. In such high-speed hot forging, the grain size does not increase during forging.
  • the cooling rate after hot forging is preferably 0.4 K / sec or more until the temperature becomes 400 ° C or less. As a result, the crystal grain size becomes coarse even after cooling Without this, fine crystal grains of 15 m or less are obtained.
  • the Sn content of the brass material is 0.9 to 7 wt%, and the cooling rate after hot extrusion or hot forging is 400. You can choose the condition 0.4 to 5KZsec until: Alternatively, as an alternative, the Sn content of the brass material is set to 0.9 to 7 wt%, and the brass forging is heated and maintained at a temperature of 400 to 550 ° C for 30 seconds or more, and thereafter 400 ° C or less. A heat treatment step of cooling at a rate of 0.4 to 5 K / sec until the heat treatment step can be added after the hot forming step.
  • the Sn content of the brass material is 0.9 to 7% by weight, and cooling after hot extrusion or hot forming.
  • the condition of 0.4 to 10 K / sec can be selected until the speed becomes 400 or less.
  • after hot forming heat the brass structure and maintain it at a temperature of 450-550 ° C for at least 30 seconds, then 4 ° 0 ° C It is possible to add a heat treatment step of cooling at a rate of 0.4 to 1 OKZsec until the temperature becomes below.
  • the Sn content of the brass material is 5 to 7 wt% and the apparent Zn content is 37 to 44%.
  • the conditions can be selected from 5 to 1000 K / sec in terms of wt%, until the cooling rate after hot extrusion or hot forging becomes 400 ° C or less.
  • the brass forging is heated and maintained at a temperature of 475 to 550 ° C for 30 seconds or more, and then reduced to 400 ° C or less.
  • a heat treatment step of cooling at a rate of 5 to 100 OKZsec or more can be added.
  • the method for producing brass according to the sixth aspect of the present invention comprises a step of heating and then cooling a brass material having an apparent Zn content of 37 to 46 wt%, and a crystal structure of the brass material after cooling.
  • Heating temperature in order to select from 3 + r
  • the copper alloy (typically, brass) according to the seventh aspect of the present invention has the following excellent cutting quality and mechanical strength. That is, the cutting resistance index based on a free-cutting brass bar in accordance with Japanese Industrial Standard JISC-3604 is 80 or more, and the 0.2% power resistance or the yield stress is 30 ON / mm 2 or more. Conventionally, there is no copper alloy having such excellent machinability and strength.
  • bronze, or with 80 or more cutting resistance index ', to include the 0.2% ⁇ Ka is 80 / mm 2
  • bronze only about tensile strength 220 N / mm 2 copper 79% or more generally One method for improving the strength of bronze is to increase the Sn content.
  • the copper alloy of the present invention particularly brass, has improved machinability and strength by appropriately balancing copper having excellent corrosion resistance and zinc having excellent machinability.
  • the copper alloy (typically brass) according to the eighth aspect of the present invention has the following excellent SCC resistance. That is, when a cylindrical sample of the copper alloy of the present invention is exposed to an ammonia atmosphere on a 14% aqueous ammonia solution for 24 hours while applying a load, the maximum stress at which the sample does not crack is 180 N / mm2 or more. To improve SCC resistance, it is necessary (although not enough) to improve strength and corrosion resistance. In the present invention, the SCC resistance is improved by utilizing the characteristics of copper having excellent corrosion resistance. Bronze is vulnerable to stress and undergoes plastic deformation with a stress of about 10 ON / mm 2 .
  • the brass according to the ninth aspect of the present invention has the following excellent cutting life and corrosion resistance. That is, the cutting resistance index based on the free-cutting brass bar is 80 or more, and When performing a zinc removal corrosion test in accordance with JBMA T-303, if the maximum zinc removal depth direction is parallel to the processing direction, the maximum zinc removal depth is 100 m or less, or the maximum zinc removal depth. When the penetration depth direction is perpendicular to the processing direction, the maximum dezincification depth is less than 0 ⁇ m. Incidentally, the free-cutting brass rod has poor corrosion resistance, and the maximum dezincification depth reaches about 200 m when the above-mentioned dezincification corrosion test is performed.
  • One way to improve the machinability of brass is to make the average grain size less than 15 m, preferably less than 10 m.
  • the softer part of the phase is another metal, for example Pb or Bi.
  • the portion harder than the phase is, for example, a / 3 phase, a ⁇ phase, an intermetallic compound such as FeSi or FeP, or an oxide of Cu or Mg. Comparing the crystal structures of ++ / S and ++ r, + r has higher machinability because the hardness difference between the two phases is larger than that of ++ / S.
  • the following methods can be used to improve the corrosion resistance as well as the machinability of brass.
  • the ⁇ + r crystal structure it is effective to include Sn in the 7 ′′ phase preferably in an amount of 8 wt% or more.
  • the / 3 phase is used to improve corrosion resistance. It is effective to contain the third element (for example, Sn, Si, Al, Sb, Ge, or Ga).
  • Sn is contained, the Sn concentration in the three phases is 1.
  • a crystal structure having an ⁇ phase, a / 3 phase, and a portion having better corrosion resistance than the three phases surrounding the crystal grains of the three phases is also effective.
  • the portion having more excellent corrosion resistance is, for example, an r phase containing at least 8 wt% of Sn.In such a crystal structure of + 3 + r, in order to prevent the brittleness of the r phase from appearing, It is desirable that the average grain size of the ⁇ phase be 8 m or less.
  • Brass having improved machinability and corrosion resistance according to the present invention can be applied to various uses, but is particularly suitable for water pipe parts. Since the brass of the present invention has a small average crystal grain size, the cold ductility is not so excellent. However, for water pipe parts, martensite and shape memory alloy Since high cold ductility as described above is not required, the brass of the present invention can sufficiently satisfy the required product quality.
  • Yet another aspect of the present invention provides various products using the metal or brass of the present invention. Yet another aspect of the present invention also provides a manufacturing facility that can be used to manufacture the metal or brass of the present invention.
  • Figure 1 shows the characteristics of the three crystalline phases of brass, pure Cu, pure Zn, and pure Sn.
  • 2A to 2C are tables showing compositions, crystal structures and various properties of various examples of the brass of the present invention and some examples of conventional brass.
  • Figure 3 is a flowchart showing an example of the brass product manufacturing process.
  • FIG. 4 is a table showing conditions of production and hot extrusion for two examples of the method for producing brass of the present invention and an example of a conventional production method.
  • FIG. 5 is a table showing the relationship between the hot working process and the crystal structure of the product in two embodiments of the brass manufacturing method of the present invention and an example of the conventional manufacturing method.
  • Figure 6 shows a graph showing the results of a ductility (strain rate and strain rate) test in the recrystallization temperature range:
  • Figure 7 shows a table showing the results of the machinability test.
  • FIG. 8 is a perspective view illustrating a method of a machinability test.
  • FIG. 9 shows a graph showing the results of the erosion corrosion resistance test.
  • Fig. 10 Diagram explaining the method of erosion corrosion resistance test.
  • FIG. 11 is a diagram for explaining a method of a stress corrosion cracking resistance test.
  • FIG. 12 is a table showing the results of the stress corrosion cracking resistance test.
  • FIG. 13 shows a table showing the composition of some samples related to the “type 3” brass and the results of the corrosion resistance test.
  • FIG. 14 is a graph showing the relationship between the Sn concentration in the phase and the cooling time to 400 ° C.
  • FIG. 15 is a table showing the effect of a heat treatment on brass of the “hi + strength) 3 type” of the present invention.
  • FIG. 16A is a microscopic view showing the crystal structure of one embodiment of the brass of the “type of the present invention”.
  • FIG. 16B is a schematic diagram created based on FIG. 16A.
  • FIG. 17A is a photomicrograph showing the crystal structure of one example of the “++ r type” brass of the present invention.
  • Figure 17B is a schematic diagram created based on Figure 17A.
  • FIG. 18 is a table showing the composition and the corrosion resistance test results of several samples related to the “hi + r type” and the “ ⁇ + / 3 + ⁇ type” brass of the present invention.
  • FIG. 19 is a flow chart showing an example of a process for producing a water contact part using brass of the “+ ⁇ type” or “hi + r eeve” type of the present invention.
  • Fig. 20 is a flow chart showing an example of a conventional water contact component manufacturing process using brass.
  • Fig. 21 is the effect of heat treatment on the "+ r type” and "hi + r type” brass of the present invention. Is shown.
  • FIG. 22A is a photomicrograph showing the crystal structure of a brass material for manufacturing manufactured at a cooling rate of 19 KZ sec after the manufacturing.
  • FIG. 22B is a schematic diagram created based on FIG. 22A.
  • Fig. 23A is a micrograph of a part of Fig. 22A.
  • FIG. 23B is a schematic diagram created based on FIG. 22A.
  • FIG. 24A is a micrograph showing the crystal structure of a brass material for forging manufactured at a cooling rate of 1.3 KZ sec after forging.
  • FIG. 24B is a schematic diagram created based on FIG. 24A.
  • Fig. 25A is a micrograph of a part of Fig. 24A.
  • Fig. 25B is a schematic diagram created based on Fig. 25A.
  • FIG. 26A is a photomicrograph showing a crystal structure of a brass billet for forging produced by hot-extruding a brass material containing 1.9 wt% of Sn and then extruding and cooling at 3 OK / sec.
  • FIG. 26B is a schematic diagram created based on FIG. 26A.
  • FIG. 27A is a photomicrograph showing the crystal structure of the brass forged product obtained by hot forging the brass billet shown in FIG. 26A and cooling it at 20 K / Sec after forging.
  • Figure 27 ⁇ is a schematic diagram created based on Figure 27 ⁇ .
  • FIG. 28A is a micrograph showing the crystal structure of a brass billet for forging produced by hot-extruding a brass material containing 2.3 wt% of Sn and then extruding and cooling at 3 OK / sec.
  • FIG. 28B is a schematic diagram created based on FIG. 28A.
  • FIG. 29A is a photomicrograph showing the crystal structure of a brass forged product made by hot forging the brass billet shown in FIG. 28A and cooling it at 2 K / sec after fabrication.
  • FIG. 29B is a schematic diagram created based on FIG. 29A.
  • FIG. 30 is a table showing preferable conditions for the crystal structure and composition of the brass of the present invention.
  • FIG. 31 is a table showing preferred production and hot extrusion cows when the brass of the present invention is finally produced by hot extrusion.
  • FIG. 32 is a table showing preferable conditions of hot extrusion and hot forging when the brass of the present invention is finally manufactured by hot forging.
  • FIG. 33 is a table showing preferred conditions of hot extrusion, hot forging, and heat treatment when the brass of the present invention is finally produced by heat treatment.
  • FIG. 34 is a perspective view showing an example of a faucet to which the brass of the present invention is applied.
  • FIG. 35 is a sectional view showing an example of a water pipe to which the brass of the present invention is applied.
  • FIG. 36 is a cross-sectional view showing another example of a water pipe to which the brass of the present invention is applied.
  • FIG. 37 is a cross-sectional view showing still another example of the water pipe to which the brass of the present invention is applied.
  • FIG. 38 is a diagram showing an example of a water heater having a pressure reducing valve and a relief valve using the brass of the present invention.
  • FIG. 39 is a view showing a pressure reducing valve of the water heater in FIG. 38.
  • FIG. 40 is a view showing a relief valve of the water heater in FIG. 38. ⁇ . BEST MODE FOR CARRYING OUT THE INVENTION
  • Cu- ⁇ -based copper alloys are wide-ranging, such as water contact parts such as faucets and water pipes, home appliances, mechanical parts, building materials, gas appliances and optical parts.
  • This type of copper alloy is required not only for general properties such as strength, cold ductility, hardness, cutting and polishing properties, but also for water contact parts such as corrosion resistance, erosion resistance, stress corrosion cracking resistance, etc. It is also desirable that these materials have excellent characteristics.
  • One principle of the present invention focuses on the properties of the crystal phase of the 11-1211 copper alloy in order to improve the above properties.
  • / 3 and r are conventionally known.
  • the r-phase has excellent corrosion resistance and strength, but because of its high brittleness, no attempt has been made to actively utilize its properties.
  • the / 3 phase has previously been evaluated as unsuitable for water contact parts due to its low corrosion resistance.
  • the phase has excellent corrosion resistance and cold ductility, but is inferior in strength and machinability.
  • the characteristics of each crystal phase are conventionally tended to be fixed, and no attempt has been made to actively modify the characteristics of the crystal phases.
  • the inventors of the present invention have conducted research on factors affecting the above-mentioned various properties, and as a result, have found that the size of crystal grains is also an important factor in addition to the type of crystal phase. According to the results of this research, firstly, the properties of brass are improved by making effective use of the 7 "phase. Second, the properties of brass are improved, especially by modifying the properties of the three phases. Third, optimizing the crystal grain size improves the properties of brass. -As one specific means for precipitating the phase and modifying the properties of the / 3 phase, the addition of Sn can be used.However, the addition of Sn causes a reduction in hot ductility, and Not suitable for brass material.
  • Figure 1 shows the three crystal phases that appear in the Cu—Zn alloy (brass). And the characteristics of pure Cu, pure Zn, and pure Sn.
  • pure Cu is excellent in corrosion resistance, ductility at room temperature and cold forgeability (easiness of cold forging), but inferior in power resistance and machinability (easiness of cutting).
  • Cu-Zn alloys (brass) to which Zn has been added have been widely used.
  • the crystal structure varies depending on the amount of Zn added.
  • the term" apparent Zn content "means that A is Cu content [wt%], B is Zn content [wt%], and t
  • the Zn equivalent of an element for example, Sn
  • Q is the content of the third element [wt%]
  • ((B + t-Q) / (A + B + t-Q) ⁇ xlOO” For the meaning, .
  • Single-phase brass is excellent in corrosion resistance and cold forgeability, but inferior in power resistance and machinability.
  • Sn is added to this, a force capable of improving corrosion resistance and power resistance ⁇
  • the ⁇ -phase has almost the opposite properties to the ⁇ -phase, and is inferior in corrosion resistance and cold workability, but is excellent in heat resistance, hot workability (easiness of hot forging) and machinability.
  • One novel finding obtained by the inventors' research is that the addition of S ⁇ to ⁇ -phase crystal grains improves both corrosion resistance and power, and particularly the corrosion resistance of ⁇ -phase single-phase It is to be improved to almost the same level as the alloys.
  • the r phase appears when S ⁇ is added in a predetermined amount or more. 7 "phase is brittle, but excellent in corrosion resistance and proof stress.
  • the “corrosion resistance” of copper alloys mainly refers to its resistance to dezincification corrosion.
  • De-zinc-free corrosion refers to a phenomenon in which ⁇ is preferentially eluted in water and the ⁇ content decreases due to the difference in ionization tendency between Cu and ⁇ , and the strength decreases with time. This is a problem when using a u—Zn-based alloy.
  • the crystal phases having the above-mentioned different properties are appropriately combined, and the crystal grain size is optimized.
  • 2A to 2C show the compositions and properties of the nineteen examples of brass according to the invention in comparison with those of the brass according to the prior art (comparative example).
  • Examples 1 to 19 have a crystal structure of (h) + r, and the crystal grains are refined (15 ⁇ zm or less) and the r phase having improved characteristics is effectively used.
  • Examples 6 to 12 have a crystal structure of (h) + 3 + r, in which the crystal grains are refined, and the / 3 phase and the r phase having improved properties are effectively used.
  • Examples 13 to 15 have a crystal structure of H + / S, and the crystal grains are refined.
  • Examples 16 to 19 have a + / S crystal structure, crystal grains are refined, and the properties of the / 3 phase are improved by the addition of Sn. Further, in Examples 1 to 19, the ratio of each crystal phase is appropriately adjusted.
  • Examples 1 to 19 were manufactured by manufacturing a brass sample having the composition shown in FIG. 2A under hot conditions under the manufacturing conditions in accordance with the principles of the present invention, hot extruding the same, and then hot forging.
  • the typical manufacturing procedure is shown in Fig. 3).
  • the heat treatment conditions in FIGS. 2A to 2C indicate the temperature during forging and the cooling method.
  • the cooling rate for air cooling was 0.8 K / sec, and the cooling rate for water cooling was 1 ⁇ 0 sec.
  • Figures 2A to 2C show the characteristics of “0.2% resistance [N / mm 2 ]” (tensile stress causing permanent elongation of 0.2%) and “cold ductility [%]” (cold Ductility in the working temperature range), “hardness [HV]”, “hot ductility” (ductility in the hot working temperature range, that is, recrystallization temperature range), “cutting resistance index”, “corrosion resistance”, “erosion resistance” Corrosion “and” stress corrosion cracking resistance “(SCC resistance) are listed.
  • SCC resistance stress corrosion cracking resistance
  • JBMA T-303 Japan Copper and Brass Association technical standard
  • JBMA T-303 Japan Copper and Brass Association technical standard
  • Examples 1 to 5 were evaluated as good ( ⁇ ) or excellent ( ⁇ ) in power resistance, cold ductility, corrosion resistance, erosion corrosion resistance, and stress corrosion cracking resistance. Was done.
  • Examples 1 and 2 were evaluated as poor (X) in machinability. The reason is that the optimum condition of 7 "phase is 3% or more and ⁇ phase is 3% or less, or r phase is 5% or more is satisfied.
  • Example 1 was also evaluated as poor (X) in hot ductility, because the apparent Zn content was less than 38 wt%, It is presumed that the three phases did not reach 30% during processing.
  • Examples 6 to 12 all properties were evaluated as good ( ⁇ ) or excellent (().
  • Examples 13 to 15 the properties other than corrosion resistance and erosion corrosion resistance were evaluated as good ( ⁇ ) or excellent ( ⁇ ).
  • FIG. 3 shows an example of a manufacturing process using hot forging of a brass product.
  • step 1 electrolytic copper, electric zinc, and scrap are mixed and melted.
  • step 2 after being manufactured, it is rapidly cooled to produce an intermediate molded body, and then the intermediate molded body is heated and extruded to form a rod-shaped or linear billet.
  • step 3 A rod or linear billet is cold drawn, annealed and pickled, and cut to a predetermined size.
  • the above-mentioned billet is heated to secure characteristics suitable for the next step forging.
  • the heated billet is set in a mold for fabrication to perform fabrication. Then, cool down to prepare for the transition to Step 6. When the cooling is completed, proceed to step 6, perform acid washing and shot blasting to remove the oxide film on the surface, and then perform deburring.
  • the product is obtained through the steps of cutting, polishing and plating.
  • FIG. 4 and 5 show two examples of the production method of the present invention (method 1 of the present invention, method 2 of the present invention) and a conventional production method according to the production process of FIG. The crystal structure is shown in comparison.
  • the "apparent Z ⁇ content” relates to the mixing ratio of the material melted in step 1 shown in Fig. 3, and the “solidification rate at the time of manufacture” and “cooling rate after the manufacture”
  • the “extrusion temperature” and “cooling after extrusion” are related to the conditions of the hot extrusion in Step 2 related to the manufacturing conditions of Step 1.
  • “grain size” refers to that of the billet after the completion of the maturation extrusion in Step 2 (the grain size of the final product is also the same in the method of the present invention).
  • “ Forging temperature ”and“ strain rate and strain rate ” are related to the forging conditions in step 5
  • “ proof strength ”and“ / 3/3, 7 ”phase ratio after forging” are those of the product completed in step 7. Point to.
  • the apparent ⁇ ⁇ ⁇ content of the brass material is larger than that of the conventional method (typically, the added amount of Sn is larger).
  • the solidification rate during hot forming (step 1) and the cooling rate after forming are faster, the temperature during hot extrusion (step 2) is lower, and the cooling rate after extrusion is faster (specifically, Cool at a rate of 0.4 K / sec or more up to 400 ° C).
  • the cross-sectional reduction rate of the extrusion was 90% or more, which was favorable. Preferably it is more than 95%.
  • the billets prepared by the methods 1 and 2 of the present invention have higher strain rates and lower strains at lower fabrication temperatures than the billets prepared by the conventional method.
  • the structure can be made with the strain rate (Step 5).
  • the billets according to the methods 1 and 2 of the present invention have a smaller crystal grain size and a lower hot temperature even at a relatively low fabrication temperature as compared with the billets according to the conventional method.
  • the ductility includes (the three phases that can be included) in an appropriate ratio.
  • the ability to forge at a lower temperature is advantageous in that the forging equipment is less deteriorated.
  • the power resistance of the products forged by the methods 1 and 2 of the present invention is significantly higher than conventional forged products.
  • Fig. 6 shows the forging temperature range of the two types of billets (specifically, Example 10 and Comparative Example 4 shown in Figs. 2A to 2C) made by the method of the present invention and the conventional method. It shows the hot ductility at. The horizontal axis shows the strain rate £ [sec], and the vertical axis shows the strain rate sL [%]. Example 10 is clearly superior to Comparative Example 4 in hot ductility.
  • Fig. 7 shows a cutting test of Comparative Example 3, Examples 8, 10, 11 and 11, a free-cutting brass bar (JISC-3604), and a single-phase brass material shown in Figs. 2A to 2C. The results are shown.
  • the main component force Fv was measured while cutting the circumference of round bar-shaped sample 1 on a lathe at two different speeds of 100 mZmin and 400 mZmin. did.
  • the cutting resistance index of each sample is the percentage of the main component of a free-cutting brass rod, which is said to have the best cutting performance with respect to the main component of each sample.
  • K19 was the erosion resistance test of Examples 8, 11 and Comparative Example 4 shown in FIGS. 2A to 2C. The results are shown, and FIG. 10 shows the method of the erosion resistance test.
  • a circular sample 5 having an orifice 7 inside was used, and water was flowed through the orifice 7 at a flow rate of 4 Om / sec for a predetermined time.
  • the tightening torque on the resin stopper 9 required to seal the orifice 7 under a water pressure of 9 10 5 Pa ( ⁇ K g / cm 2 ) was measured.
  • FIG. 9 it can be seen that Examples 8 and 11 have better erosion resistance than Comparative Example 4.
  • FIG. 12 shows the test results (relationship between main stress and crack generation) of Examples 8, 11, 15, and Comparative Example 4 shown in FIGS. 2A to 2C.
  • FIG. 12 shows that Examples 8, 11, and 15 have better SCC resistance than Comparative Example 4.
  • Examples 1 to 19 of the present invention shown in FIGS. 2A to 2C have good characteristics.
  • Examples 16 to 19 have a + / 3 crystal structure in which the crystal is refined (15 m or less) and the characteristics are improved by adding Sn to the 0 phase.
  • this type is hereinafter referred to as “ten strengthening / 3 type”.
  • the crystal grain is refined in the crystal structure of the "hi + 7" crystal, and the characteristics are improved by using the r phase. This type is hereinafter referred to as "hi + r type”.
  • the crystal grain is refined in the ⁇ + i3 + r crystal structure and the characteristics are improved by using the r phase.
  • Fig. 13 lists seven types of brass samples No. i to 7 related to "Phase + Strengthened 3 types" (different from those listed in Figs. 2A to 2C).
  • Figure 13 shows the composition of Sample Nos. 1 to 7, the apparent Zn content, the Sn concentration in the three phases, and the results of the corrosion resistance (dezincification corrosion resistance) test.
  • the Sn concentration in the / 3 phase was adjusted by heat treatment and cooling treatment, and quantified by EPMA analysis.
  • the results of the corrosion resistance determination were performed in the same manner as described above with reference to FIGS. 2A to 2C.
  • FIG. 14 is a graph showing the results of an experiment in which the relationship between the cooling time to 400 '° C after the heat treatment and the Sn concentration in the three phases was examined when the heat treatment temperature was 550 ° C. From Fig. 14, if the cooling rate from the start of cooling to 40 ° C is 0.4KZsec or more (the area to the left of point ⁇ in Fig. 14), the Sn concentration in the / 3 phase will be 1.5wt%. It turns out that it becomes above. Further experiments have confirmed that the upper limit of the cooling rate is acceptable up to at least 1 000 K / sec. The same experimental results were obtained not only when the heat treatment temperature was 550 ° C but also when other heat treatment temperatures such as 510 ° C were used.
  • Figure 15 shows the heat treatment temperature (the temperature of the sample during heat treatment) and the heat treatment time (holding the heat treatment temperature). The figure shows the experimental results of investigating the effect of (holding time) on the Sn concentration in the / 3 phase and the area occupancy of the / 3 phase.
  • FIG. 16A is a micrograph showing the crystal structure of brass sample No. 7 shown in FIG. 18 described later, and FIG. 16B is a schematic diagram of the crystal structure created based on FIG. 16A.
  • FIG. 17A is a micrograph showing the crystal structure of the brass sample No. 4 shown in FIG. 18, and FIG. 17B is a schematic diagram of the crystal structure created based on FIG. 17A.
  • the r phase black part in the figure precipitates and grows at the boundary of the ⁇ phase crystal grains (white part in the figure), and the three phases have almost disappeared.
  • the crystal structure shown in Fig. 17 ⁇ contains a sphing phase and three phases, and the crystal grain boundary of the phase (large white part in the figure) and the / 3 phase (small white part in the figure) surrounds the phase.
  • the r phase (the black part in the figure) precipitates in the surface. This is a typical example of the “a + / 3 + r type” of the present invention.
  • the average particle size of the r phase (in this case, the average of the minor axis) is desirably smaller than the average particle size of the sphing and / 3 phases, for example, 8 m or less, more preferably 5 m or less.
  • FIG. 18 shows seven types related to the “a + r type” and “hi + 3 + r type” of the present invention. List the troublesome brass samples No. i to No. 7 (different from the samples shown in FIGS. 2A to 2C). The Zn content, the area occupation ratio of the ⁇ phase, the results of the corrosion resistance (dezincification corrosion resistance) test, and the Sn concentration in the ⁇ phase are shown. The corrosion resistance test was performed in the same manner as described with reference to FIGS. 2A to 2C.
  • FIG. 19 shows an example of a method for producing a brass product according to the present invention.
  • hot forging or hot extrusion is performed on a Cu-Zn-Sn-based brass material having a composition like Sample No. 3 to No. 7 shown in Fig. 18.
  • Mold with Next this molded body is subjected to a heat treatment at a temperature of 40 ° C. or more and a temperature of 550 ° C. or less and a holding time of 30 seconds or more.
  • the crystal structure of the compact becomes the “hi +?” Type or “13 + r” of the present invention. Apply plating and the like.
  • FIG. 21 shows the results of an experiment in which the relationship between the area occupancy ratio of the r phase and the heat treatment conditions was examined.
  • Cu-Zn-Sn-based copper alloy having the composition of sample No. 3 shown in Fig. 18 was heat-treated at different processing temperatures (sample temperatures) and temperature holding times. After each heat treatment, the area occupancy ratio (%) of the r phase was examined. When the temperature was below 45 ° C, it was 5-1 OKZec.
  • Figure 21 shows that if the heat treatment temperature is between 550 ° C and 400 ° C, the holding time is 30 seconds or more, and the cooling rate is between 5 K / sec and 1 OKZsec, the area occupancy ratio of the r phase
  • the heat treatment temperature should be lower than 550 ° C to make the area occupation ratio (%) of r phase more than 3%.
  • the crystal structure of “h + r type” is formed, and in the heat treatment in the treatment temperature range of 450 ° C to 550 ° C, + 3 + r type ”crystal structure.
  • the average crystal grain size is 15 m or less, preferably 10 m or less.
  • Such fine crystal grains have the advantage that they can be hot forged at a considerably lower temperature than conventional products, and have considerably higher hot ductility (ductility in the forging temperature range) and yield point strength (yield strength). No.
  • the ratio of the phases to the three phases in the recrystallization temperature range is in an appropriate range, that is, the ratio of the three phases is 30%. Adjust the amount of zinc to be ⁇ 80%. The ratio of the / 3 phase within the above range is useful for causing dynamic recrystallization during subsequent hot extrusion or hot working.
  • the grain refinement Effective ⁇ Another method to help refine the crystal grains during the manufacturing stage is to add elements such as B, Fe, i, P, Co, b, ⁇ i, and Zr to the raw material. is there.
  • B is ⁇ . 005 to 0.5
  • Fe is 0.01 to 2.0
  • Ni is 0. 05 to 0.2
  • P is ⁇ . 0. 2
  • Co is 0.0 1 ⁇ 2.
  • T i is 0. 01 ⁇
  • Z r is from 0.005 to 0.5 is appropriate c
  • P is added together with Fe, a synergistic effect is observed.
  • the above-mentioned intermediate molded body is heated to a temperature in the range of 480 to 650 ° C (more preferably, in the range of 4 to 80 to 600 ° C), and hot-extrusion is performed at that temperature to obtain a rod or a wire.
  • the area reduction rate is set to 90% or more (more preferably 95%), and dynamic recrystallization is effectively generated to prevent coarsening of crystal grains.
  • it is rapidly cooled at a rate of 0.4 KZsec or more until the temperature becomes 400 ° C or less to prevent the crystal grains from becoming coarse. Further, lowering the heating temperature of the intermediate compact and shortening the heating time are also effective for preventing the crystal grains from becoming coarse.
  • the bar or wire is cold-drawn, annealed and pickled, cut to a predetermined size, and a billet for fabrication is obtained (step 3).
  • the resulting billet is heated to ensure properties for subsequent hot forging.
  • the heating temperature is in the range of 480 to 750 ° C, and fine crystal grains are maintained by shortening the heating time.
  • the heated billet is set in a forging die, and hot forging is performed at a temperature within a range of 480 to 750 ° C (step 5). At this time, it is effective to reduce the time from heating to forging in order to suppress the growth of coarse grains and maintain fine crystal grains.
  • cooling is performed to shift to pickling shot blast. The cooling rate was set to ⁇ .4KZs to prevent crystal grains from coarsening after dynamic recrystallization during hot forging. It is useful to make it ec or more.
  • the cooling rate after extrusion and extrusion conditions contribute to the refinement of crystal grains.
  • the contribution of the cooling rate to the refinement of crystal grains will be specifically described with reference to FIGS.
  • FIG. 22A is a micrograph showing the crystal structure of the brass material produced at a cooling rate of 19 K / sec after fabrication.
  • FIG. 22B is a schematic diagram created based on FIG. 22A.
  • FIG. 23A is an enlarged micrograph of a part of FIG. 22B
  • FIG. 23B is a schematic diagram created based on FIG. 22A.
  • Fig. 24A is a micrograph showing the crystal structure of the brass material when the cooling rate after fabrication is 1.3 K / sec
  • Fig. 24B is a schematic diagram created based on Fig. 24A.
  • FIG. 25A is an enlarged micrograph of a part of FIG. 24A
  • FIG. 25B is a schematic diagram created based on FIG. 25A.
  • the crystal can be refined by increasing the cooling rate after fabrication.
  • the cooling rate was set to 19 KZsec
  • the average crystal grain size was less than 15 am, and almost all regions had a mixed structure of the sphing and ⁇ phases.
  • the cooling rate was set to 1.3 K / sec
  • the average crystal grain size was 15 m or more, and the r phase was precipitated at the boundary between the single phase and the zero phase.
  • JIS Japanese Industrial Standards
  • Figure 26A shows a brass material with a composition of 58.3wt% Cu, 1.9wt% Sn, and the balance of Zn, with an extrusion temperature of 550 ° C; an extrusion ratio of 50%, 5 is a micrograph showing the crystal structure of a rod-shaped extruded product extruded under the condition that the cooling rate by forced air cooling is 3 OK / sec.
  • Figure 26B is a schematic created based on Figure 26A
  • FIG. Fig. 27A shows the rod-shaped extruded product shown in Fig. 26, ⁇ cylindrical shape, compression method uniaxial compression, forging rate 50%, forging temperature 550 ° (: cooling rate after forging is 20 K /
  • Fig. 27B is a micrograph showing the crystal structure of a forged product forged under the condition of sec
  • Fig. 27B is a schematic diagram created based on Fig. 27A.
  • the brass material shown in Figs. 26A and 26B is a mixture of ⁇ phase and / 3 phase.
  • the ratio of / 3 phase during structural heating is 30% or more and 80% or less, and the average crystal grain size is 15 m or less. It belongs to the “ ⁇ + enhanced three types” of the present invention.
  • this brass material does not change in the crystal grain size, the ratio between the ⁇ phase and the / 3 phase and the shape of the crystal grains even after forging. ⁇ No cracking occurred.
  • Figure 28 28 shows a brass material with a composition of 18.7% by weight, 2.3% by weight of Sn, and the balance of Zn, with an extrusion temperature of 550 ° C, an extrusion ratio of 50%, and after extrusion.
  • 3 is a photomicrograph showing the crystal structure of a rod-shaped extruded product extruded under the condition that the cooling rate by forced air cooling is 30 K / sec.
  • FIG. 28B is a schematic diagram created based on FIG. 28A.
  • Fig. 29A shows the rod-shaped extruded product shown in Fig.
  • FIG. 29B is a schematic diagram created based on FIG. 29A.
  • the brass material shown in FIG. 28 also belongs to the “+ strengthened / 3 type” of the present invention.
  • this material did not cause forging cracks, even though the Sn content ratio was much higher than 1 wt%, which was conventionally considered to cause forging cracking. The reason is presumed to be that the crystal grain size is fine.
  • the energy sources that cause dynamic recrystallization are thermal energy due to heating and strain energy due to external force.
  • dislocation occurs in the soft three-phase particles due to stress from the hard phase particles. If the grain size of the phase is large, the strain in the three phases is concentrated locally (perhaps because the movement of the dislocation-generated / 3 grain is hindered by large grains).
  • the crystals of the phase are fine, the strain in the phase is dispersed (possibly due to grain boundary sliding between the ⁇ grains and the grains moving). Dispersed strains have higher overall potential energy of strains than local strains, so they recrystallize beyond the threshold, and thus have good hot ductility.
  • FIG. 30 shows the preferred conditions for the final crystal structure at room temperature, the crystal structure during hot working (that is, in the recrystallization temperature range), and the composition for the four types of brass of the present invention.
  • FIG. 31 shows typical conditions for initially producing a brass material and typical conditions for hot extrusion when the brass material is hot extruded to obtain the final composition shown in FIG. 30.
  • Figure 32 shows the typical conditions for extrusion and forging when a brass material is hot extruded and hot forged to obtain the final composition.
  • Figure 33 shows extruding, forging, and brazing when brass material is hot extruded, then hot forged, and then heat treated to obtain the final composition.
  • the typical conditions of heat treatment are shown. Particularly preferred numerical ranges are shown in parentheses in the figure.
  • the “hi +” type brass has a crystal structure of hi + r.
  • the area ratio of the phase is 97 to 70%-, the area ratio of the phase is 3 to 30%, preferably the area ratio of the sphing phase is 95 to 70% and the area ratio of the ⁇ phase is 5 to 30%.
  • the average particle size of the sphing phase is 15 m or less, preferably 10 m or less.
  • the average particle size (minor diameter in this case) of the phase is not more than 8 ⁇ m, preferably not more than 5 m. According to the micrographs, a thin layer (less than 8 m thick) of the phase is formed at the grain boundary of the phase.
  • the Sn concentration of the r phase was 8 wt% or more, for example, 14 to 18% in Examples 1 to 5 shown in FIGS. 2A to 2C.
  • “+ / 3 + T” type brass has a + 3 + r crystal structure.
  • the area ratio of the sphing phase is 40-94%, and the area ratio of each of the / 3 phase and the r phase is 3-30%.
  • the phase was 65 to 82.5%, the / 3 phase was 9.8 to 13.4%, and the r phase was 4 to 24%.
  • the average particle size of the sphing and / 3 phases is less than 15 ⁇ m, preferably less than 10 ⁇ m.
  • the average particle size (in this case, the minor axis) of the r phase is 8 ⁇ m or less, preferably 5 or less.
  • a thin layer of r-phase (8 m or less in thickness) is formed so as to surround the / 3-phase crystal.
  • the Sn concentration of the phase was 8 wt.% Or more, for example, 11 to 13.4% in Examples 6 to 12 shown in FIGS. 2A to 2C.
  • the "+ Normal 3 type” brass has a + / 3 crystal structure.
  • the area ratio of the three phases was 20% or more, and preferably 25% or more. For example, in Examples 13 to 15 shown in FIGS. 2A to 2C, the area ratio was 23.1 to 25.6%.
  • the average crystal grain size of the phase and the phase is 15 m or less, preferably 10 m or less.
  • the brass of " ⁇ + Strength / 3-Yu-type” has a crystal structure of Hi + / 3.
  • the area ratio of the three phases was 15% or more, and preferably 20% or more. For example, in Examples 16 to 19 shown in FIGS. 2A to 2C, the area ratio was 23 to 38%.
  • the average crystal grain size of the sphing and / 3 phases is 15 ⁇ m or less, preferably 10 ⁇ m or less.
  • the Sn concentration of the / 3 phase is 1.5 wt% or more, for example, 2.5 to 7.1 wt% in Examples 16 to 19 shown in FIGS. 2A to 2C. Met.
  • All types of brass have a +0 crystal structure in the recrystallization temperature range, and the area ratio of the / 3 phase is 30 to 80%.
  • the average crystal grain size of the phase and the / 3 phase is 15 m or less, preferably 10 m or less.
  • the crystal grains are present substantially uniformly dispersed.
  • the apparent Zn content is 37 to 46 wt%, and 38 to 46 wt% is preferable to obtain good hot ductility. Good.
  • the overall Sn content is between 0.9 and 7 wt%.
  • the apparent Zn content is 37.8 to 44 wt%, and the overall Sn content is 1 to 5 w. t%.
  • the apparent Zn content was 41.5 to 44 wt%, and the overall Sn content was 1.5 to 3.5 wt%. there were.
  • the apparent Zn content is 37-44 wt%, and preferably 38-44 wt% in order to obtain good hot ductility.
  • the apparent Zn content was 41.8 to 44 wt%.
  • the overall Sn content is less than 0.5 wt%.
  • the apparent Zn content is 37 to 44 wt%, and 38 to 44 wt% is preferable for obtaining good ripeness ductility.
  • the overall Sn content is ⁇ .5-7 wt%.
  • the apparent Zn content is 40.1 to 42.6 wt%, and the overall Sn content is 0. It was 8 to 3.6 wt%.
  • the solidification rate during the production is 5 ⁇ 10 1 to 10 5 K / sec, preferably 10 2 to 10 5 KZ sec.
  • the solidification rate 1 0 5 KZs ec is the upper limit value does not become an amorphous state.
  • the cooling rate after solidification is 5KZsec or more until it becomes 40 ° C or less.
  • Hot extrusion conditions when the final structure is obtained by hot extrusion (FIG. 31)
  • the temperature at the time of extrusion is 480 to 650 ° C, preferably 480 to 600 ° C.
  • the area reduction rate is 90% or more, preferably 95% or more.
  • “F + r type” is 0.4 to 5K / sec
  • “+ / S + type” is 0.4 to i OKZs ec, + Normal 3 types ”is 0.4 ° CZs ec or more
  • “ H + Strength / 3 types ” is 5-10 ⁇ OKZs ec.
  • the conditions for hot extrusion are the same as those described in (6) above, except that the cooling rate after extrusion must be 0.4 ° C or higher until the cooling rate is 400 ° C or lower, regardless of the type. It is.
  • the hot working temperature is 480 to 750 ° C, for example, 500 to 600 ° C in the embodiment shown in FIGS. 2A to 2C.
  • the strain rate of forging is preferably 1 / sec or more.
  • the cooling rate is the same as that after extrusion described in (6) above.
  • the conditions for hot extrusion are the same as those described in (7) above.
  • the conditions for hot forging are the same as those described in (7) above, except that the cooling rate after forging must be at least 0.4 ° C until it falls to 400 ° C or less, regardless of the type. It is.
  • the heat treatment is not necessary when making “ ⁇ + Normal 3 type” (that is, if the hot structure is performed under the above conditions, the final composition of “H + Normal / 3 type” is obtained).
  • the “H + + ⁇ type” is held at 400 to 550 ° C for 30 seconds or more, and the “H + / 3 + r type” is 450 ⁇ Hold at 550 ° C for 30 seconds or more, and “H + Reinforced 3 types” hold at 475 to 55 CTC for 30 seconds or more.
  • the cooling rate after the heat treatment is the same as that after the extrusion described in (6) above.
  • water contact parts such as valves and faucets, sanitary ware fittings, various fittings, pipes, gas appliances.
  • water contact parts such as valves and faucets, sanitary ware fittings, various fittings, pipes, gas appliances.
  • water contact parts in which the brass according to the present invention can be used include a fitting for a water faucet, a water heater, a hot water flush toilet seat, a water supply pipe, a connection pipe, and a valve.
  • FIG. 34 shows an example of a faucet fitting using the brass of the present invention.
  • the spurt 25 is connected to the main pressure-resistant main body 21 to which the primary pressure is applied, via the low pressure-resistant joint 23 on the secondary pressure side. It is connected.
  • the minimum thickness of the main body 21 is 0.2 mm or more, and the minimum thickness of the joint and the spout is 0.1 mm or more.
  • a brass structure of the present invention is used for an elbow pipe 29 connected to a water pipe 27.
  • the brass structure according to the present invention is used for the fitting 33 to the shower hose 31.
  • a forged product of brass according to the present invention is used for a joint 41 between the pipes 35, 37, and 39.
  • Figures 38, 39 and 40 show parts of a water heater using the brass of the present invention.
  • Figure 38 shows a cross-sectional view of the entire water heater.
  • the brass of the present invention is used for the pressure reducing valve 53 connected to the water inlet pipe 51 and the relief valve 57 connected to the water supply pipe 55 from the pressure reducing valve 53.
  • the valve box 6 1 and the valve 6 3 are provided, and in the relief valve 57 shown in FIG. (Parts indicated by hatching) uses the brass of the present invention.
  • the brass according to the present invention is excellent in corrosion resistance and acid resistance, when used for the above-mentioned water contact parts, the strength change due to aging of the water contact parts is small. Further, the brass of the present invention not only has excellent corrosion resistance and acid resistance but also has high strength, so that the wall thickness of the water contact component can be reduced.
  • the JIS standard for lined faucets requires a pressure-resistant performance of 17.5 kg Z cm 2 for the metal part of the water pressure resistance to which the primary pressure is applied. It is necessary to determine the wall thickness of the water contact parts in consideration of the reduction in wall thickness due to temporary corrosion to this pressure resistance performance. Conventionally, the minimum wall thickness of a cylindrical faucet of 10 O mm has been determined to be about 1.0 to 1.5 mm. On the other hand, when the brass according to the present invention is used, the minimum thickness can be reduced to about 0.8 mm to about 2 mm.
  • the brass of the present invention has good machinability, so that the cutting time can be shortened, and since the hot ductility is high, it can be formed in a short time by forging or the like. Furthermore, since it is possible to form by forging, the degree of freedom in design increases. Since it has high hot ductility and can be forged at a low temperature of 600 ° C or less, the accuracy of forged products and surface accuracy are improved, and there is no oxide film. (+ + R, + r, + normal 3 and ⁇ + reinforced) according to the present invention) This includes those where other metals such as steel were used, and those where traditionally non-metallic materials were used.
  • Brass materials of various shapes such as materials, pipes, rods, wires and lumps, intermediate products, finished products, their assemblies, and composite products combined with other material products. Welding, fusion welding, brazing, bonding, thermal cutting, thermal processing, forging, extrusion, drawing, rolling, shearing, sheet forming, roll forming, rolling, spinning, bending, straightening, high energy speed processing, powder processing Brass materials, intermediate products, final products, their assemblies, and composite products combined with other materials manufactured by various processes such as cutting, grinding and grinding. Brass materials, intermediate products, final products, their assemblies, and composite products combined with other materials that have been subjected to various surface treatments such as metal coating treatment, chemical conversion treatment, surface hardening treatment, non-metallic coating treatment, and painting .
  • Transmission parts such as synchro gears and bearings.
  • Engine parts such as timing gears, pulleys, bearings, fittings, fuel pipes, exhaust pipes, gaskets, injection nozzles, engine blocks, etc.
  • Raje Yuichi parts such as fittings.
  • Vehicle body Exterior parts, such as malls, door handles, wipers, etc.
  • Interior parts such as meters and alarms.
  • Drivetrain components such as tire air nozzles, axles, wheelbases, etc.
  • Brake parts such as fittings.
  • Serpentine parts such as hydraulic joints and gears.
  • Air conditioner parts such as fittings.
  • Suspension parts such as bearings, etc.
  • Hydraulic pump parts such as bodies, valves, pistons, etc.
  • Engine parts such as timing gears, pulleys, bearings, joints, fuel pipes, exhaust pipes, gaskets, injection nozzles, engine blocks, etc. Hull. Outfitting parts, such as railings, moldings, door handles, masts, etc. Drivetrain components, such as screws, propellers, shafts, etc. Instrument parts, such as casings and handles. Manipulation parts. Air conditioner parts. Hydraulic pump section DDo
  • Engine parts such as timing gears, pulleys, bearings, joints, fuel pipes, exhaust pipes, gaskets, injection nozzles, engine blocks, etc.
  • Motor parts for example, body, bearings, cooling joints, etc.
  • Transmission parts such as synchro gears, bearings, etc.-Rage Yuichi parts, such as joints.
  • Vehicle body Exterior parts, such as malls, door handles, wipers, etc.
  • Interior parts such as meters, alarms, and handrails.
  • Drivetrain components such as tire air nozzles, axles, wheelbases, etc.
  • Brake parts such as fittings.
  • Serpentine parts such as hydraulic fittings, gears, and handles.
  • Air conditioner parts such as fittings.
  • Suspension parts such as bearings.
  • Hydraulic pump parts such as body, valve, piston, etc. Pantograph parts, such as joints. Overhead parts, such as joints.
  • Engine parts such as timing gears, pulleys, bearings, joints, fuel pipes, exhaust pipes, gaskets, injection nozzles, engine blocks, etc.
  • Motor parts such as body parts, bearings, cooling joints, etc.
  • Transmission parts such as synchro gears and bearings.
  • Raje Yuichi parts such as fittings.
  • Exterior parts such as malls, door handles, wipers, etc.
  • Interior parts such as meters and alarms.
  • Brake parts such as fittings.
  • Serpentine parts such as hydraulic joints, gears, and handles.
  • Sky Conditioning parts such as joints.
  • Suspension parts such as bearings.
  • Hydraulic pump parts such as body, valve, piston etc.
  • Parts for gas welding machines such as torches.
  • Boiler parts such as bodies and valves.
  • Solar water heater parts such as body and valve.
  • Piano parts such as pedals, joints, etc.
  • Electone parts such as pedals and joints.
  • Organ parts such as pedals, fittings, resonance pipes, etc.
  • Transit parts such as body parts, pistons, levers, joints, etc.
  • Tonbon parts such as bodies, pistons, levers, and fittings.
  • Tuba parts such as bodies, pistons, levers, fittings, etc.
  • Clarinet parts such as pistons, levers, joints, etc.
  • Bass parts such as pistons, levers, and joints.
  • Drum parts such as holders and cymbals.
  • Taiko parts such as holders and kettles.
  • Xylophone parts such as resonance pipes and frames.
  • Parts for amplifiers, video players, cassette players, CD players, and LD players such as adjustment knobs, legs, chassis, and speaker cones.
  • Room air conditioner parts such as joints, refrigerant pipes, valves, etc.
  • Water heater and electric water heater parts such as casing, hot water storage container, gas piping, gas nozzle, wrench, pressure reducing valve, relief valve, proportional valve, solenoid valve, and pump parts.
  • Room heater and room cooler parts such as vaporizers, refrigerant pipes, service valves, and flarenuts.
  • Washing machine parts such as casings and washing tubs.
  • Pachinko machine parts Slot machine parts.
  • Vending machine parts for example, coin slot, coin exchange, etc.
  • Control board a printed wiring board, switchboard electrodes, switch parts, resistor parts, power plug parts, lamp cap, the lamp holder component, discharge electrodes, water-immersed electrodes, copper wires, battery terminals, casing, solder s.
  • Exterior building materials building material mounting parts, wall panels, reinforcing bars, steel frames, etc.
  • Door parts such as door panels, knobs, locks, moldings, hinges, etc.
  • Gate parts such as gate posts, gates, malls, hinges, etc. ⁇ Parts, such as ⁇ body, mall, etc. Outside light Parts, such as casings, shades, struts, etc. shutter. Veranda fuence. Mailbox. Keep in rain. Rain gutter bracket. roof. sprinkler. Flexible tube.
  • Handrail parts such as handrail pipes and fittings.
  • Door parts such as knobs, locks, moles, hinges, etc.
  • Kitchen utensils such as gas pans and stove tops.
  • Bathroom products for example, water distribution holes, drain cocks, drain cocks, shower hangers, sprinklers, etc.
  • Toiletries counter fittings if it's clear, evening olver, etc.
  • Living room accessories such as chandelier parts, lighting parts, decorative figurines, etc.
  • Toilet supplies such as the outer wall panel of a toilet booth. Furniture parts, such as chair legs, table legs, table tops, hinges, handles, rails, shelf adjustment screws, etc.
  • Handrail parts such as handrail pipes and fittings.
  • Buddhist altar parts such as Buddha statues, malls, candlesticks, bells, etc.
  • Parts for cameras, telescopes, microscopes and electron microscopes such as bodies, mounts and lens cases.
  • Parts of watches, wall clocks and clocks such as bodies, hands, moldings, gears, and pendulums.
  • Drain plugs fittings for rigid PVC pipes, drain grooves, elbow pipes, fittings, bellows for flexible fittings, plumbing cocks, valves, connecting flanges for toilet bowls, stems, spindles, ball valves, balls, seat rings, knocking nuts , KCP joint, header, branch tap, flexible hose, hose nipple, faucet body, faucet accessory, valve body, ball tap, water stopcock, single function faucet, thermos with water Faucet, 2 valve wall faucet, 2 valve stand faucet, spurt, UB elbow, mixi
  • Golf club parts such as shafts, heads, toes, heels, soles, etc.
  • Cups, replicas, Rai Yuichi candlesticks, character goods, medals, bells, hairpins, hot curlers, ashtrays, vases, keys, coins, fishing tackle, lures, eyeglass frames, claws, pachinko balls, insect cages, Umbrellas, sword mountains, needles, pruning scissors, horticultural supports, horticultural frames, horticultural shelves, flower arrangements, finger pulls, lanterns, safes, casters, etc.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Forging (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Conductive Materials (AREA)
  • Metal Extraction Processes (AREA)
  • Extrusion Of Metal (AREA)
  • Domestic Plumbing Installations (AREA)
  • Chemically Coating (AREA)
  • Laminated Bodies (AREA)
  • Adornments (AREA)

Abstract

Cette invention concerne un procédé de fabrication d'un matériau métallique, et notamment du laiton, qui présente d'excellentes caractéristiques de résistance mécanique, de capacité de coupe, de malléabilité lors du corroyage et de pouvoir anticorrosif. Le laiton fabriqué conformément à l'invention peut être classé grossièrement en quatre types: 'α + η', 'α + β + η', 'α + β normal' et 'α + β renforcé'. Le laiton de type α + η est α + η à température ambiante et sa phase α possède un rapport surfacique compris entre 70 et 97 %. Le laiton de type α + β + η est α + β + η à température ambiante et ses phases β et η possèdent chacune des rapports surfaciques compris entre 3 et 30 %. Dans ces deux types de laiton, la phase η contient au moins 8 % en poids d'étain (Sn). Le laiton de type α + β normal est α + β à température ambiante et sa phase β possède un rapport surfacique supérieur ou égal à 20 %. Le laiton de type α + β renforcé est α + β à température ambiante, sa phase β possède un rapport surfacique supérieur ou égal à 15 % et cette phase β contient au moins 1,5 % en poids de Sn. Ces différents types de laiton sont α + β au voisinage de la température de recristallisation et leurs phases β possèdent des rapports surfaciques compris entre 30 et 80 %. Les tailles moyennes des grains cristallins des phases α et β sont inférieures ou égales à 15 νm, et de préférence inférieures ou égales à 10 νm. Un grain cristallin moyen de phase η possède un petit axe moyen inférieur ou égal à 8 νm, et de préférence inférieur ou égal à 5 νm. Les laitons de type α + η et α + η + β possèdent une teneur apparente en zinc (Zn) comprise entre 37 et 46 % en poids, et une teneur totale en Sn comprise entre 0,9 et 7 % en poids. Les laitons des deux autres types possèdent une teneur apparente en Zn comprise entre 37 et 44 % en poids.
PCT/JP1997/003152 1996-09-09 1997-09-08 Alliage de cuivre et procede de fabrication correspondant WO1998010106A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002265812A CA2265812A1 (fr) 1996-09-09 1997-09-08 Alliage de cuivre et procede de fabrication correspondant
DE69720261T DE69720261T2 (de) 1996-09-09 1997-09-08 Kupferlegierung und verfahren zu deren herstellung
EP97939214A EP0947592B1 (fr) 1996-09-09 1997-09-08 Alliage de cuivre et procede de fabrication correspondant
AT97939214T ATE235573T1 (de) 1996-09-09 1997-09-08 Kupferlegierung und verfahren zu deren herstellung
JP51249198A JP3303301B2 (ja) 1996-09-09 1997-09-08 銅合金及びその製造方法
AU41360/97A AU4136097A (en) 1996-09-09 1997-09-08 Copper alloy and method of manufacturing same

Applications Claiming Priority (20)

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JP8/237591 1996-09-09
JP23759196 1996-09-09
JP29177596 1996-11-01
JP8/291775 1996-11-01
JP9/4027 1997-01-13
JP402797 1997-01-13
JP9/31849 1997-02-17
JP3184997 1997-02-17
JP7411197 1997-03-26
JP9/74111 1997-03-26
JP16783697 1997-05-20
JP9/167836 1997-05-20
JP9/167837 1997-05-20
JP16783797 1997-05-20
JP9/167834 1997-05-20
JP16783597 1997-05-20
JP9/167833 1997-05-20
JP16783397 1997-05-20
JP9/167835 1997-05-20
JP16783497 1997-05-20

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EP (2) EP0947592B1 (fr)
JP (1) JP3303301B2 (fr)
KR (1) KR20000068520A (fr)
CN (1) CN1100152C (fr)
AT (1) ATE235573T1 (fr)
AU (1) AU4136097A (fr)
CA (1) CA2265812A1 (fr)
DE (1) DE69720261T2 (fr)
ID (2) ID19391A (fr)
WO (1) WO1998010106A1 (fr)

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JP2006520850A (ja) * 2003-03-21 2006-09-14 スイスメタル−ユエムエス・ユジン・メタルリュルジク・スイス・エスア 銅系合金
JP3951604B2 (ja) * 1997-11-11 2007-08-01 Ｔｏｔｏ株式会社 金属材料、黄銅及びその製造方法
WO2009136552A1 (fr) 2008-05-07 2009-11-12 独立行政法人科学技術振興機構 Poudre de laiton spécial, matière extrudée de laiton spécial et procédé pour la fabrication de la matière extrudée de laiton spécial
US7883589B2 (en) 2005-09-22 2011-02-08 Mitsubishi Shindoh Co., Ltd. Free-cutting copper alloy containing very low lead
US8506730B2 (en) * 1998-10-09 2013-08-13 Mitsubishi Shindoh Co., Ltd. Copper/zinc alloys having low levels of lead and good machinability
WO2015166998A1 (fr) * 2014-04-30 2015-11-05 株式会社キッツ Procédé de production pour des articles forgés à chaud à l'aide de laiton, article forgé à chaud et produit destiné à être en contact avec des fluides tel qu'une valve ou un robinet moulé à l'aide de ce dernier
WO2017204252A1 (fr) * 2016-05-25 2017-11-30 三菱伸銅株式会社 Article de formage à chaud en alliage de laiton, et procédé de fabrication de celui-ci
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FR2856411B1 (fr) * 2003-06-17 2007-03-02 Trefimetaux ALLIAGES CuZnPbSn DESTINES AU MATRICAGE A CHAUD
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ES2294604T3 (es) * 2005-07-28 2008-04-01 Gebr. Kemper Gmbh + Co. Kg Metallwerke Procedimiento de fabricacion de piezas fundidas en cobre, con tendencia a la migracion reducida.
EP2119801A4 (fr) 2006-12-28 2013-07-24 Kitz Corp Alliage de laiton exempt de plomb présentant une excellente résistance à la fissuration de corrosion sous contrainte
JP4630323B2 (ja) * 2007-10-23 2011-02-09 株式会社コベルコ マテリアル銅管 破壊強度に優れた熱交換器用銅合金管
DE102009038657A1 (de) * 2009-08-18 2011-02-24 Aurubis Stolberg Gmbh & Co. Kg Messinglegierung
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JP5873175B2 (ja) 2012-08-09 2016-03-01 Ykk株式会社 ファスニング用銅合金
US10287653B2 (en) 2013-03-15 2019-05-14 Garrett Transportation I Inc. Brass alloys for use in turbocharger bearing applications
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3951604B2 (ja) * 1997-11-11 2007-08-01 Ｔｏｔｏ株式会社 金属材料、黄銅及びその製造方法
US8506730B2 (en) * 1998-10-09 2013-08-13 Mitsubishi Shindoh Co., Ltd. Copper/zinc alloys having low levels of lead and good machinability
JP2006520850A (ja) * 2003-03-21 2006-09-14 スイスメタル−ユエムエス・ユジン・メタルリュルジク・スイス・エスア 銅系合金
US7883589B2 (en) 2005-09-22 2011-02-08 Mitsubishi Shindoh Co., Ltd. Free-cutting copper alloy containing very low lead
WO2009136552A1 (fr) 2008-05-07 2009-11-12 独立行政法人科学技術振興機構 Poudre de laiton spécial, matière extrudée de laiton spécial et procédé pour la fabrication de la matière extrudée de laiton spécial
WO2015166998A1 (fr) * 2014-04-30 2015-11-05 株式会社キッツ Procédé de production pour des articles forgés à chaud à l'aide de laiton, article forgé à chaud et produit destiné à être en contact avec des fluides tel qu'une valve ou un robinet moulé à l'aide de ce dernier
JPWO2015166998A1 (ja) * 2014-04-30 2017-04-20 株式会社キッツ 黄銅を用いた熱間鍛造品の製造方法と熱間鍛造品及びこれを用いて成形したバルブや水栓などの接液製品
US10533244B2 (en) 2014-04-30 2020-01-14 Kitz Corporation Method of producing hot forged product using brass and hot forged product and wetted product such as valve and water faucet molded using the same
WO2017204252A1 (fr) * 2016-05-25 2017-11-30 三菱伸銅株式会社 Article de formage à chaud en alliage de laiton, et procédé de fabrication de celui-ci
JP6304915B1 (ja) * 2016-05-25 2018-04-04 三菱伸銅株式会社 黄銅合金熱間加工品及び黄銅合金熱間加工品の製造方法
US11473172B2 (en) 2017-03-24 2022-10-18 Ihi Corporation Wear-resistant copper-zinc alloy and mechanical device using same

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EP0947592A1 (fr) 1999-10-06
CA2265812A1 (fr) 1998-03-12
EP0947592B1 (fr) 2003-03-26
DE69720261T2 (de) 2003-11-27
KR20000068520A (ko) 2000-11-25
ATE235573T1 (de) 2003-04-15
EP1270758A3 (fr) 2003-03-05
EP0947592A4 (fr) 2000-03-22
ID19391A (id) 1998-07-09
AU4136097A (en) 1998-03-26
JP3303301B2 (ja) 2002-07-22
EP1270758A2 (fr) 2003-01-02
ID21785A (id) 1999-07-22
CN1100152C (zh) 2003-01-29
DE69720261D1 (de) 2003-04-30
CN1230230A (zh) 1999-09-29

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