EP3279347A1 - Alliage d'acier pour élément d'alimentation en eau - Google Patents

Alliage d'acier pour élément d'alimentation en eau Download PDF

Info

Publication number: EP3279347A1
Authority: EP; European Patent Office
Prior art keywords: mass; less; content; balance; comparative example
Prior art date: 2015-03-31
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

EP15887566.6A

Other languages

German (de)

English (en)

Other versions

EP3279347A4 (fr

EP3279347B1 (fr

Inventor

Takeaki Miyamoto

Masaaki Yamamoto

Syohei MATSUBA

Hiroshi Yamada

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.)

Kurimoto Ltd

Original Assignee

Kurimoto 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.)

2015-03-31

Filing date

2015-03-31

Publication date

2018-02-07

2015-03-31 Application filed by Kurimoto Ltd filed Critical Kurimoto Ltd

2018-02-07 Publication of EP3279347A1 publication Critical patent/EP3279347A1/fr

2018-03-14 Publication of EP3279347A4 publication Critical patent/EP3279347A4/fr

2021-02-17 Application granted granted Critical

2021-02-17 Publication of EP3279347B1 publication Critical patent/EP3279347B1/fr

Status Active legal-status Critical Current

2035-03-31 Anticipated expiration legal-status Critical

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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

Definitions

the present invention relates to a material for use in a member for water works, which is made of a copper alloy and in which the level of lead leaching is not more than a stipulated value.
a cast bronze metal (JIS H5120 CAC406), which has been conventionally used for parts in materials and equipment for water works and in feed water supply systems, is excellent in castability, corrosion resistance, machinability, and/or water pressure resistance and used for parts in materials and equipment for water works and in feed water supply systems, and the like in various fields.
This cast bronze metal (CAC406) contains from 4.0 to 6.0% by weight of lead so as to have the high machinability, and has characteristics of easy workability.
this lead contained has a property to leach into the tap water in contact with the same, which fails to satisfy recent leaching lead amount regulations.
a copper alloy containing a reduced content of lead, or a lead-free copper alloy which contains no lead have been examined.
Patent Document 1 discloses a brass alloy having an adjusted composition containing from 8 to 40% by mass of Zn, 0.0005 to 0.04% by mass of Zr, 0.01 to 0.25% by mass of P, at least one or more kinds of 0.005 to 0.45% by mass of Pb, 0.005 to 0.45% by mass of Bi, 0.03 to 0.45% by mass af Se, and 0.01 to 0.45% by mass ofTe, and the balance of Cu and unavoidable impurities.
This brass alloy is an alloy in which solid metals and liquid metals mixed in a semi-solid state are solidified, and in the course of its solidification, granular a primary crystals are crystallized or an a solid phase exists.
one or more kinds of 2 to 5% by mass of Si, 0.05 to 6% by mass of Sn, and 0.05 to 3.5% by mass of Al may be contained and in particular, Zr with the coexistence with P is effective in the size reduction in a semi-solid state.
Patent Document 2 discloses a copper alloy for use in a member for water works, the copper alloy containing: less than 0.5% by mass of Ni in a limited manner; less than the detection limit of Pb; 0.2% by mass or more and 0.9% by mass or less of Bi; 12.0% by mass or more and 20.0% by mass or less of Zn; 1.5% by mass or more and 4.5% by mass or less of Sn; and 0.005% by mass or more and 0.1% by mass or less of P; in which a total content of Zn and Sn is 21.5% by mass or less, and the balance being unavoidable impurities and Cu. Further, it is proposed that 0.0003 to 0.006% by mass of B is additionally contained.
the alloy of Patent Document 1 has a problem in that in a range in which the Zn content is high, the dezincification corrosion is prone to occur, and has a property in which in a range in which the Pb content is high, the lead leaching level fails to be satisfied. Moreover, since Bi is contained, there has been a recycle problem as described above.
the improvement in properties is effectively made during a casting process having a small temperature range of solidification, such as that of solidification from a semi-solid state, whereas if in a range in which the Zn content is low and the Sn content is high, Zr is contained and in a process of casting a metal, which is not in a semi-solid state but completely liquid, in a mold, a temperature range to solidification is large so that a compound of Zr may be generated and shrinkage cavities may be facilitated to reduce mechanical properties.
an object of the present invention is to provide a copper alloy for use in a member for water works, which has suitable mechanical properties and castability, while not only inhibiting lead leaching but also maintaining the recyclability.
the present invention has solved the above mentioned problems by a copper alloy for use in a member for water works, the copper alloy consisting of: 0.5% by mass or less of Ni; 12% by mass or more and 21% by mass or less of Zn; 1.4% by mass or more and 4.5% by mass or less of Sn, a total content of Zn and Sn being 23.5% by mass or less; 0.005% by mass or more and 0.15% by mass or less of P; 0.05% by mass or more and 0.30% by mass or less of Pb; less than 0.2% by mass of Bi; and the balance, wherein the balance is Cu and unavoidable impurities.
Bi is limited to be less than 0.2% by mass so as to be capable of being used even when mixed with another alloy in recycling. Meanwhile, even when Bi is less than 0.2% by mass as described above, if Pb is 0.30% by mass or less, effects of improving properties, such as the machinability, due to addition of Pb can be exhibited, while leaching lead amount regulations are satisfied. Further, values of Zn and Sn are adjusted together so as to be such a blending as to be capable of exhibiting sufficient mechanical properties without using Bi which has a large influence in recycling.
Ni is 0.5% by mass or less so as to be capable of inhibiting an occurrence of shrinkage cavities.
this copper alloy may contain in a limited manner an element which may be mixed therein as another unavoidable impurity. Note that its total amount is required to fall within such as range as not to inhibit effects of the present invention, and is preferably less than 1.0% by mass and the content of each of such element is preferably less than 0.5% by mass.
the present invention relates to a copper alloy for use in a member for water works, which contains Pb in a limited manner and is blended without containing Bi.
a Zn content is required to be 12% by mass or more, and preferably 13% by mass or more.
the Zn content of less than 12% by mass results in producing curled machining chips so as to reduce the machinability.
the Zn content is required to be 21% by mass or less, and is preferably 20% by mass or less and more preferably 18% by mass or less. Too high a Zn content results in not only a reduction in mechanical properties but also an increase of zinc residue so as to complicate the casting.
a Sn content is required to be 1.4% by mass or more, and preferably 2.0% by mass or more.
the Sn content of less than 1.4% by mass results in producing curled machining chips so as to reduce the machinability, similarly to effects of Zn.
an oxide film which protects a surface of a member for water works is removed by the water stream so that the resistance to erosion-corrosion in which the corrosion of the alloy progresses becomes insufficient.
the Sn content is required to be 4.5% by mass or less, and is preferably 4.3% by mass or less and more preferably 3.0% by mass or less. This is because too high a Sn content results in a reduced elongation and/or an occurrence of shrinkage cavities during the sand casting.
a total content of Zn and Sn is required to be 23.5% by mass or less, and preferably 21.0% by mass or less. If an amount of Zn solid-solubilized in Cu is too high, the solid solubility of Sn is reduced to result in an increased concentration of Sn in the residual liquid phase during the solidification, and as a result, the crystallization of ⁇ -phase due to peritectic reaction is more likely to occur. Eventually, ⁇ + ⁇ phases, composed of ⁇ -phases scattered in hard ⁇ -phases (Cu 31 Sn 8 ), are generated between dendrites, resulting in a reduction in the tensile strength.
the casting is carried out under the conditions of low solidification rate, such as when producing a thick wall casting or sand casting, there is a potential risk that the resulting casting may develop casting defects during the final solidification, such as a defect referred to as "tin sweat", a state where Sn exudes from the surface of the alloy as if it is sweating, or shrinkage cavity defects. If the total content of Zn and Sn exceeds 23.5% by mass, a reduction in mechanical properties and an occurrence of casting defects will be unignorable.
a P content is required to be 0.005% by mass or more, and preferably 0.01% by mass or more. Since P produces a deoxidizing effect, too low a P content reduces the deoxidizing effect during the casting, resulting not only in an increased occurrence of gas defects, but also in a decreased flowability of molten metal due to oxidation of the molten metal.
the P content is required to be 0.15% by mass or less, and preferably 0.05% by mass or less. If the P content is too high, P reacts with water in the mold to increase the occurrence of gas defects and shrinkage cavity defects in the resulting casting, and the mechanical properties thereof are also reduced.
a Pb content is required to be 0.05% by mass or more, and preferably 0.07% by mass or more. This is because while Pb is contained slightly so as to greatly improve the machinability, the Pb content of less than 0.05% by mass results in its effects insufficient. On the other hand, the Pb content is required to be 0.30% by mass or less, and preferably 0.20% by mass or less. Pb is an element whose leaching should be prevented as much as possible, and if the Pb content exceeds 0.30% by mass, it will be difficult to satisfy a leaching reference value in a leaching test.
Ni content is required to be 0.5% by mass or less. Ni may not be contained but produces effects exhibiting stable mechanical properties, and, at the same time, produces effects of inhibiting an occurrence of shrinkage cavities, which facilitates production of a decent casting. On the other hand, if the Ni content exceeds 0.5% by mass, the machinability is prone to be reduced.
the above mentioned copper alloy may contain another impurities as the balance, in addition to Cu, within such a range as not to inhibit effects of the present invention.
the content is preferably restricted to such an extent as to be contained as unavoidable impurities which are unavoidably contained in view of problems of raw materials and problems during production.
a total amount of the elements which constitute the unavoidable impurities is preferably less than 1.0% by mass, and more preferably less than 0.5% by mass. This is because, if too much unexpected elements are incorporated in the alloy, even if the above mentioned elements are contained within the above mentioned ranges, there is a potential risk that the physical properties of the alloy may be deteriorated.
a content of each element is preferably less than 0.4% by mass.
a content of Bi is preferably less than 0.2% by mass, more preferably less than 0.1% by mass, and still more preferably less than the detection limit. Since Bi is not solid-solubilized in Cu, but dispersed, a higher Bi content is more prone to cause a reduction in the strength, such as the tensile strength. Further, such dispersed Bi leads to a tendency to easily cause an occurrence of shrinkage cavities during the sand casting.
a content of Si is preferably less than 0.01% by mass, and more preferably less than 0.005% by mass. Too high a Si content results in facilitation of shrinkage cavities so that a decent casting fails to be produced.
a content of Al is preferably less than 0.01% by mass, and more preferably less than 0.005% by mass.
Si too high an Al content results in facilitation of shrinkage cavities so that a decent casting fails to be produced.
a content of Sb is preferably less than 0.05% by mass, more preferably less than 0.03% by mass, and still more preferably less than the detection limit. Since Sb tends to form Cu-Sn-Sb-based intermetallic compounds, which tend to reduce the toughness of the alloy, there is a risk that the mechanical properties of the alloy may be reduced.
a content of Zr is preferably less than 0.01% by mass, more preferably less than 0.0005% by mass, and still more preferably less than the detection limit. Containing Zr results in degradation of mechanical properties and facilitation of shrinkage cavities so that a decent casting fails to be produced.
the content of each of the unavoidable impurities is preferably less than 0.4% by mass, more preferably less than 0.2% by mass, and still more preferably less than the detection limit.
impurities include Fe, Mn, Cr, Mg, Ti, Te, Se, Cd, etc.
the content of Se and Cd, which are known to be toxic is each desirably less than 0.1 % by mass, and more preferably less than the detection limit.
the values of the content of the elements as described in the present invention denote the values of the content of elements in the resulting casting or forging, not the content thereof in the raw materials.
the balance of the above mentioned copper alloy is Cu.
the copper alloy according to the present invention can be produced by a common method for producing a copper alloy.
a common casting method such as sand casting
a member for water works can be prepared by a method in which an alloy is melted using an oil furnace, gas furnace, or high frequency induction melting furnace, and then cast using molds in various shapes.
a sample prepared by being cast into a shape of type A sample defined in JISH 5120 was processed into a type 4 test specimen defined in JISZ 2241. Specific shapes are each indicated in FIGS. 1 and 2 .
a type A test specimen in FIG. 1 is a hatched portion in the figure, and the unit of the size is mm.
a diameter d o is 14 ⁇ 0.5 mm
an original gauge length of the test specimen L o is 50 mm
a length of a parallel portion L c is 60 mm or more
a radius of a shoulder portion R is 15 mm or more.
test specimen With respect to this test specimen, the tensile strength and elongation were then measured in accordance with JIS Z2241. The mechanical properties of each of the test specimens were evaluated based on the thus obtained values.
threshold values are reference values for JIS H5120 CAC406 generally used in a member for water works.
a sample prepared by casting in a metal mold having a size of 20 mm diameter ⁇ 120 mm (length) was processed to have a cylindrical shape having a size of 16 mm diameter, as illustrated in FIG. 3 , so as to be a test specimen 12, a nozzle 11 having a diameter of 1.6 mm is provided at a position spaced apart from this test specimen 12 by 0.4 mm, 1% CuCl 2 solution 13 was made to flow from the nozzle 11 toward the sample at the flow rate of 0.4 L/min in the normal flow direction for 5 hours, and the weight loss (abrasion amount) and the maximum depth of the sample before and after the test were measured.
the drilling test using a drilling machine was carried out.
the drilling test was carried out using each of the samples formed by machining to cylindrical samples having a size of 18 mm diameter ⁇ 20 mm (height), and using a drilling machine, times required to drill a hole having a 5 mm depth from a deep part of the cylinder were measured under the drilling conditions as indicated in Table 1. Times with the results of less than 6 seconds were evaluated as " ⁇ "; times with the results of 6 seconds or more and less than 7 seconds were evaluated as " ⁇ "; and times with results of 7 seconds or more were evaluated as "x".
each of the copper alloys of Examples and Comparative Examples was heated and melted, and then cast using a spiral-shaped test mold as illustrated in FIGS. 4(a) and 4(b) , to obtain a spiral-shaped test specimen. Since each of the alloys varying in its Zn content has a different temperature at which solidification starts, it is impossible to evaluate the proper flowability of molten metal for each of the alloys, using the same pouring temperature. Therefore, the temperature at which the solidification starts was measured for each of the alloys, by thermal analysis method, and then the casting was carried out at a temperature of +110° C above the measured temperature. Then, the flow length of the spiral-shaped portion of the thus cast spiral-shaped test specimen was measured.
liquid penetrant testing was performed using a step-shaped sample, and evaluation of casting defects was performed.
"-" in the Table denotes that the evaluation was not carried out.
the testing was carried out as follows.
a step-shaped CO 2 mold as illustrated in FIG. 5 was prepared (casting temperature at 1120°C), which was provided with three stepped portions with varying wall thicknesses of 10, 20 and 30 mm, so that the feeding effect was reduced and the resulting casting was more likely to develop casting defects, and the thus obtained casting was cut in half in the middle, and the liquid penetrant testing was carried out in accordance with JIS Z2343 so that occurrences of casting defects and minute gaps in this liquid penetrant testing were examined.
CAC406 of Comparative Example 12 will be described.
CAC406 has mechanical properties, such as a tensile strength of 195 MPa or more and an elongation of 15% or more, which are values defined in JIS.
CAC406 contains 5.38% by mass of Pb, good results were obtained in the drilling test.
the flow length measured in the test for flowability of molten metal was 298 mm, which was evaluated as " ⁇ ".
Comparative Example 12 has a problem in lead leaching.
Comparative Example 1 and Examples 1 to 4 were prepared to have a varying Zn content, with the contents of elements other than Zn being as close to each other as possible. These were arranged in the first group in Table 2 and Table 3 in ascending order of Zn content. With respect to the mechanical properties, each showed values exceeding the tensile strength of 195 MPa and the elongation of 15%, whereas in Comparative Example 1 in which Zn is less than 12% by mass, the time required for machining was too long. On the other hand, in Example 4 in which Zn is nearly 21% by mass which is the upper limit, it was found that the machinability tended to be reduced.
Example 2 Comparative Example 2
Examples 5, 6, and 7, and Comparative Example 3 were prepared to have a varying Sn content, with the contents of elements other than Sn being as close to each other as possible. These were arranged in the second group in Table 2 and Table 3 in ascending order of the Sn content.
Example 5 in which the Sn content is 1.43% by mass which is close to the lower limit value, the erosion-corrosion resistance had a tendency to be slightly reduced, and in Comparative Example 2 in which the Sn content is 0.99% by mass, the erosion-corrosion resistance remarkably lacked.
Example 7 in which Zn is 4.5% by mass, the machinability had a tendency to be reduced, and in Comparative Example 3 in which the Sn content is 4.92% by mass which exceeds 4.5% by mass, a problem in elongation and machinability occurred.
Examples 5, 3, and 4 were arranged in ascending order of the total content of Zn+Sn in Table 2, and Comparative Example 4 in which the content of Zn+Sn further exceeds as compared to those and exceeds 23.5% by mass was prepared, and those were arranged in the third group in Table 2 and Table 3 in ascending order of the total content of Zn+Sn.
Comparative Example 4 both the tensile strength and the elongation were greatly reduced.
Comparative Example 5 Example 5 in which the P content is less than 0.005% by mass and Comparative Example 6 in which the P content exceeds 0.15% by mass, there consequently occurred a problem in flowability. Further, the results for the liquid penetrant testing are indicated in FIG. 6 . In Comparative Example 6 in which the P content exceeds 0.15% by mass, there entirely occurred shrinkage cavities.
Comparative Example 7 Example 10, Example 11, and Comparative Example 8 were prepared to have a varying Pb content, with the contents of elements other than Pb being as close to each other as possible. These were arranged in the fifth group in Table 2 and Table 3 in ascending order of the Pb content.
Comparative Example 7 in which the Pb content is 0.03% by mass which is less than 0.05% by mass, there consequently occurred a problem in machinability.
Examples 13, 14, and 15 and Comparative Examples 9 and 10 were prepared to contain Ni. None of those had a problem in mechanical properties. However, in Comparative Examples 9 and 10 in which the Ni content exceeds 0.5% by mass, there occurred a problem in machinability.
Comparative Example 11 was prepared to contain 0.3% by mass of Bi.
the tensile strength was greatly reduced so that there occurred a problem in mechanical properties. Moreover, this content exhibited a problem in view of recyclability.

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EP15887566.6A 2015-03-31 2015-03-31 Alliage de cuivre pour élément d'alimentation en centre de distribution des eaux Active EP3279347B1 (fr)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
PCT/JP2015/060141 WO2016157413A1 (fr)	2015-03-31	2015-03-31	Alliage d'acier pour élément d'alimentation en eau

Publications (3)

Publication Number	Publication Date
EP3279347A1 true EP3279347A1 (fr)	2018-02-07
EP3279347A4 EP3279347A4 (fr)	2018-03-14
EP3279347B1 EP3279347B1 (fr)	2021-02-17

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EP15887566.6A Active EP3279347B1 (fr)	2015-03-31	2015-03-31	Alliage de cuivre pour élément d'alimentation en centre de distribution des eaux

Country Status (6)

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US (1)	US20180087130A1 (fr)
EP (1)	EP3279347B1 (fr)
JP (1)	JP6561116B2 (fr)
CN (1)	CN107429326A (fr)
ES (1)	ES2856029T3 (fr)
WO (1)	WO2016157413A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
JP2018172726A (ja) *	2017-03-31	2018-11-08	株式会社栗本鐵工所	接液部材用銅合金
JP7202235B2 (ja) *	2018-03-28	2023-01-11	株式会社栗本鐵工所	低鉛銅合金

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US6136104A (en) *	1998-07-08	2000-10-24	Kobe Steel, Ltd.	Copper alloy for terminals and connectors and method for making same
JP2001064742A (ja) *	1999-06-24	2001-03-13	Chuetsu Metal Works Co Ltd	耐食性、被削性、熱間加工性に優れた黄銅合金
JP2004244672A (ja) *	2003-02-13	2004-09-02	Dowa Mining Co Ltd	耐脱亜鉛性に優れた銅基合金
DE602005023737D1 (de) *	2004-08-10	2010-11-04	Mitsubishi Shindo Kk	Gussteil aus kupferbasislegierung mit raffinierten kristallkörnern
DE602005026465D1 (de) *	2005-09-30	2011-03-31	Mitsubishi Shindo Kk	Aufgeschmolzene und erstarrte kupferlegierung die phosphor und zirkon enthält
JP5116976B2 (ja) *	2006-02-10	2013-01-09	三菱伸銅株式会社	半融合金鋳造用原料黄銅合金
JP5335558B2 (ja) *	2009-05-26	2013-11-06	滋賀バルブ協同組合	機械的特性に優れた鋳物用無鉛銅合金
WO2011066581A1 (fr) *	2009-11-30	2011-06-03	Moen Incorporated	Alliage de laiton usinable et résistant à la corrosion du cuivre
DE102012013817A1 (de) *	2012-07-12	2014-01-16	Wieland-Werke Ag	Formteile aus korrosionsbeständigen Kupferlegierungen
JP5501495B1 (ja) *	2013-03-18	2014-05-21	三菱マテリアル株式会社	電子・電気機器用銅合金、電子・電気機器用銅合金薄板、電子・電気機器用導電部品及び端子
JP5406405B1 (ja) *	2013-06-12	2014-02-05	株式会社栗本鐵工所	水道部材用銅合金

2015
- 2015-03-31 US US15/562,684 patent/US20180087130A1/en not_active Abandoned
- 2015-03-31 ES ES15887566T patent/ES2856029T3/es active Active
- 2015-03-31 CN CN201580078224.7A patent/CN107429326A/zh active Pending
- 2015-03-31 WO PCT/JP2015/060141 patent/WO2016157413A1/fr not_active Ceased
- 2015-03-31 EP EP15887566.6A patent/EP3279347B1/fr active Active
- 2015-03-31 JP JP2017508926A patent/JP6561116B2/ja active Active

Also Published As

Publication number	Publication date
ES2856029T3 (es)	2021-09-27
CN107429326A (zh)	2017-12-01
JPWO2016157413A1 (ja)	2018-02-15
JP6561116B2 (ja)	2019-08-14
WO2016157413A1 (fr)	2016-10-06
EP3279347A4 (fr)	2018-03-14
EP3279347B1 (fr)	2021-02-17
US20180087130A1 (en)	2018-03-29

Publication	Publication Date	Title
CA2619357C (fr)	2012-05-01	Alliage de cuivre de decolletage presentant une tres faible teneur en plomb
US10017841B2 (en)	2018-07-10	Copper alloy casting and method of casting the same
EP2761042B1 (fr)	2018-10-10	Alliage de décolletage en cuivre sans plomb
US9982327B2 (en)	2018-05-29	Brass alloy for tap water supply member
JP6359523B2 (ja)	2018-07-18	アンチモン−変性低−鉛銅合金
CA2926331A1 (fr)	2015-04-16	Alliage de cuivre antimicrobien blanc
US9963765B2 (en)	2018-05-08	Copper alloy for use in a member for use in water works
EP3279347B1 (fr)	2021-02-17	Alliage de cuivre pour élément d'alimentation en centre de distribution des eaux
US20140112821A1 (en)	2014-04-24	Lead-free brass alloy for hot working
CA2889459A1 (fr)	2014-05-01	Alliage de cuivre antimicrobien blanc
EP3128020B1 (fr)	2019-03-06	Alliage de laiton à faible teneur en plomb pour élément de plomberie
CA2611919C (fr)	2013-08-06	Element en alliage de cuivre utilise pour l'alimentation en eau
JP4455507B2 (ja)	2010-04-21	飲料水用のバルブ
JP7202235B2 (ja)	2023-01-11	低鉛銅合金
KR20070023646A (ko)	2007-02-28	결정립이 미세화된 구리기합금주물

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