CN105821240A - Brass having excellent castability and corrosion resistance - Google Patents
Brass having excellent castability and corrosion resistance Download PDFInfo
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- CN105821240A CN105821240A CN201610034407.5A CN201610034407A CN105821240A CN 105821240 A CN105821240 A CN 105821240A CN 201610034407 A CN201610034407 A CN 201610034407A CN 105821240 A CN105821240 A CN 105821240A
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- Organic Chemistry (AREA)
- Domestic Plumbing Installations (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
The invention provides a brass in which the content of lead and nickel is reduced or the lead and the nickel are not contained. The brass has the excellent castability and the corrosion resistance. Particularly the brass having the excellent castability and the corrosion resistance includes more than 0.05 mass% and less than 0.2 mass% of Sn; more than 0.05 mass% and less than 0.32 mass% of at least one element selected from Sb, As and P; more than 0.1 mass% and less than 0.5 mass% of Al; more than 33.0 mass% and less than 40.0 mass% of Zn; more than 0.005 mass% and less than 0.25 mass% of at least one element selected from Pb and Bi; less than 0.5 mass% of Ni; less than 0.5 mass% of Si; and more than 0.0001 mass% and less than 0.3 mass% of at least one element selected from Fe and B, with the balance consisting of Cu and unavoidable impurities. The brass contains an apparent Zn content of more than 36% and less than 41%.
Description
Technical field
The present invention relates to reduce lead and the content of nickel or do not comprise the pyrite of lead and nickel, more specifically, relate to being preferred for only comprising micro lead and nickel or do not comprise the castability of water bolt part etc. and the casting pyrite of excellent corrosion resistance of lead and nickel.
Background technology
Water bolt part generally with pyrite, bronze manufacture for material, and in order to improve its processability, corrosion resistance and be added with lead (Pb) and nickel (Ni).But in recent years, start to worry the impact that Pb and Ni brings to human body, environment, thus various countries actively develop the restraint for Pb and Ni.Such as, at California, USA, from January, 2010, make the Pb content of the component contacted with water of hydrant become the restriction that weighted average is below 0.25 mass % and enter into force.It addition, in the U.S. and China, each leaching content for Pb and Ni enters into force in the restriction of 5 μ g/L and 20 below μ g/L respectively.The countries in the world headed by Europe, Korea S beyond the U.S., such restraint is the most notable, thus requirement is developed and leached quantitative limitation to corresponding material with these Pb content or Pb and Ni.
As the conventional pyrite typically comprising lead, in Japanese Unexamined Patent Publication 8-337831 publication (patent documentation 1), for the purpose of the copper alloy that diecasting and excellent corrosion resistance are provided, propose there is diecasting copper alloy, described diecasting copper alloy comprises: Sn, in 0.05～0.2 weight %；Element more than at least one of Sb, As and P, in 0.05～0.3 weight %；Al, in 0.1～0.5 weight %；Zn, in 33.0～37.0 weight %；And Pb, in 0.5～3.0 weight %, and remainder is made up of Cu, and zinc equivalent is 35.7～41.0 weight %, and the area ratio/occupancy ratio of β phase is less than 15%, and solidification temperature range is less than 17 DEG C.According to this patent documentation, it is added with the Pb of 0.5～3.0 weight % to improve the machinability of copper alloy.It addition, in this patent documentation, the element that comprised as copper alloy and non-publicity has Ni.
Patent documentation 1: Japanese Unexamined Patent Publication 8-337831 publication
Summary of the invention
This time, the inventors discovered that in reducing the content of Pb and Ni or not comprising the pyrite of Pb and Ni, by adding antimony (Sb) and stannum (Sn) with ormal weight respectively, the corrosion resistance originally giving pyrite because comprising Pb and Ni can be made to significantly increase, although and the interpolation of Sb and Sn there are and ruptures the situation bringing impact to casting, but its impact can be by improving with ormal weight interpolation ferrum (Fe) and/or boron (B).The present invention is based on this kind of opinion.
Thus, the technical problem to be solved is to provide and a kind of reduce lead and the content of nickel or do not comprise the pyrite that lead and nickel and castability and corrosion resistance etc. are excellent.
Then, the pyrite of the present invention, it is characterised in that it comprises:
Sn, more than 0.05 mass % and below 0.2 mass %；
Element more than at least one of Sb, As and P, it is aggregated in below more than 0.05 mass % and 0.32 mass %；
Al, more than 0.1 mass % and below 0.5 mass %；
Zn, more than 33.0 mass % and below 40.0 mass %；
Element more than at least one of Pb and Bi, it is aggregated in below more than 0.005 mass % and 0.25 mass %；
Ni, below 0.5 mass %；
Si, below 0.5 mass %；
Element more than at least one of Fe and B, it is aggregated in below more than 0.0001 mass % and 0.3 mass %,
And remainder is actually made up of Cu and inevitable impurity,
And apparent Zn content is more than 36% and less than 41%.
Accompanying drawing explanation
Fig. 1 is the figure of the shape representing the mould 1 used in the two ends fixed pattern test method(s) being evaluated casting disruptiveness.
Detailed description of the invention
Definition
In the present invention, in the case of not having special declaration, " inevitable impurity " is meant less than the element of the amount of 0.1 mass %.Such as, the element such as manganese (Mn) and chromium (Cr) is comprised in inevitable impurity.The preferably amount of this inevitable impurity is less than 0.05 mass %.
Element more than at least one of Pb and Bi
The pyrite of the present invention comprises the element more than at least one of Pb and Bi (bismuth), and it is aggregated in below more than 0.005 mass % and 0.25 mass %.In the present invention, it is possible to make the content of Pb become such very small amount.According to the preferred form of the present invention, the addition of the element more than at least one of Pb and Bi is formed it and is aggregated in below more than 0.15 mass % and 0.25 mass %.It addition, according to other the preferred form of the present invention, the addition of Pb is formed below more than 0.13 mass % and 0.23 mass %.
It addition, Bi replaces Pb to give the processability (such as, machinability) that pyrite is equal with Pb.Thus, in the present invention, it is preferred to the addition of Bi is below more than 0.13 mass % and 0.23 mass %.
Ni
The pyrite of the present invention comprises the Ni of below 0.5 mass %.In the present invention, it is possible to make the content of Ni become such very small amount.According to the preferred form of the present invention, the addition of Ni is formed below below 0.2 mass %, and more preferably 0.1 mass %.
Element more than at least one of Sb, As and P
The pyrite of the present invention comprises the element more than at least one of Sb, As (arsenic) and P (phosphorus), and it is aggregated in below more than 0.05 mass % and 0.32 mass %.Owing to the addition of the Ni of the pyrite of the present invention is trace as previously mentioned, therefore there are the trend that cannot obtain corrosion resistance fully, but by comprising the element of more than its at least one selected from Sb, As and P being aggregated in below more than 0.05 mass % and 0.32 mass %, it is possible to make corrosion resistance improve.By adding Sn described later with ormal weight, with compared with single interpolation, this action effect is played synergistically.Due to when the addition of these elements is more than 0.32 mass %, then there are the trend that corrosion resistance becomes not significantly improve, therefore considering economy and making higher limit is 0.32 mass %.According to the preferred form of the present invention, the addition of the element more than at least one of Sb, As and P is formed it and adds up to below more than 0.056 mass % and 0.315 mass %.It addition, according to other the preferred form of the present invention, the respective addition of Sb, As and P is formed below more than below more than below more than 0.01 mass % and 0.30 mass %, 0.001 mass % and 0.30 mass % and 0.005 mass % and 0.30 mass %.
Sn
The pyrite of the present invention comprises the Sn of below more than 0.05 mass % and 0.2 mass %.Owing to the addition of the Ni of the pyrite of the present invention is trace as previously mentioned, therefore there are the trend that cannot obtain corrosion resistance fully, but by comprising the Sn of below more than 0.05 mass % and 0.2 mass %, it is possible to make corrosion resistance improve.By adding the element of more than the above-mentioned at least one selected from Sb, As and P with ormal weight, compared with individually adding, this action effect is played synergistically.
Element more than at least one of Fe and B
The pyrite of the present invention comprises the element more than at least one of Fe and B, and it is aggregated in below more than 0.0001 mass % and 0.3 mass %.The present invention is based on following opinion, i.e. in view of the impact bringing to as mentioned above human body, environment, and the addition of Pb and Ni is reduced and is adjusted to trace, the content of described Pb and Ni or leaching content have been limited or will have been limited, and can be by adding the element more than at least one of Sb, As and P with ormal weight respectively and Sn supplies and results from this reduction of corrosion resistance.It is on the other hand, the present invention is additionally based upon the following opinion simultaneously found, i.e., although because of the reduction of addition of Pb and Ni and Sb etc. and the interpolation of Sn, and there are the danger becoming cannot to obtain the castability of pyrite fully, but by comprising the element more than at least one of Fe and B within the above range, it is possible to improve the castability of the pyrite of the present invention.That is, each Fe and B can promote to crystallize the miniaturization of (especially primary crystal β phase), thus rupturing when being effectively prevented casting.It addition, according to the result of this miniaturization, the pyrite of the present invention also shows that good performance for mechanical property.
Additionally, there are following danger, i.e. B Yu Fe, Cr described later etc. form intermetallic compound, and form hard spot, caused producing inconvenience during the Surface Machining of formed products after casting.Thus, in the case of requiring surface to have flatness, preferably reduce the addition of B and/or reduce the content of Fe, Cr etc..Specifically, preferably making B is below 0.005 mass %, below more preferably 0.003 mass %, is even more preferably below 0.002 mass %, and making Fe is below 0.10 mass %, and makes Cr be less than 0.1 mass %.
Zn
The pyrite of the present invention comprises the Zn of below more than 33.0 mass % and 40.0 mass %.By making the addition of Zn be more than 33.0 mass %, it is possible to make the yield rate of casting become good.It addition, be below 40.0 mass % by making the addition of Zn, it is possible to the increase of the β alpha region of suppression corrosion-resistant, in order to make Dezincification corrosion resistant to reduce.
Al
The pyrite of the present invention comprises the Al of below more than 0.1 mass % and 0.5 mass %.By making the addition of Al more than 0.1 mass %, it is possible to make castability improve.Specifically, it is possible to make mobility, cast(ing) surface character improve.In the present invention, the preferred addition of Al is more than 0.3 mass %.Thereby, it is possible to make mobility, cast(ing) surface character more improve.It addition, by making the addition of Al below 0.5 mass %, it is possible to suppression stretch-proof value, the reduction of shock resistance value.
Si
The pyrite of the present invention comprises the Si of below 0.5 mass %.As described later, for Si, the Zn equivalent that Guillet is advocated is 10, thus apparent Zn content increases, thus there are and separate out γ phase or the danger of the such out-phase of κ phase in crystalline structure.In the present invention, owing to the addition of Si is below 0.5 mass %, the probability that therefore γ phase, the such out-phase of κ phase separate out in crystalline structure is relatively low.According to the preferred form of the present invention, the addition of Si is below 0.1 mass %.
Cu and inevitably impurity
The remainder of the part being made up of above-mentioned elemental composition of the pyrite of the present invention is actually made up of copper (Cu) and inevitable impurity.According to the preferred form of the present invention, the pyrite of the present invention comprises the Cu of below more than 55 mass % and 70 mass %.It it is below 70 mass % by the addition of Cu, it is possible to the generation of the crackle that suppression causes because of the ingotism of primary crystal α phase.It addition, be more than 55 mass % by the addition of Cu, it is possible to suppress the reduction of castability, corrosion resistance and mechanical property as pyrite.According to the preferred form of the present invention, the lower limit of the addition of Cu is 58 mass %, and the upper limit is 66 mass %.
It addition, in order to improve the characteristic of pyrite, the pyrite of the present invention can comprise various adding ingredient.It addition, in the present invention, it is impossible to get rid of the existence of inevitable impurity, but preferably make them the fewest.
In the present invention, there are following danger, i.e. Cr and above-mentioned Fe, B etc. form intermetallic compound, and form hard spot, cause producing inconvenience during the Surface Machining of formed products after casting.Thus, in the case of requiring surface to have flatness, preferably reduce the content of Cr.Specifically, preferably few than 0.1 mass %, fewer than 0.01 mass %.
In the present invention, Mn makes the intensity of pyrite improve.When being added with Mn, then there are following danger, i.e. form the intermetallic compound of Mn and Si, and form hard spot, thus during the Surface Machining of formed products after casting, produce inconvenience.Thus, in order to suppress such impact on castability, preferably reduce the content of Mn.Specifically, preferably few than 0.1 mass %, fewer than 0.01 mass %.
Apparent Zn content
According to the preferred form of the present invention, the apparent Zn content of the pyrite of the present invention is more than 36% and less than 41%.By apparent Zn content in such range, it is possible to do not produced the pyrite that casting ruptures.In this manual, apparent Zn content refers to the amount that the following formula advocated by Guillet is calculated.This formula is based on following opinion, i.e. the addition element beyond Zn demonstrates the trend identical with the interpolation of Zn.
Apparent Zn content (%)=[(B+tq)/(A+B+tq)] × 100
In formula, A=Cu mass %, B=Zn mass %, t refers to the Zn equivalent of addition element, and q refers to addition quality % of addition element.And, the Zn equivalent of each element is Si=10, Al=6, Sn=2, Pb=1, Fe=0.9, Mn=0.5, Ni=-1.3.Though the Zn equivalent of Bi is not expressly stated, but in this manual, it is contemplated that document etc. and calculate as 0.6.Further, since the addition of the element beyond it is trace, the impact brought to the value of Zn equivalent is the least, is therefore " 1 ".
The ratio of β phase
According to the preferred form of the present invention, the ratio of the β phase in the crystalline structure of the pyrite of the present invention is less than 15%.By becoming such crystalline structure, it is possible to realize the pyrite that corrosion resistance is good.It addition, according to the preferred form of the present invention, the ratio of β phase is less than 8%.Thereby, it is possible to realize the diecasting pyrite of the excellent corrosion resistance of water bolt part.Especially, the resistance to splenium of water bolt part it is suitable for.Additionally, in the present invention, on the basis of the ratio of β phase area ratio in crystallization cross section, such as, image procossing is carried out to the crystalline structure photo of optics microscope photographing, it is possible to obtain the area ratio of β phase.
Purposes
Owing to the content of Pb and Ni is reduced into trace by the pyrite of the present invention or does not comprise Pb and Ni, and on the other hand, its castability and corrosion resistance have equal with the pyrite comprising Pb and Ni or that it is above performance, are therefore preferably used to water bolt part material.Specifically, the material of water supply part, draining part, valve etc. it is preferably used as.
Manufacture method
The preferably pyrite of the present invention is manufactured by following method, i.e. carry out heat treatment after being included in casting to the method reducing the ratio of the β phase in its crystalline structure.Owing to the least then corrosion resistance of the ratio of β phase is the highest, therefore, it is possible to obtain the pyrite of excellent corrosion resistance.According to the preferred form of the present invention, more than 450 DEG C and less than 550 DEG C carry out more than 30 minutes and less than 3 hours heat treatments.According to this heat treatment, it is possible to the ratio obtaining β phase is less than 15%, the pyrite of preferably less than 8%, and the excellent corrosion resistance of the pyrite so obtained.
In the present invention, by more than 450 DEG C and 550 DEG C of heat treatment below, because β alpha region is reduced, and Sn, Sb concentration in β phase rises, thus the corrosion resistance of β phase increases tremendously.By suppressing increasing and the reduction of suppression corrosion resistance of β alpha region 550 DEG C of heat treated below.It addition, by 450 DEG C of heat treatments carried out above, the inclined cloth in local of the element being present in grain boundary (grainboundary) was eliminated without the cost time, and β alpha region is reduced.
In the present invention, by more than 30 minutes and 3 hours heat treatment below, obtain β phase and reduce effect.It addition, can fully obtain this effect with the heat treatment time within 3 hours.Due to more than 3 hours, even if carrying out heat treatment also there is no very good effect, within therefore preferably making the upper limit of heat treatment time be 3 hours in view of economy.
Further, since the good castability of the formed products with the pyrite of the present invention as material, therefore can by diecasting, sand casting any one manufacture, but can more enjoy the effect of its good castability in diecasting.Further, since the pyrite of the present invention is also good in its machinability, machining the most also can be carried out after casting.It addition, the pyrite of the present invention also can form the cutting bar of molding, forging bar by extruding after casting continuously, and the wire rod of molding can be formed further by stretching.
Embodiment
By below example, the present invention is illustrated in more detail, but the present invention is not limited to these embodiments.
Evaluation test
The detailed content of each evaluation test in below example is as follows.
(1) casting disruptiveness test
By two ends fixed pattern test method(s), casting disruptiveness is evaluated.The shape of the mould 1 used is as shown in Figure 1.In FIG, being provided with adiabator 2 on central part, so that the cooling of central part is slower than two ends fixed part 3, this extenal fixation end distance (2L) is 100mm, adiabator length (2l) is 70mm.
Whether test is carried out as follows, i.e. makes fixed part chilling and fixes its two ends, promote solidification at central part the most further, and investigate because of produced solidification shrinkage stress, and produce on the test film central part constituting final solidification portion and rupture.
Its result, is judged to ◎ by non-cracked situation, local is had crackle but the situation that is not reaching to rupture is judged to zero, by have crackle and there occurs situation about rupturing be judged to ×.
(2) corrosion resistance test
Obtain diameter 35mm, the ingot bar of length 100mm made by diecasting, as test film, tested for standard with Shen Tong association of Japan technical standard JBMAT-303-2007.It is that below 100 μm are judged to ◎ by maximum depth of erosion, below 150 μm, will be judged to zero, and will be judged to more than 150 μm ×.
Example 1-1～10-8
Cast the pyrite of composition described in following table.I.e., using electrolysis Cu, the raw gold of electrolysis Zn, Bi, the raw gold of electrolysis Pb, Sn, the raw gold of Sb, Cu-30%Ni foundry alloy, electrolysis Al, Cu-15%Si foundry alloy, Cu-2%B foundry alloy, Cu-30%Mn foundry alloy, Cu-10%Cr foundry alloy, Cu-15%P foundry alloy, Cu-10%Fe, Cu-20%As foundry alloy etc. as raw material, composition adjustment is carried out while melting by high frequency melting furnace, first, carry out casting and have rated casting disruptiveness in two ends fixation test mould.
It follows that carry out casting the ingot bar making diameter 35mm, length 100mm in cylindrical mold, and ingot bar is carried out the evaluation of corrosion resistance as sample.Its evaluation result is as shown in the table.
Table 1
Table 2
Table 3
Table 4
Example in table specify that the meaning impact of following addition element especially.
Example 11-1,11-2,11-8,12-1,12-2,12-8:Sb, As and P
Example 11-3,11-4,12-3,12-4:Sn
Example 11-5,11-6,12-5,12-6:Al
Example 11-7,12-7:Si
Example 13-1～13-5,14-1～14-5:Pb and Bi
Example 13-6,14-6:Ni
Example 13-7,14-7:Mn
Example 13-8,14-8:Cr
Table 5
Example 15-1～15-8,16-1～16-8 are considered as preferred composition.
Example in table specify that the meaning impact of following addition element especially.
Example 17-1,17-3,17-5,17-7,18-1,18-3,18-5,18-7:Sb, As and P
Example17-2,17-4,17-6,17-8,18-2,18-4,18-6,18-8:Sn
Table 6
Example in table specify that the meaning impact of following addition element especially.
Example 19-1～19-8,20-1～20-8,21-1,21-3,21-5,21-7:Sb, As and P
Example 19-1～19-8,20-1～20-8,21-2,21-4,21-6,21-8:Sn
Example 22-1～22-8: apparent Zn content
Example 22-1,22-2,22-5,22-6:Al
Example 22-3,22-4,22-7,22-8:Zn
Table 7
Example in table specify that the meaning impact of following addition element especially.
Example 23-1～23-8: inevitably impurity
Example 23-1,23-2,23-5,23-6:Mn
Example 23-3,23-4,23-7,23-8:Cr
Example 24-1,24-5:Si
Example 24-1,24-5: apparent Zn content
Example 24-2,24-3,24-6,24-7:Cu and inevitable impurity
Claims (6)
1. a pyrite, it is characterised in that it comprises:
Sn, more than 0.05 mass % and below 0.2 mass %；
Element more than at least one of Sb, As and P, it is aggregated in below more than 0.05 mass % and 0.32 mass %；
Al, more than 0.1 mass % and below 0.5 mass %；
Zn, more than 33.0 mass % and below 40.0 mass %；
Element more than at least one of Pb and Bi, it is aggregated in below more than 0.005 mass % and 0.25 mass %；
Ni, below 0.5 mass %；
Si, below 0.5 mass %；
Element more than at least one of Fe and B, it is aggregated in below more than 0.0001 mass % and 0.3 mass %,
And remainder is actually made up of Cu and inevitable impurity,
And apparent Zn content is more than 36% and less than 41%.
Pyrite the most according to claim 1, it is characterised in that the ratio of the β phase in the crystalline structure of described pyrite is less than 15%.
Pyrite the most according to claim 2, it is characterised in that by after casting more than 450 DEG C and less than 550 DEG C carry out more than 30 minutes and 3 hours heat treatment below and obtain.
4. a manufacture method, the manufacture method of its pyrite according to any one of claims 1 to 3, it is characterised in that manufactured by casting, comprise after casting more than 450 DEG C and less than 550 DEG C carry out more than 30 minutes and 3 hours heat treatment below.
5. a water bolt part, it is characterised in that be made up of the pyrite described in any one of claims 1 to 3.
Water bolt part the most according to claim 5, it is characterised in that manufactured by diecasting.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| JP2015-014370 | 2015-01-28 | ||
| JP2015014370 | 2015-01-28 | ||
| JP2015239068A JP6056947B2 (en) | 2015-01-28 | 2015-12-08 | Brass with excellent castability and corrosion resistance |
| JP2015-239068 | 2015-12-08 |
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| CN105821240A true CN105821240A (en) | 2016-08-03 |
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| CN107980068A (en) * | 2016-10-25 | 2018-05-01 | 广东伟强铜业科技有限公司 | A kind of cutting brass alloy and its manufacture method |
| WO2018076165A1 (en) * | 2016-10-25 | 2018-05-03 | 广东伟强铜业科技有限公司 | Free-cutting brass alloy and manufacturing method therefor |
| CN109963954A (en) * | 2017-02-10 | 2019-07-02 | 国立铜业股份公司 | The copper alloy of low lead content |
| CN111945031A (en) * | 2017-08-11 | 2020-11-17 | 骊住集团株式会社 | Copper alloy, use of a copper alloy, sanitary fitting and method for producing a sanitary fitting |
| CN114008227A (en) * | 2019-06-25 | 2022-02-01 | 三菱综合材料株式会社 | Free-cutting copper alloy and method for producing free-cutting copper alloy |
| CN111235427A (en) * | 2020-01-15 | 2020-06-05 | 宁波博威合金材料股份有限公司 | Free-cutting brass alloy and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
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| JP2016145411A (en) | 2016-08-12 |
| JP6056947B2 (en) | 2017-01-11 |
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