CN112553502A - Zinc alloy and method for producing same - Google Patents

Zinc alloy and method for producing same Download PDF

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Publication number
CN112553502A
CN112553502A CN202010875674.1A CN202010875674A CN112553502A CN 112553502 A CN112553502 A CN 112553502A CN 202010875674 A CN202010875674 A CN 202010875674A CN 112553502 A CN112553502 A CN 112553502A
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Prior art keywords
mass
content
zinc alloy
less
melt
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CN202010875674.1A
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Inventor
才川清二
饭岛正彦
附田之欣
麻生早纪
山端达也
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Nidec Corp
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Nidec Corp
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C18/00Alloys based on zinc
    • C22C18/04Alloys based on zinc with aluminium as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/027Casting heavy metals with low melting point, i.e. less than 1000 degrees C, e.g. Zn 419 degrees C, Pb 327 degrees C, Sn 232 degrees C
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/165Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon

Abstract

The present invention provides a zinc alloy with excellent hardness and a manufacturing method thereof. [ solution ] A zinc alloy which contains Al, Mg, Sr and Ca in the following contents, and the balance of Zn and unavoidable impurities. The content of Al is 3.5-4.3 mass%. The content of Mg is 0.02 mass% or more and 0.06 mass% or less. The Sr content is 0.0008 mass% or more and 0.0048 mass% or less. The content of Ca is 0.0008 mass% or more and 0.0048 mass% or less.

Description

Zinc alloy and method for producing same
Technical Field
The present invention relates to a zinc alloy and a method for producing the same.
Background
Zinc alloys have high dimensional accuracy and also have impact resistance, and are used as constituent materials for parts of precision equipment, parts of portable electronic devices, toys, automobile parts, building hardware, office equipment, accessories, and the like.
Patent document 1 describes, as a zinc alloy having high strength and excellent toughness and wear resistance, a zinc alloy containing Ca in a range of 0.005 wt% to 0.1 wt%, Sr in a range of 0.005 wt% to 0.1 wt%, and Al, Cu, and Mg in predetermined contents.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-
Disclosure of Invention
Problems to be solved by the invention
However, the technique described in patent document 1 leaves room for improvement in obtaining a zinc alloy having excellent hardness.
The present invention has been made in view of the above problems, and an object thereof is to provide a zinc alloy having excellent hardness and a method for producing the same.
Means for solving the problems
Exemplary zinc alloys of the present invention contain Al, Mg, Sr, and Ca in the following contents, respectively, with the balance being Zn and unavoidable impurities. The content of Al is 3.5-4.3 mass%. The content of Mg is 0.02 mass% or more and 0.06 mass% or less. The Sr content is 0.0008 mass% or more and 0.0048 mass% or less. The content of Ca is 0.0008 to 0.0048 mass%.
An exemplary method for producing a zinc alloy of the present invention includes: a pouring step of pouring the melt into a mold; and a cooling step of cooling the poured melt. The molten metal contains Al, Mg, Sr, and Ca at the following contents, and the balance of Zn and unavoidable impurities. The content of Al is 3.5-4.3 mass%. The content of Mg is 0.02 mass% or more and 0.06 mass% or less. The Sr content is 0.0008 mass% or more and 0.0048 mass% or less. The content of Ca is 0.0008 to 0.0048 mass%.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the exemplary invention, a zinc alloy excellent in hardness and a method for producing the same can be provided.
Drawings
FIG. 1 is a scanning electron micrograph of a zinc alloy of example 1.
FIG. 2 is a scanning electron micrograph of a zinc alloy of comparative example 1.
Detailed Description
Preferred embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments, and can be implemented in various forms without departing from the scope of the invention. Note that, for parts that will be described repeatedly, descriptions thereof may be omitted as appropriate.
First, terms used in the present specification will be described. The content (unit: mass%) of each element constituting the zinc alloy is the content of each element with respect to the total mass of the zinc alloy. The content (unit: mass%) of each element constituting the melt is the content of each element with respect to the total mass of the melt.
The content of each element constituting the melt is equal to the content of each element constituting the zinc alloy obtained by cooling the melt.
"hardness" means Vickers hardness (unit: HV) measured by a Vickers hardness tester.
< embodiment 1: zinc alloy >
The zinc alloy of embodiment 1 contains Al, Mg, Sr, and Ca in the following contents, and the balance of Zn and unavoidable impurities.
The content of Al in the zinc alloy of embodiment 1 is 3.5 mass% to 4.3 mass%. The content of Mg in the zinc alloy of embodiment 1 is 0.02 mass% or more and 0.06 mass% or less. The Sr content in the zinc alloy of embodiment 1 is 0.0008 mass% or more and 0.0048 mass% or less. The content of Ca in the zinc alloy of embodiment 1 is 0.0008 mass% or more and 0.0048 mass% or less.
The zinc alloy of embodiment 1 is excellent in hardness. The reason for this is presumed as follows.
The zinc alloy generally has a phase composed of primary crystals (hereinafter, sometimes referred to as an α phase) and a phase composed of eutectic crystals (hereinafter, sometimes referred to as a β phase). The alpha phase is, for example, an alpha-Zn phase. The β phase includes, for example, an α — Zn phase and an intermetallic compound phase containing Zn and a metal other than Zn.
The zinc alloy of embodiment 1 contains Sr at a content of 0.0008 mass% to 0.0048 mass% and also contains Ca at a content of 0.0008 mass% to 0.0048 mass%, and therefore the β phase is refined. Since the stress concentration is suppressed when the β phase is refined, the zinc alloy of embodiment 1 is excellent in hardness.
The zinc alloy according to embodiment 1 is obtained by casting, for example. The casting method for obtaining the zinc alloy of embodiment 1 is not particularly limited, and examples thereof include gravity die casting, and sand die casting. The zinc alloy of embodiment 1 obtained by casting can be used as a constituent material of a zinc alloy member, and can also be used as a raw material for producing a zinc alloy cast product.
The composition of the zinc alloy of embodiment 1 will be described below. In the following description, the zinc alloy of embodiment 1 may be referred to as a specific zinc alloy.
[ Al (aluminum) ]
The specific zinc alloy contains Al at a content of 3.5 to 4.3 mass%. When the Al content is 3.5 mass% or more and 4.3 mass% or less, the melting point of the specific zinc alloy is lowered, and thus the castability of the specific zinc alloy is improved. In order to further improve the castability of the specific zinc alloy, the content of Al is preferably 3.7 mass% or more and 4.1 mass% or less, and more preferably 3.8 mass% or more and 4.0 mass% or less.
[ Mg (magnesium) ]
The specific zinc alloy contains Mg at a content of 0.02 to 0.06 mass%.
By setting the Mg content to 0.02 mass% or more and 0.06 mass% or less, intergranular corrosion of the specific zinc alloy can be suppressed. In order to further suppress intergranular corrosion of the specific zinc alloy, the content of Mg is preferably 0.03 mass% or more and 0.05 mass% or less.
[ Sr (strontium) and Ca (calcium) ]
The specific zinc alloy contains Sr at a content of 0.0008 to 0.0048 mass%, and contains Ca at a content of 0.0008 to 0.0048 mass%. The beta phase of the specific zinc alloy is refined by setting the Sr content to 0.0008 mass% or more and 0.0048 mass% or less and setting the Ca content to 0.0008 mass% or more and 0.0048 mass% or less.
In order to make the β phase finer and obtain a specific zinc alloy having more excellent hardness, the Sr content is preferably 0.0009 mass% or more and 0.0047 mass% or less, and more preferably 0.0009 mass% or more and 0.0046 mass% or less.
In order to make the β phase finer and obtain a specific zinc alloy having more excellent hardness, the content of Ca is preferably 0.0009 mass% or more and 0.0047 mass% or less, and more preferably 0.0010 mass% or more and 0.0046 mass% or less.
In order to further refine the β phase and obtain a specific zinc alloy having further excellent hardness, the total content of Sr and Ca is preferably 0.0018% by mass or more and 0.0093% by mass or less, more preferably 0.0019% by mass or more and 0.0092% by mass or less, and still more preferably 0.0020% by mass or more and 0.0091% by mass or less.
In order to further refine the β phase and obtain a specific zinc alloy having further excellent hardness, the ratio of the content of Ca to the content of Sr (content of Ca/content of Sr) is preferably 0.99 to 1.13.
In order to further refine the β phase and obtain a specific zinc alloy having further excellent hardness, it is preferable that the total content of Sr and Ca is 0.0020 mass% or more and 0.0091 mass% or less, and the ratio of the content of Ca to the content of Sr (content of Ca/content of Sr) is 0.99 to 1.13.
[ Zn (Zinc) and unavoidable impurities ]
In the specific zinc alloy, the balance of Zn and inevitable impurities excluding Al, Mg, Sr and Ca. Zn is the component most contained in a specific zinc alloy on a mass basis. Examples of the inevitable impurities include Cu (copper), Fe (iron), Pb (lead), Cd (cadmium), and Sn (tin). In order to obtain a specific zinc alloy having further excellent hardness, the content of inevitable impurities is preferably reduced. In order to obtain a specific zinc alloy having further excellent hardness, the content of Cu as an inevitable impurity is preferably 0.25 mass% or less. In order to obtain a specific zinc alloy having further excellent hardness, the content of Fe as an inevitable impurity is preferably 0.10 mass% or less. In order to obtain a specific zinc alloy having further excellent hardness, the content of Pb as an inevitable impurity is preferably 0.005 mass% or less. In order to obtain a specific zinc alloy having further excellent hardness, the content of Cd as an inevitable impurity is preferably 0.004 mass% or less. In order to obtain a specific zinc alloy having further excellent hardness, the content of Sn as an inevitable impurity is preferably 0.003 mass% or less.
In addition, when the specific zinc alloy contains components other than Cu, Fe, Pb, Cd, and Sn (other unavoidable impurities) as unavoidable impurities, the total content of the other unavoidable impurities is preferably 0.01 mass% or less in order to obtain a specific zinc alloy having further excellent hardness.
< embodiment 2: method for producing Zinc alloy
Next, a method for producing a zinc alloy according to embodiment 2 will be described. Hereinafter, description of the overlapping contents with those of embodiment 1 may be omitted.
The method for producing a zinc alloy according to embodiment 2 includes: a pouring step of pouring the melt into a mold; and a cooling step of cooling the poured melt. The molten metal contains Al, Mg, Sr, and Ca at the following contents, and the balance of Zn and unavoidable impurities.
The Al content in the melt is 3.5-4.3 mass%. The content of Mg in the melt is 0.02 mass% or more and 0.06 mass% or less. The Sr content in the melt is 0.0008 mass% or more and 0.0048 mass% or less. The content of Ca in the melt is 0.0008 to 0.0048 mass%.
The preferred content of each element in the melt is equal to the preferred content of each element in the specific zinc alloy. The preferred total content of Sr and Ca in the molten metal and the preferred content ratio of Sr and Ca in the molten metal (content of Ca/content of Sr) are also equal to the preferred total content of Sr and Ca in the specific zinc alloy and the preferred content ratio of Sr and Ca in the specific zinc alloy (content of Ca/content of Sr), respectively.
According to the method for producing a zinc alloy of embodiment 2, the zinc alloy (specific zinc alloy) of embodiment 1 can be easily produced.
The method for producing a zinc alloy according to embodiment 2 may further include other steps, which will be described later, in addition to the pouring step and the cooling step. Hereinafter, each step included in the manufacturing method of embodiment 2 will be described.
[ casting Process ]
In the casting step, the melt is cast into a mold. The molten metal is obtained by melting each raw material of the zinc alloy. When obtaining the melt, the raw materials are used in such a proportion as to achieve the target specific composition of the zinc alloy. The heating temperature of the raw material when obtaining a melt is preferably 500 ℃ to 600 ℃ in order to uniformly melt the raw material. In addition, when the heating temperature of the raw material is 500 ℃ to 600 ℃, the temperature of the obtained melt can be easily adjusted to a preferable pouring temperature described later.
In order to uniformly melt the raw material, the heating time of the raw material in obtaining a melt is preferably 2 hours to 4 hours.
In order to obtain a specific zinc alloy having a finer β phase and more excellent hardness, the casting temperature in the casting step (the temperature of the molten metal during casting) is preferably 490 ℃ to 510 ℃, more preferably 493 ℃ to 507 ℃, and still more preferably 495 ℃ to 505 ℃. The pouring temperature can be adjusted by changing at least one of the heating temperature at the time of obtaining the melt and the time required until the melt in a heated state (for example, the melt having a temperature of 500 ℃ to 600 ℃) is poured into the mold.
[ Cooling Process ]
In the cooling step, the poured melt is cooled. The molten metal is cooled to solidify the molten metal, and as a result, a specific zinc alloy is obtained. Examples of the method of cooling the melt include a method of cooling by heat radiation from a mold (natural cooling), air cooling (forced air cooling), and water cooling.
In order to further refine the β phase and obtain a specific zinc alloy having more excellent hardness, the molten metal is preferably cooled at a cooling rate (a lowering rate of the molten metal temperature) of 10 ℃/sec or more and 100 ℃/sec or less in the cooling step.
In the case of cooling the melt by natural cooling, the cooling rate can be adjusted by changing the material of the mold. For example, when a mold made of a metal having high thermal conductivity (more specifically, copper or the like) is used as the mold, the cooling rate is increased.
[ other Processes ]
The method for producing a zinc alloy according to embodiment 2 may further include other steps in addition to the pouring step and the cooling step described above. The other step includes, for example, a step of heat-treating the solidified product obtained in the cooling step (heat treatment step). When the method for producing a zinc alloy according to embodiment 2 further includes a heat treatment step, a specific zinc alloy having excellent dimensional stability can be obtained. In order to obtain a specific zinc alloy having more excellent dimensional stability, the heat treatment temperature is preferably 95 ℃ to 105 ℃. In order to obtain a specific zinc alloy having further excellent dimensional stability, the heat treatment time is preferably 15 hours to 20 hours.
[ examples ]
The present invention will be described below with reference to examples, but the present invention is not limited to the scope of the examples. The content of each element constituting the zinc alloy was measured with a fluorescence X-ray analyzer ("JSX-3202 EV", manufactured by japan electronics corporation) for an element having a content of 0.1 mass% or more, and with an inductively coupled plasma mass spectrometer ("7500 ce", manufactured by Agilent Technologies corporation) for an element having a content of less than 0.1 mass%. The temperature of the melt was measured using a K thermocouple.
< preparation of Zinc alloy >
The following describes the production methods of the zinc alloys A1 to A4 and B1 to B15.
[ production of Zinc alloy A1 ]
As the raw materials, zinc alloy a1 was produced by gravity die casting using bulk zinc, bulk aluminum, bulk magnesium, bulk strontium, and bulk calcium. Specifically, first, the raw materials were weighed so that the total mass thereof became 3kg at a ratio to the composition of the zinc alloy a1 shown in table 1 below. Subsequently, weighed raw materials were charged into a graphite crucible, and then the raw materials were heated in a constant temperature bath at an atmosphere temperature of 565 ℃ ± 5 ℃ for 3 hours, thereby melting the raw materials to obtain a melt.
Next, the obtained melt was poured into a copper mold (internal volume: 50mL) preheated to 100 ℃ in advance (pouring step). The casting temperature in the casting step is in the range of 495 ℃ to 505 ℃.
Subsequently, the molten metal poured into the mold is naturally cooled by heat dissipation from the mold, and the molten metal is solidified, thereby obtaining a zinc alloy a1 (cooling step). The cooling rate in the cooling step is in the range of 10 ℃/sec to 100 ℃/sec.
Subsequently, the obtained zinc alloy a1 was water-cooled to a temperature of 25 ℃, and then a rectangular parallelepiped alloy piece having a size of 10mm × 12mm × 45mm was cut out from the water-cooled zinc alloy a1 by a cutter. Subsequently, the cut rectangular parallelepiped alloy piece was put in an oil bath set at a temperature of 100 ℃ and heat-treated for 15 hours (heat treatment step). Next, the rectangular parallelepiped alloy piece after the heat treatment was air-cooled to a temperature of 25 ℃, and then the oil adhering to the surface of the rectangular parallelepiped alloy piece was wiped off to obtain an alloy piece for testing (test piece).
[ production of Zinc alloys A2-A4 and B1-B15 ]
Zinc alloys a2 to a4 and B1 to B15 were obtained in the same manner as the production method of zinc alloy a1 except that the raw materials were weighed so that the total mass thereof became 3kg at a ratio of the component composition of each zinc alloy shown in table 1 below. Using the obtained zinc alloys a2 to a4 and B1 to B15, test pieces of zinc alloys a2 to a4 and B1 to B15 were obtained by the same method as the method for obtaining the test piece of the zinc alloy a 1.
< evaluation of hardness >
[ evaluation method ]
The vickers hardness of the test pieces (any of the test pieces of zinc alloys a1 to a4 and B1 to B15) was measured using a vickers hardness tester ("MVK-200" manufactured by sanfeng corporation). The measurement conditions are as follows.
(conditions for measurement of Vickers hardness)
Atmosphere temperature: 25 deg.C
Load of diamond indenter: 500gf
Pressing time (time for applying a load of 500 gf): 10 seconds
Number of measurement sites: 7 parts
(evaluation criteria)
The arithmetic mean of the measured values of the vickers hardnesses of 5 sites excluding the maximum value and the minimum value among the measured values of the vickers hardnesses of 7 sites obtained was calculated, and the obtained arithmetic mean was used as an evaluation value (vickers hardnesses shown in table 1 below). When the evaluation value was 78.3HV or more (1.05 times or more the evaluation value of zinc alloy B1), the evaluation was "excellent hardness". On the other hand, when the evaluation value is less than 78.3HV, the evaluation is "hardness is not excellent".
[ evaluation results ]
Table 1 shows the composition (content of each element) and vickers hardness (evaluation value) of each of zinc alloys a1 to a4 (examples 1 to 4) and zinc alloys B1 to B15 (comparative examples 1 to 15).
[ Table 1]
Figure BDA0002652597740000081
As shown in table 1, the zinc alloys a1 to a4 had an Al content of 3.5 mass% or more and 4.3 mass% or less, an Mg content of 0.02 mass% or more and 0.06 mass% or less, an Sr content of 0.0008 mass% or more and 0.0048 mass% or less, and a Ca content of 0.0008 mass% or more and 0.0048 mass% or less, with the balance being Zn and unavoidable impurities.
As shown in Table 1, the Vickers hardness (evaluation value) of the zinc alloys A1 to A4 was 78.3HV or more. Therefore, the zinc alloys a1 to a4 have excellent hardness.
As shown in table 1, the content of Sr in the zinc alloy B1 was less than 0.0008 mass%, and the content of Ca was less than 0.0008 mass%. In the zinc alloys B2-B5, the content of Ca is less than 0.0008 mass%. In the zinc alloys B6 and B7, the Sr content was more than 0.0048 mass%, and the Ca content was less than 0.0008 mass%. In the zinc alloys B8-B11, the Sr content is less than 0.0008 mass%. In the zinc alloys B12 and B13, the Sr content is less than 0.0008 mass%, and the Ca content is greater than 0.0048 mass%. In the zinc alloys B14 and B15, the Sr content is greater than 0.0048 mass%, and the Ca content is greater than 0.0048 mass%.
As shown in Table 1, the Vickers hardness (evaluation value) of the zinc alloys B1 to B15 was less than 78.3 HV. Therefore, the zinc alloys B1 to B15 are not excellent in hardness.
< Observation with microscope >
The test pieces used for the evaluation of the vickers hardness of the zinc alloys a1 and B1 were observed with a Scanning Electron Microscope (SEM) (JSM-6700F manufactured by japan electronics corporation). Specifically, of the surfaces of test pieces (any of the test pieces of zinc alloys a1 and B1), which were not used for vickers hardness measurement, the surfaces were polished with sandpaper (#80, #500, and #1200), and then polished with diamond slurry (particle size: 0.1 μm). Subsequently, the polished surface of the test piece was etched with an ethanol solution of nitric acid (concentration of nitric acid: 1% by volume). Next, the etched surface of the test piece was observed with the scanning electron microscope and photographed.
An SEM photograph (secondary electron image) of the β phase of zinc alloy a1 is shown in fig. 1. Fig. 2 shows an SEM photograph (secondary electron image) of the β phase of zinc alloy B1. From a comparison of fig. 1 and 2, it was confirmed that the β phase of zinc alloy a1 is finer than the β phase of zinc alloy B1.
Industrial applicability
The zinc alloy of the present invention is useful as a component of precision equipment, a component of portable electronic equipment, a toy, an automobile component, building hardware, an office appliance, or a component of accessories. The method for producing a zinc alloy of the present invention is useful as a method for producing a component of precision equipment, a component of portable electronic equipment, a toy, an automobile component, building hardware, office equipment, or accessories.

Claims (5)

1. A zinc alloy containing Al, Mg, Sr and Ca,
the Al content is 3.5-4.3 mass%,
the content of Mg is 0.02 mass% or more and 0.06 mass% or less,
the Sr content is 0.0008 to 0.0048 mass%,
the content of Ca is 0.0008 to 0.0048 mass%,
the balance of Zn and inevitable impurities.
2. The zinc alloy according to claim 1, wherein a total content of the Sr and the Ca is 0.0018 mass% or more and 0.0093 mass% or less.
3. A method for producing a zinc alloy, comprising:
a pouring step of pouring the melt into a mold; and
a cooling step of cooling the poured melt,
the molten liquid contains Al, Mg, Sr and Ca,
the Al content is 3.5-4.3 mass%,
the content of Mg is 0.02 mass% or more and 0.06 mass% or less,
the Sr content is 0.0008 to 0.0048 mass%,
the content of Ca is 0.0008 to 0.0048 mass%,
the balance of Zn and inevitable impurities.
4. The method for producing a zinc alloy according to claim 3, wherein in the cooling step, the melt is cooled at a cooling rate of 10 ℃/sec or more and 100 ℃/sec or less.
5. The method for producing a zinc alloy according to claim 3 or 4, wherein the casting temperature in the casting step is 490 to 510 ℃.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
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CN102146535A (en) * 2010-02-08 2011-08-10 日曹金属化学株式会社 Zinc base alloy
CN103290264A (en) * 2013-05-21 2013-09-11 中南大学 Strontium containing casting zinc alloy and preparation method thereof
CN108504900A (en) * 2018-04-27 2018-09-07 厦门格欧博新材料科技有限公司 A kind of corrosion-resistant Environment-friendlyzinc zinc alloy

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Application publication date: 20210326