CN112301245A - Modification treatment method for epsilon phase in zinc-copper alloy - Google Patents

Modification treatment method for epsilon phase in zinc-copper alloy Download PDF

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CN112301245A
CN112301245A CN202011070711.8A CN202011070711A CN112301245A CN 112301245 A CN112301245 A CN 112301245A CN 202011070711 A CN202011070711 A CN 202011070711A CN 112301245 A CN112301245 A CN 112301245A
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王振卿
马静
刘金宇
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University of Jinan
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    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C1/00—Making non-ferrous alloys
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/003—Alloys based on aluminium containing at least 2.6% of one or more of the elements: tin, lead, antimony, bismuth, cadmium, and titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent

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Abstract

The invention belongs to the technical field of alloy materials, and particularly relates to a modification treatment method of an epsilon phase in a zinc-copper alloy. Adding a TiC particle-containing intermediate alloy into a zinc-copper alloy melt, wherein the TiC-containing intermediate alloy is Al-Ti-C or Zn-Al-Ti-C intermediate alloy. In the process of solidification, TiC solid particles can provide a large number of heterogeneous nucleation cores for epsilon-phase crystals in the zinc-copper alloy, so that epsilon-phase crystal grains are greatly increased in number and greatly reduced in size, and branches of the crystal grains are inhibited and greatly reduced. The melting point of the Zn-Al-Ti-C intermediate alloy is lower (about 500-.

Description

Modification treatment method for epsilon phase in zinc-copper alloy
Technical Field
The invention belongs to the technical field of alloy materials, and particularly relates to a modification treatment method of an epsilon phase in a zinc-copper alloy.
Background
Zinc with copper content between 3 and 16wt.%The microstructure of the-copper binary alloy is mainly composed of eta-Zn phase and epsilon (CuZn)4Or CuZn5Compound) phase grain mixture. When the zinc-copper alloy is solidified, epsilon phase is firstly separated out from liquid phase through peritectic reaction and grows freely, when the copper content is lower than about 3.5wt.%, the quantity of epsilon phase is smaller, when the copper content is higher than 3.5%, because a large quantity of epsilon phase crystal grains are separated out in a wider temperature range, finally dendrite which contains a large quantity of secondary and tertiary branches and has larger size is formed, and when the copper content is higher than 10%, a large quantity of epsilon phase dendrite is easy to be mutually connected to form a net structure. The generation of the developed dendrites can bring a series of product quality and production process problems of micro shrinkage porosity, micro segregation, heat cracking, toughness reduction, casting process performance (such as fluidity and mold filling capacity) reduction and the like to the alloy. The strength property can be improved by adding a small amount of aluminum element in the zinc-copper binary alloy, when the aluminum content is 5wt.% or less, the aluminum element mainly exists in the alloy in a Zn-Al eutectic structure and has no influence on an epsilon phase, and when the aluminum content is more than 5wt.%, the aluminum element mainly exists in the alloy in a Zn-Al eutectic structure and primary alpha-Al grains, and meanwhile, part of the aluminum element is in solid solution in the epsilon phase. When the aluminum content is more than 10wt.% and is gradually increased, the developed dendrites of the epsilon phase are gradually divided into discontinuous fine phases by the influence of the aluminum element.
The zinc-copper binary alloy containing 3.5-16wt.% of copper or the zinc-copper alloy containing a small amount of aluminum (less than 10 wt.%) and other elements is subjected to modification treatment to change the developed dendritic crystal characteristics of the epsilon phase, so that the epsilon phase with few branches or even no branches and fine grain size is obtained, and the method is an effective method for improving the service performance and the process performance of the zinc-copper alloy. Patent documents 201810869355.2 and 201810869291.6 disclose that antimony or bismuth is added as a simple substance to perform modification treatment, and the modification treatment has a certain effect, but the price of antimony or bismuth is high (several times the price of pure zinc). Therefore, in the actual production of zinc-copper alloy, an alterant or an alteration treatment method which has high efficiency, convenient operation and low cost is needed to be found. In addition, in actual production, different trace elements are often required to be added to the zinc-copper base alloy for alloying, so that different actual requirements are required for the element components of the alterant, and accordingly, various types of zinc-copper alloy alterants are required to be suitable for being selected and used under different conditions.
Disclosure of Invention
In view of the above problems, the present invention provides a method for modifying an epsilon phase having developed dendrites in a zinc-copper alloy with a master alloy containing TiC particles. By adding the intermediate alloy containing TiC particles into the zinc-copper alloy melt, in the solidification process, the TiC solid particles can provide a large amount of heterogeneous nucleation cores for epsilon-phase crystals in the zinc-copper alloy, so that the quantity of epsilon-phase crystal grains is greatly increased, the size is greatly reduced, and the branching of the crystal grains is greatly reduced by inhibiting; meanwhile, the smelting treatment time is shortened, and the production cost is saved.
The technical scheme of the invention is as follows:
a modification treatment method of epsilon phase in zinc-copper alloy is characterized in that master alloy containing TiC particles is added into zinc-copper alloy melt.
The intermediate alloy containing TiC particles is Al-Ti-C intermediate alloy.
Preferably, the content of Ti element in the Al-Ti-C intermediate alloy is 1-10wt.%, the content of C element is 0.1-2.5wt.%, and the mass percentage ratio of Ti element to C element is greater than or equal to 4: 1.
The modification treatment method of the zinc-copper alloy comprises the following steps:
(1) melting the zinc-copper alloy to be refined to 660-730 ℃ to obtain a zinc-copper alloy melt;
(2) adding the Al-Ti-C intermediate alloy into the zinc-copper alloy melt in the step (1), stirring, keeping the temperature for 5-35 minutes, and stirring the melt again to uniformly distribute Ti and C elements in the melt;
(3) and (3) pouring the alloy melt obtained in the step (2) into a mold for cooling, and solidifying to obtain the zinc-copper alloy subjected to modification treatment.
Preferably, the Al-Ti-C master alloy is added in the above step (2) in an amount such that the percentage of C element in the zinc-copper alloy is 0.001wt.% to 0.05 wt.%.
The zinc-copper alloy is obtained by adopting the modification treatment method of the zinc-copper alloy.
Optionally, the TiC particle-containing intermediate alloy is a Zn-Al-Ti-C intermediate alloy.
Preferably, the content of Ti element in the Zn-Al-Ti-C master alloy is 0.1-10wt.%, and the content of C element is 0.01-2.5 wt.%; the mass percentage of the Ti and the C is more than or equal to 4: 1.
The modification treatment method of the epsilon phase in the zinc-copper alloy comprises the following steps:
(1) melting the zinc-copper alloy to be refined to 40-100 ℃ above the liquidus line of the zinc-copper alloy to obtain a zinc-copper alloy melt;
(2) adding a certain proportion of Zn-Al-Ti-C intermediate alloy into the zinc-copper alloy melt in the step (1), stirring, keeping the temperature for 2-25 minutes, and stirring the melt again to uniformly distribute Ti and C elements in the melt;
(3) and (3) pouring the alloy melt obtained in the step (2) into a mold for cooling, and solidifying to obtain the zinc-copper alloy subjected to modification treatment.
Preferably, the Zn-Al-Ti-C master alloy is added in the above step (2) in an amount such that the percentage of C element in the zinc-copper alloy is 0.001wt.% to 0.05 wt.%.
The zinc-copper alloy is obtained by adopting the modification treatment method of the epsilon phase in the zinc-copper alloy.
When the intermediate alloy containing TiC particles is Al-Ti-C intermediate alloy and the mass percentage content ratio of Ti to C is 4:1, the structure of the intermediate alloy consists of aluminum crystal grains and TiC particles embedded in the aluminum crystal grains; when the mass percentage of the Ti and the C is more than 4:1, the structure of the intermediate alloy consists of aluminum crystal grains and TiC and TiAl embedded in the aluminum crystal grains3Particles.
When the intermediate alloy containing TiC particles is Zn-Al-Ti-C intermediate alloy and the mass percentage content ratio of Ti to C is 4:1, the structure of the intermediate alloy consists of aluminum and zinc grains and TiC particles embedded in the aluminum and zinc grains; when the mass percentage of the Ti and the C is more than 4:1, the structure of the intermediate alloy consists of aluminum and zinc grains and TiC and TiAl embedded in the aluminum and zinc grains3-xZnx（0<x<3) Particles.
The intermediate alloy containing TiC particles is added into the zinc-copper alloy melt and then melted to release TiC solid particles which are uniformly distributed in the melt. In the subsequent solidification process, TiC solid particles can provide a large amount of heterogeneous nucleation cores for the crystallization of epsilon phase in the zinc-copper alloy, so that epsilon phase crystal grains are greatly increased in number and greatly reduced in size, and the branching of the crystal grains is inhibited and greatly reduced. The melting point of the Zn-Al-Ti-C intermediate alloy is lower (about 500 ℃ F.) -570 ℃), and the Zn-Al-Ti-C intermediate alloy can be quickly melted after being added into a zinc-copper alloy melt to release particles and elements with crystallization and nucleation effects, so that the smelting treatment time is shortened, and the production cost is favorably saved.
The invention has the beneficial effects that:
the melting point of TiC particles is higher than 2000 ℃, the TiC particles are stable in zinc-copper alloy performance and can generate high-efficiency heterogeneous nucleation on epsilon phase; TiC particles are added into the zinc-copper alloy in a mode of intermediate alloy, the operation process is convenient, and the absorption rate reaches 100%; the zinc, aluminum, titanium and carbon elements required by producing the intermediate alloy such as Al-Ti-C or Zn-Al-Ti-C are wide in raw material source and low in cost, and the production process of the intermediate alloy is easy to carry out; therefore, the intermediate alloy containing TiC particles as the alterant of the zinc-copper alloy has the advantages of high effect, convenient operation and low raw material cost, and provides more optional alterant types for the production of different types of zinc-copper alloys under different conditions.
Drawings
FIG. 1 is a structural view of an optical microscope of a Zn-7Cu alloy which has not been subjected to a modification treatment; wherein the shiny dendritic phase is the epsilon phase.
FIG. 2 is a structural diagram of an optical microscope with a Zn-7Cu alloy added with 4% pure Al; wherein the shiny dendritic phase is the epsilon phase.
FIG. 3 is a structural diagram of an optical microscope of a Zn-7Cu alloy after modification treatment with 1wt.% Al-5Ti-0.35C master alloy according to an embodiment of the present invention; wherein the shiny dendritic phase is the epsilon phase.
FIG. 4 is an optical microscopic structure diagram of a Zn-7Cu alloy after modification treatment with 1wt.% Al-6Ti master alloy; wherein the shiny dendritic phase is the epsilon phase.
FIG. 5 is a Scanning Electron Microscope (SEM) backscattered electron image of an alloy modified by adding 1wt.% Al-5Ti-0.35C master alloy in the first example, wherein the dendrites at 2 are identified as the epsilon phase by EDS spectroscopy, and the black particles at the center 1 of the epsilon phase are TiC (the EDS spectrum is shown in FIG. 6).
FIG. 6 is an EDS spectrum of the black particles at 1 in FIG. 5, showing that the particles contain elements Ti and C, illustrating that the particles are from TiC particles in an Al-Ti-C master alloy.
FIG. 7 is an optical microscope microstructure of a Zn-7Cu alloy after modification treatment with 4wt.% Al-10Ti-1C master alloy added in example IV; wherein the shiny dendritic phase is the epsilon phase.
FIG. 8 is a comparison of the results of example seven: an optical microscope structure diagram of the alloy obtained after 2 percent of pure aluminum is added into the Zn-12Cu-2Al alloy; wherein the shiny dendritic phase is the epsilon phase.
FIG. 9 is an optical microscopic structural diagram of an alloy obtained by modification treatment of a Zn-12Cu-2Al alloy in accordance with example VII with 2wt.% Al-10Ti-1C master alloy; wherein the shiny dendritic phase is the epsilon phase.
Figure 10 compares the nine metamorphic effects of the embodiment: adding 4% pure aluminum into the Zn-10Cu-4Al alloy to obtain an optical microscope tissue structure diagram of the alloy; wherein the shiny dendritic phase is the epsilon phase.
FIG. 11 is a structural diagram of an optical microscope of a Zn-10Cu-4Al alloy modified by adding 4wt.% Al-10Ti-1C master alloy in example nine; wherein the shiny dendritic phase is the epsilon phase.
Detailed Description
The invention is further illustrated by the following specific examples. The following examples are only for explaining the present invention and do not limit the content of the present invention.
Example one
And (3) modifying the epsilon-phase dendrites in the Zn-7Cu alloy (wherein the mass percentage of Cu is 7%) by using an Al-5Ti-0.35 intermediate alloy. Al-5Ti-0.3The mass contents of Ti and C in the 5C intermediate alloy are respectively 5% and 0.35% (the contents of the above percentages are the same as the meanings of the expression methods in the whole patent), C and Ti are combined to form a TiC phase, and Ti is also TiAl3The phase mode exists. The method comprises the following specific steps.
(1) And melting the Zn-7Cu alloy to 670 ℃ to obtain an alloy melt.
(2) 1wt.% of Al-5Ti-0.35C master alloy was added to the above melt, the melt was stirred and then held for 30 minutes.
(3) Stirring the alloy melt again to obtain TiAndthe element C is uniformly distributed in the melt. And then pouring the melt into a mold, and cooling to obtain the modified Zn-7Cu alloy.
To illustrate the effect of pure Al, Al-Ti intermediate alloy and Al-Ti-C intermediate alloy on epsilon phase in zinc-copper alloy, the structure diagrams of the following four alloys obtained under the same cooling condition are shown in the attached drawings 1, 2, 3 and 4 respectively: zn-7Cu and Zn-7Cu were obtained by adding 4wt.% Al, Zn-7Cu was obtained by adding 1wt.% Al-5Ti-0.35C master alloy (obtained in this example), and Zn-7Cu was obtained by adding 1wt.% Al-6Ti master alloy. Comparing fig. 1 and 2, it can be seen that the epsilon phase characteristics are the same in both alloys: the branch is developed and has large size, the primary dendrite contains a large amount of secondary dendrite and a small amount of tertiary dendrite, and the sizes of the primary dendrite and the secondary dendrite can reach more than 150 and 30 mu m respectively; comparing the Zn-7Cu (FIG. 3) obtained by modification in this example with the above two alloys, it can be seen that: after 1wt.% of Al-5Ti-0.35C master alloy is added, the developed dendrites before modification are converted into petal-like grains (about 40 μm in size) with smaller size, or polyhedral and spherical grains with smaller size. Comparing fig. 4 with fig. 1 and 2, it can be seen that: the size of the epsilon phase in the Zn-7Cu alloy after addition of the 1wt.% Al-6Ti master alloy is reduced, producing some metamorphic effect, but the epsilon phase in fig. 4 is still a developed dendrite containing primary and secondary branches and is several times larger in size than the epsilon phase in fig. 3. It can be seen that: when the aluminum element is added alone, no modification effect is generated on the epsilon phase, and the modification effect of the Al-5Ti-0.35C intermediate alloy is far higher than that of the Al-6Ti intermediate alloy.
The modification principle of the Al-Ti-C intermediate alloy is as follows: a large amount of TiC particles released by the Al-5Ti-0.35C intermediate alloy serve as a solid phase substrate for epsilon phase crystallization nucleation in the alloy solidification process, and the generation of more epsilon phase particles is promoted, so that the growth of epsilon phase is inhibited, and efficient metamorphism is generated. FIG. 5 is an SEM back-scattered electron image of Zn-7Cu after modification with 1wt.% Al-5Ti-0.35C master alloy of this example, showing that TiC particles located at the center of the epsilon phase grains are clearly observed (FIG. 6 is an EDS energy spectrum thereof).
Example two
In the first example, the Al-5Ti-0.35C master alloy was replaced with the Zn-40Al-5Ti-0.35C master alloy, the 670 ℃ in the step (1) was changed to 580 ℃, the 30 minutes in the step (2) was changed to 10 minutes, and the other steps and contents were not changed, whereby the Zn-7Cu alloy modification effect similar to that of the first example was obtained.
EXAMPLE III
In the first embodiment, the Al-5Ti-0.35C master alloy is replaced by the Al-5Ti-1.25C master alloy, and the modification effect of the Zn-7Cu alloy similar to that of the first embodiment can be obtained without changing the steps and the content. The Al-5Ti-1.25C intermediate alloy contains two phases of aluminum and TiC.
Example four
The method for modifying epsilon-phase dendrites in the Zn-7Cu alloy comprises the following specific steps:
(1) and melting the Zn-7Cu alloy to 720 ℃ to obtain an alloy melt.
(2) Adding Al-10Ti-1C intermediate alloy with the proportion of 4wt.% into the melt, stirring the melt, and then preserving the heat for 15 minutes.
(3) And stirring the alloy melt again to ensure that the Ti and the C elements are uniformly distributed in the melt. And then pouring the melt into a mold, and cooling to obtain the alloy subjected to modification treatment.
The epsilon phase in the Zn-7Cu alloy modified by the method of the embodiment is converted into polyhedral or petaloid grains, the size is only about 25 mu m (figure 7), and obvious modification effect is generated.
EXAMPLE five
In the fourth example, the same Zn-7Cu-4Al alloy modification effect as in the fourth example was obtained by replacing the Al-10Ti-1C master alloy with the Zn-50Al-5Ti-0.35C master alloy, changing 720 ℃ to 570 ℃ in step (1), and changing 15 minutes to 10 minutes in step (2), with the remainder being unchanged.
EXAMPLE six
In the fourth example, the Al-10Ti-1C master alloy was replaced with the Al-8Ti-2C master alloy (containing only two phases of Al and TiC), and the modification effect of the Zn-7Cu-4Al alloy similar to that of the fourth example was obtained without changing the steps and the content.
EXAMPLE seven
The method for modifying the epsilon-phase dendrite in the Zn-12Cu-2Al alloy comprises the following specific steps:
(1) and melting the Zn-12Cu-2Al alloy to 730 ℃ to obtain an alloy melt.
(2) Adding an Al-10Ti-1C intermediate alloy in a proportion of 2wt.% into the melt, stirring the melt, and then keeping the temperature for 20 minutes.
(3) And stirring the alloy melt again to ensure that the Ti and the C elements are uniformly distributed in the melt. And then pouring the melt into a mold, and cooling to obtain the alloy subjected to modification treatment.
The Al-10Ti-1C master alloy in this example was changed to pure aluminum, and the other conditions were not changed, and the epsilon phase in the obtained alloy was a developed dendrite containing a large number of primary and secondary branches and having a size of 100 μm or more (FIG. 8). In the embodiment, after 2 percent of Al-10Ti-1C master alloy is added for modification, the epsilon phase is converted into polyhedral or petaloid grains, the size is only about 40 mu m (figure 9), and obvious modification effect is generated.
Example eight
In the seventh embodiment, the temperature of 730 ℃ in the step (1) is changed to 670 ℃, the Al-10Ti-1C master alloy in the step (2) is changed to Zn-50Al-8Ti-2C master alloy, and the other parameters and the steps are the same, so that similar modification treatment effects can be obtained.
Example nine
The method for modifying the epsilon-phase dendrite in the Zn-10Cu-4Al alloy comprises the following specific steps:
(1) and melting the Zn-10Cu-4Al alloy to 710 ℃ to obtain an alloy melt.
(2) Adding Al-10Ti-1C intermediate alloy with the proportion of 4wt.% into the melt, stirring the melt, and then preserving the heat for 20 minutes.
(3) And stirring the alloy melt again to ensure that the Ti and the C elements are uniformly distributed in the melt. And then pouring the melt into a mold, and cooling to obtain the alloy subjected to modification treatment.
The Al-10Ti-1C intermediate alloy in the present example was changed to pure aluminum, and the other conditions were unchanged, and the epsilon phase of the obtained alloy was developed columnar dendrites with a size of 200 μm or more (FIG. 10). In this example, after 4% of Al-10Ti-1C master alloy is added for modification, the epsilon phase is transformed into polyhedral or petaloid grains, the size is only about 50 μm (figure 11), and efficient modification is generated.
Example ten
The method for modifying the epsilon-phase dendrite in the Zn-10Cu-4Al alloy comprises the following specific steps:
(1) and melting the Zn-10Cu-4Al alloy to 650 ℃ to obtain an alloy melt.
(2) Adding a Zn-50Al-5Ti-0.5C master alloy in a proportion of 4wt.% into the melt, stirring the melt, and then keeping the temperature for 15 minutes.
(3) And stirring the alloy melt again to ensure that the Ti and the C elements are uniformly distributed in the melt. And then pouring the melt into a mold, and cooling to obtain the modified Zn-10Cu-8Al alloy.
The alloy modification effect obtained in this example is similar to that of example nine.

Claims (10)

1. A modification treatment method of epsilon phase in zinc-copper alloy is characterized in that master alloy containing TiC particles is added into zinc-copper alloy melt.
2. The method of claim 1, wherein the TiC particles-containing master alloy is an Al-Ti-C master alloy.
3. The method for modifying epsilon phase in zinc-copper alloy as recited in claim 2, wherein said Al-Ti-C master alloy contains 1-10wt.% of Ti element, 0.1-2.5wt.% of C element, and the mass percentage ratio of Ti to C element is greater than or equal to 4: 1.
4. A method for the modification of epsilon phase in zinc-copper alloy according to claim 2 or 3, characterized by comprising the steps of:
(1) melting the zinc-copper alloy to be refined to 660-730 ℃ to obtain a zinc-copper alloy melt;
(2) adding the Al-Ti-C intermediate alloy into the zinc-copper alloy melt in the step (1), stirring, keeping the temperature for 5-35 minutes, and stirring the melt again to uniformly distribute Ti and C elements in the melt;
(3) and (3) pouring the alloy melt obtained in the step (2) into a mold for cooling, and solidifying to obtain the zinc-copper alloy subjected to modification treatment.
5. The method for the deterioration of epsilon phase in zinc-copper alloy according to claim 4, characterized in that Al-Ti-C master alloy is added in the step (2) in such an amount that the percentage of C element in zinc-copper alloy is 0.001wt.% to 0.05 wt.%.
6. The method of claim 1, wherein the master alloy containing TiC particles is a Zn-Al-Ti-C master alloy.
7. The method for the deterioration of epsilon phase in zinc-copper alloy according to claim 6, characterized in that the content of Ti element in said Zn-Al-Ti-C master alloy is 0.1-10wt.%, the content of C element is 0.01-2.5 wt.%; the mass percentage of the Ti and the C is more than or equal to 4: 1.
8. The method for modifying an epsilon phase in a zinc-copper alloy as set forth in claim 6 or 7, characterized by comprising the steps of:
(1) melting the zinc-copper alloy to be refined to 40-100 ℃ above the liquidus line of the zinc-copper alloy to obtain a zinc-copper alloy melt;
(2) adding a certain proportion of Zn-Al-Ti-C intermediate alloy into the zinc-copper alloy melt in the step (1), stirring, keeping the temperature for 2-25 minutes, and stirring the melt again to uniformly distribute Ti and C elements in the melt;
(3) and (3) pouring the alloy melt obtained in the step (2) into a mold for cooling, and solidifying to obtain the zinc-copper alloy subjected to modification treatment.
9. The method for the deterioration of epsilon phase in zinc-copper alloy according to claim 8, characterized in that the Zn-Al-Ti-C master alloy in step (2) is added in such an amount that the percentage of C element in the zinc-copper alloy is 0.001wt.% to 0.05 wt.%.
10. An alloy obtained by the method for modifying an epsilon phase in a zinc-copper alloy according to claim 1, 4 or 8, which is characterized in that: a zinc-copper alloy containing TiC particles.
CN202011070711.8A 2020-10-09 2020-10-09 Modification treatment method for epsilon phase in zinc-copper alloy Pending CN112301245A (en)

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