1. the high-strength high-elasticity corrosion-resistant high-nickel-manganese-copper alloy is characterized by comprising the following components in percentage by weight: 35 to 45wt% of Ni, 5 to 15wt% of Zn, 3.01 to 5wt% of Mn, 0.0001 to 0.1wt% of P, and the balance of Cu and unavoidable impurities.

2. The high-strength high-elasticity corrosion-resistant high-nickel-manganese-white copper alloy according to claim 1, wherein the weight percentage of Ni, Zn and Mn in the composition of the alloy satisfies the following requirements: 13 is less than or equal to 0.2Ni-0.01Zn +2Mn is less than or equal to 19.

3. The high-strength high-elasticity corrosion-resistant high-nickel-manganese-white copper alloy according to claim 1, which is characterized by comprising the following components in percentage by weight: 38-43 wt% of Ni, 8-12 wt% of Zn, 3.2-4.5 wt% of Mn, 0.0003-0.06 wt% of P, and the balance of Cu and inevitable impurities.

4. The high-strength high-elasticity corrosion-resistant high-nickel-manganese-cupronickel alloy as claimed in claim 1, further comprising 0.001-1.0 wt% of an element X selected from at least one of Mg, Al, Co, Si and Fe.

5. The high-strength high-elasticity corrosion-resistant high-nickel-manganese-cupronickel alloy as claimed in claim 1, wherein the microstructure of the alloy contains a Ni-Mn-P ternary compound.

6. The high-strength high-elasticity corrosion-resistant high-nickel-manganese cupronickel alloy as claimed in claim 5, wherein the Ni-Mn-P ternary compound is formed by multi-stage annealing.

7. The high-nickel-manganese-cupronickel alloy with high strength, high elasticity, corrosion resistance as claimed in claim 1, wherein the elastic modulus of the alloy is 152GPa or more.

8. The preparation method of the high-strength high-elasticity corrosion-resistant high-nickel-manganese-white copper alloy as claimed in any one of claims 1 to 7, characterized in that the preparation process flow is as follows: batching → horizontal continuous casting → cold working → recrystallization annealing → cold working → softening annealing → cold working → finished product, wherein the temperature of the softening annealing is 500-750 ℃, the time of heat preservation is 1-5 h, and furnace cooling or air cooling is carried out after the softening annealing.

9. Use of the high-strength high-elasticity corrosion-resistant high-nickel-manganese-copper alloy according to any one of claims 1 to 7 in spectacle fittings, electromagnetic shielding parts and heat dissipation parts.

Background

Nickel-containing white copper and nickel alloy are among the most commonly used alloy materials in the high-end eyeglass processing industry. Because of the characteristics of glasses processing and application, the alloy is required to have excellent strength and corrosion resistance and good plastic processability, while the nickel-containing white copper and nickel alloy generally has excellent strength and hardness, good plasticity and excellent corrosion resistance, and therefore, the nickel-containing white copper and nickel alloy is widely applied to the glasses processing industry. Generally, low nickel cupronickel is used for middle and low end glasses, while high nickel cupronickel and nickel-based alloy materials are used for high end glasses.

Because the requirements on the strength and the corrosion resistance of the material are high, high-end glasses accessories are mainly processed by nickel-based alloy, the cost of raw materials is high, the dependence on noble metal resources is high, and the development of the high-end glasses accessory processing industry is seriously restricted. Therefore, there is a need for an alloy material having a low noble metal content. At present, nickel-based alloys are mainly replaced by high-nickel cupronickel in the market, but the material cost is reduced simply by replacing nickel by copper, but the material properties, especially the elastic properties, are slightly considered, and belong to extensive low-cost replacement. On one hand, in order to ensure the quality of high-end glasses accessories, an alloy system needs to be researched, and a copper alloy material with relatively low cost and excellent elasticity is developed to meet the requirements of relevant markets; on the other hand, for application scenes of electromagnetic shielding materials, heat dissipation components and the like, the corrosion resistance and elasticity directly affect the overall shielding or heat dissipation performance of the electromagnetic shielding materials, so that the application has higher requirements on the corrosion resistance and elasticity of the alloy, and how to further improve the corrosion resistance and elasticity is one of the development directions of the high-nickel cupronickel.

Disclosure of Invention

The first technical problem to be solved by the invention is to provide a high-nickel-manganese-copper alloy with high strength, high elasticity and corrosion resistance, aiming at the defects of the prior art.

The technical scheme adopted by the invention for solving the first technical problem is as follows: the high-strength, high-elasticity, corrosion-resistant and high-nickel-manganese-white copper alloy comprises the following components in percentage by weight: 35 to 45wt% of Ni, 5 to 15wt% of Zn, 3.01 to 5wt% of Mn, 0.0001 to 0.1wt% of P, and the balance of Cu and unavoidable impurities.

Ni is used as a main alloy element, can be infinitely dissolved with Cu, can improve the strength, hardness and corrosion resistance of the alloy when being dissolved in a copper matrix, and can form Ni-Mn and other compounds with Mn and other elements through smelting and deformation processing. The formation of the compound is beneficial to further improving the strength and the corrosion resistance of the alloy. If the Ni content is too high, the alloy has high strength and hardness, the processing difficulty is high, and the cost is increased; and the Ni content is too low, the alloy strength and the corrosion resistance are reduced, and the product requirements cannot be met. Therefore, 35 to 45wt% of Ni is preferable.

Zn element can be dissolved in the solid solution of the copper-nickel alloy in a large amount to form a wide single-phase alpha solid solution zone, which plays a role in solid solution strengthening and improves the strength and hardness of the alloy. The addition of Zn can greatly improve the atmospheric corrosion resistance of the cupronickel. Furthermore, the addition of Zn can improve the elastic properties of the cupronickel alloy. However, the high Zn content can cause the alloy to generate beta phase, reduce the plastic deformation capacity of the alloy, reduce the alloy processability and can not meet the processing requirement; and the Zn content is too low, the elasticity and the corrosion resistance of the alloy are reduced, and the product requirement cannot be met. Therefore, 5 to 15wt% of Zn is preferable.

In the invention, Mn can be dissolved in Cu and Cu-Ni alloy in a solid mode, Mn can form a compound with Ni under certain conditions, the strength and the corrosion resistance of the material are improved, and meanwhile, due to the synergistic effect of Mn and a Cu-Ni-Zn system, the elasticity and the impact corrosion resistance of the material are also improved. If the content of Mn is too high, excessive second phase can be caused to the alloy, the plastic deformation capacity of the alloy is reduced, the alloy processability is reduced, the processing requirement cannot be met, and meanwhile, the stress corrosion resistance of the alloy is reduced to a certain extent; and the Mn content is too low, so that the effects of improving the strength, elasticity and corrosion resistance of the alloy cannot be achieved, and the product requirements cannot be met. Therefore, 3.01 to 5wt% of Mn is preferable.

The trace amount of P in the invention can play the roles of degassing, deoxidizing, decarbonizing and forming Ni-Mn-P compounds with Ni-Mn in the alloy. The existence of the Ni-Mn-P compound can further change the coherent relation with the matrix, generate large lattice distortion and further generate large elastic interaction, thereby greatly improving the elastic modulus of the material. If the content of P is too high, intergranular corrosion is easy to generate at the grain boundary of the matrix, and the toughness of the material is adversely affected; and the P content is too low to play the roles of degassing, deoxidizing, decarbonizing and forming Ni-Mn-P compounds with Ni-Mn. Therefore, P is preferably 0.0001 to 0.1 wt%.

Preferably, in the composition of the alloy in percentage by weight, the content of Ni, Zn and Mn in percentage by weight satisfies: 13 is less than or equal to 0.2Ni-0.01Zn +2Mn is less than or equal to 19. The content of Ni, Zn and Mn elements in the alloy can influence the neutral salt spray corrosion resistance of the alloy to a certain extent. Because the content of Ni is higher, the alloy is a single-phase structure, only alpha phase exists, the corrosion resistance is relatively excellent, and the effect of adjusting the content of Ni on the corrosion resistance is not obvious; in the case that the alloy is a single-phase structure, the change of the Zn content has small influence on the phase proportion, so that the negative influence on the corrosion resistance of the alloy is relatively minimum; while Mn in this range promotes Ni filling of cation vacancies when corrosion occurs, thereby reducing the number of cation vacancies in the corrosion product, resulting in Cl^-The resistance to diffusion in corrosion products is increased, and the corrosion resistance of the alloy is improved under the combined action of the resistance and the Ni element. The weight percentage content of Ni, Zn and Mn is preferably less than or equal to 15 and less than or equal to 0.2Ni-0.01Zn +2Mn and less than or equal to 18.

Preferably, the alloy comprises the following components in percentage by weight: 38-43 wt% of Ni, 8-12 wt% of Zn, 3.2-4.5 wt% of Mn, 0.0003-0.06 wt% of P, and the balance of Cu and inevitable impurities.

Preferably, the alloy further comprises 0.001-1.0 wt% of X element in percentage by weight, wherein the X element is at least one selected from Mg, Al, Co, Si and Fe. The addition of the X element is helpful for refining grains, deoxidizing and removing carbon, and improves the purity of the alloy. In addition, the X element can form a precipitation strengthening phase through a special thermomechanical treatment process, so that the precipitation of alloy elements is promoted, the alloy strengthening effect is improved, and the copper alloy has higher strength, elasticity and corrosion resistance. The above effects are exhibited when the content of the element X is 0.001% or more, but if the content exceeds 1.0% by weight, the solubility limit of the element X is lowered, coarse precipitated phase particles are precipitated, the plasticity of the material is seriously lowered, and the alloy processing application is not facilitated. Therefore, the content of the X element is controlled to be 0.001 to 1.0 wt%.

Preferably, the microstructure of the alloy contains a Ni-Mn-P ternary compound. Further, the Ni-Mn-P ternary compound is formed by multi-stage annealing. The Ni-Mn-P ternary compound is uniformly and dispersedly distributed in the crystal, and the ternary compound can obviously improve the elastic property of the alloy. The existence of the Ni-Mn-P ternary compound further changes the coherent relationship between the Ni-Mn-P ternary compound and a Cu matrix, so that the matrix generates larger lattice distortion and further generates larger elastic interaction, thereby greatly improving the elastic modulus of the material to over 152 GPa.

The second technical problem to be solved by the invention is to provide a preparation method of the high-nickel-manganese-cupronickel alloy with high strength, high elasticity and corrosion resistance, aiming at the defects of the prior art.

The technical scheme adopted by the invention for solving the second technical problem is as follows: a preparation method of a high-strength high-elasticity corrosion-resistant high-nickel-manganese-white copper alloy comprises the following preparation process flows: batching → horizontal continuous casting → cold working → recrystallization annealing → cold working → softening annealing → cold working → finished product, wherein the temperature of the softening annealing is 500-750 ℃, the time of heat preservation is 1-5 h, and furnace cooling or air cooling is carried out after the softening annealing.

(1) Horizontal continuous casting: the alloy of the invention adopts a horizontal continuous casting mode to produce a casting blank, the ingredient amount is calculated according to the components of the alloy, then the raw material is melted in a medium-frequency induction furnace, and the casting blank is drawn from a heat preservation furnace. The smelting temperature is 1200-1450 ℃, the casting temperature is 1300-1450 ℃, the casting speed is 15-35 m/h, and a crystallizer is adopted for carrying out drawing casting.

(2) Cold processing: reasonable cold processing can break the alloy casting structure to form proper dislocation and deformation structure, so as to provide structure guarantee for later recrystallization annealing, be beneficial to later forming an ideal microstructure, and further achieve the effect of improving material performance. The large overall work rate helps the alloy achieve the final properties. If the pass machining rate is too high, the deformation resistance of the material is increased rapidly, the material machining is influenced, and even the material is broken; if the pass working rate is too low, the alloy is unevenly deformed, and the material is damaged. The preferable pass processing rate of the alloy is more than or equal to 15 percent, and the total processing rate between two times of softening and annealing is more than or equal to 50 percent. The most important cold work of the alloy of the present invention is cold work in the first stage after the billet is cogging (i.e., cold work after horizontal continuous casting). The cold working at this stage serves to break up the cast structure, to provide structure assurance for the subsequent recrystallization annealing, and to provide assurance for the elimination of the influence of residual stress. In order to achieve the effect, various cold deformation methods such as stretching, rolling and the like can be adopted, the complete breakage of the alloy casting structure can be ensured through the cold processing rate of not less than 50%, and meanwhile, a large amount of crystal defects such as dislocation and the like are generated in the processing process, so that good conditions are provided for subsequent recrystallization. During the subsequent recrystallization, the already present broken structure provides conditions for the nucleation of the recrystallization, so that uniform and fine grains are formed after recrystallization. Therefore, cold working in the first stage after the casting slab is opened is one of important processes for achieving the alloy structure and properties.

(3) Annealing: the recrystallization and softening annealing temperatures of the alloy are as follows: and keeping the temperature for 1-5 h at 500-750 ℃. The recrystallization annealing is to eliminate the casting structure and the cold deformation structure in the alloy structure, form equiaxed crystal grains with uniform grains, help to eliminate the casting stress of the material and lay the structure foundation for the realization of subsequent deformation processing and performance. The softening annealing is to eliminate cold deformation structure of alloy, eliminate crystal defects such as dislocation formed in the cold deformation process, improve the plasticity of the material and facilitate the continuous cold deformation processing. Meanwhile, the softening annealing combination which is carried out for a plurality of times is beneficial to forming a more uniform grain structure with adjustable grain size, provides power for forming NiMn compound phases and lays a foundation for realizing final performance. The temperature is lower than 500 ℃, the alloy only has the function of eliminating stress, and recrystallization and dislocation elimination cannot be completed, thereby influencing the plastic recovery of the material. And the temperature is higher than 750 ℃, the recrystallized grains of the alloy grow up, the grains become coarse, particularly coarse grains are locally generated, and the strength and the toughness of the alloy are reduced.

Aiming at different applications, the high-strength, high-elasticity, corrosion-resistant and high-nickel-manganese-white copper alloy can be processed into the forms of bars, wires or plates, strips and the like so as to meet the processing requirements of different downstream products.

The third technical problem to be solved by the invention is to provide the application of the high-strength, high-elasticity, corrosion-resistant and high-nickel-manganese-white copper alloy in glasses fittings, electromagnetic shielding parts and heat dissipation parts aiming at the defects of the prior art.

Compared with the prior art, the invention has the advantages that:

(1) according to the invention, by adding Mn, P and other elements into the zinc-copper alloy matrix, the strong elastic interaction between the zinc-copper alloy and the Cu matrix is formed under the action of Ni, Mn and P, so that the high-performance nickel-manganese-copper alloy with higher strength, better corrosion resistance and excellent elastic property is obtained.

(2) According to the invention, Ni, Mn and P form a Ni-Mn-P ternary compound, and the compound and a Cu matrix are subjected to elastic interaction to realize the strengthening effect on the alloy, so that the excellent comprehensive properties of the product, such as tensile strength, elastic modulus, corrosion resistance and the like, are finally realized.

(3) The alloy can realize the elastic modulus of over 152GPa, has excellent corrosion resistance, and can be applied to spectacle accessories, electromagnetic shielding parts and heat dissipation parts.

Drawings

FIG. 1 is a scanning electron micrograph of an alloy wire rod of example 4.

Detailed Description

The invention is described in further detail below with reference to the accompanying examples.

Alloy wire samples were prepared and dosed according to the compositions of examples 1-10, comparative example 1: according to the copper alloy ingredients shown in the components of each example and comparative example in the table 1, carrying out fusion casting at 1200-1450 ℃ to obtain a phi 16mm casting blank with qualified chemical components; drawing or rolling a phi 16mm casting blank at a cold working rate of not less than 50% to obtain a phi 10mm blank; carrying out recrystallization annealing on the blank with the phi 10mm at the temperature of 500-750 ℃ for 1-5 h, and then drawing at a cold working rate of not less than 50% to obtain a phi 6mm drawn blank; softening and annealing the phi 6mm stretched blank at 500-750 ℃ for 1-5 h, and then stretching at a cold working rate of not less than 50% to obtain a phi 4mm stretched blank; softening and annealing the phi 4mm drawing blank at 500-750 ℃ for 1-5 h, and then performing cold machining to finally obtain a phi 3.5mm wire rod sample.

The obtained wire rod samples were subjected to characteristic evaluation under the following conditions.

Tensile test at room temperature according to GB/T228.1-2010 Metal Material tensile test part 1: room temperature test method tests the tensile strength, elongation, yield strength and other properties on an electronic universal mechanical property testing machine.

Elastic modulus test the elastic modulus is tested on a Buzz elastic modulus tester according to the GB/T22315 + 2008 test method for the elastic modulus and Poisson ratio of the metal material.

And observing the information such as the microstructure of the sample under an optical microscope, a scanning electron microscope and a transmission electron microscope.

The alloy compositions of examples 1 to 10 and comparative example 1 are shown in Table 1, and the properties are shown in Table 2.

The scanning electron micrograph of the alloy wire of example 4 is shown in FIG. 1, and the energy spectrum analysis results at the "spectrogram 1" point in FIG. 1 are shown in Table 3.

The overall performance comparison of the alloy of the embodiment of the invention and the alloy of the comparative example shows that the tensile strength of the alloy of the invention can reach more than 900MPa at most, and the elastic modulus of the alloy can reach more than 152 GPa. Aiming at different application states, the elongation of the alloy can reach more than 30 percent.

TABLE 1 ingredients of examples and comparative examples

Formula 1 ═ 0.2Ni-0.01Zn +2Mn

TABLE 2 Properties of examples and comparative examples

Serial number	Tensile strength/MPa	Elongation/percent	Modulus of elasticity/GPa
				Example 1	580	29.5	152
Example 2	586	29.8	153
				Example 3	591	28.9	155
Example 4	607	34	157
				Example 5	611	31	158
Example 6	627	28	158
				Example 7	646	29	157
Example 8	662	25	159
				Example 9	782	14	159
Example 10	921	3	160
				Comparative example 1	585	15	148

Table 3 results of energy spectrum analysis of alloy of example 4

Element(s)	wt％	Atomic percent
			P	5.77	10.73
Mn	6.27	6.50
			Ni	54.49	52.88
Cu	28.31	25.39
			Zn	5.17	4.50
Total amount:	100.00	100.00