CN116411203A - Heterogeneous lamellar structure copper-zinc alloy and preparation method thereof - Google Patents
Heterogeneous lamellar structure copper-zinc alloy and preparation method thereof Download PDFInfo
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- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 64
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 84
- 229910002535 CuZn Inorganic materials 0.000 claims abstract description 71
- 238000000137 annealing Methods 0.000 claims abstract description 48
- 238000003466 welding Methods 0.000 claims abstract description 25
- 229910000905 alloy phase Inorganic materials 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims description 45
- 229910045601 alloy Inorganic materials 0.000 claims description 44
- 238000005096 rolling process Methods 0.000 claims description 31
- 238000005097 cold rolling Methods 0.000 claims description 18
- 238000005520 cutting process Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 15
- 238000005457 optimization Methods 0.000 abstract description 13
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 238000003754 machining Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0004—Cutting, tearing or severing, e.g. bursting; Cutter details
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
Abstract
The invention discloses a heterogeneous lamellar structure copper-zinc alloy, which is formed by alternately arranging lamellar coarse-grain Cu phases and lamellar fine-grain CuZn alloy phases; the grain size of the coarse-grain Cu phase is 3-10 mu m; the grain size of the fine-grain CuZn alloy phase is 100 nm-2 mu m. The structured coarse/fine grain heterogeneous lamellar structure not only comprises high-strength lamellar fine grains but also comprises high-ductility lamellar coarse grains, and the cooperative optimization of the strength and ductility of the copper-zinc alloy is realized through the mutual matching of soft/hard phases; in addition, the preparation method combines the accumulated stitch welding deformation with the subsequent annealing treatment, and the process not only can realize the fine regulation and optimization of the coarse/fine crystal heterogeneous lamellar structure, but also can prepare the large-size high-strength high-plasticity copper zinc alloy block material for light weight engineering application, and is hopeful to be popularized to the creation of other high-strength high-plasticity metal material systems.
Description
Technical Field
The invention relates to a copper alloy material, in particular to a heterogeneous lamellar structure copper-zinc alloy and a preparation method thereof.
Background
Copper zinc alloy plays an irreplaceable role in applications in fields of petrochemical industry, ocean engineering, electric power engineering, military engineering and the like due to excellent corrosion resistance and excellent electric/heat conductivity. With the rapid development of modern industry, increasingly severe service conditions put higher demands on the mechanical properties of copper-zinc alloys. However, the traditional strengthening mechanism such as solid solution strengthening, deformation strengthening, second phase strengthening and fine grain strengthening is easy to cause plastic deterioration while improving the strength of the copper-zinc alloy, and shows a strong strength-plastic inverted relation, so that the application of the copper-zinc alloy is greatly limited.
Inspired by the high strength and toughness matching effect of a natural biological material 'multi-stage multi-scale structure', material scientists at home and abroad in recent years provide a new thought for solving the problem of the strength-plasticity inversion relationship by orderly constructing the internal microstructure of the material such as crystal grains, crystal defects, phase compositions and the like and introducing micro/nano trans-scale heterogeneous structures with the space in non-uniform distribution such as gradient, double peaks, lamellar, core-shell and other structures. The microstructure of the coarse/fine grain heterogeneous lamellar tissue formed by alternately superposing micron coarse grains and nanometer (superfine) grains has the outstanding advantages of multiple layers, easiness in regulation and control, simple configuration, strong designability and the like, and becomes an ideal model for strong plasticization research of copper-zinc alloy.
At present, the coarse/fine grain heterogeneous lamellar structure metal is usually prepared by combining cold rolling deformation with a subsequent annealing process, and the principle of the process route is that the heterogeneous plastic deformation is firstly introduced into the metal, then incomplete recrystallization is controlled by utilizing the heterogeneous deformation, and finally the coarse/fine grain heterogeneous lamellar structure is obtained. The method can not accurately control the microstructure characteristics such as the size, the ratio, the spatial distribution and the like of the coarse/fine grain in the coarse/fine grain heterogeneous lamellar structure metal, so that the performance repeatability of the coarse/fine grain heterogeneous lamellar structure metal is poor, and finally, the industrial production and the application can not be carried out.
In summary, through massive search by the applicant, at least the problems of incapability of accurately controlling microstructure characteristics such as coarse/fine grain size, ratio, spatial distribution and the like in the heterogeneous structure metal exist in the field, so that the performance repeatability of the coarse/fine grain heterogeneous lamellar structure metal is poor, and finally industrial production and application cannot be performed. Therefore, there is a need to develop or improve a heterogeneous lamellar structure copper-zinc alloy and a preparation method thereof.
Disclosure of Invention
Based on the problems, the microstructure characteristics of coarse/fine grain size, ratio, space distribution and the like in the heterogeneous structure metal cannot be accurately controlled, and the like, the invention provides a heterogeneous lamellar structure copper-zinc alloy and a preparation method thereof, and the specific technical scheme is as follows:
a heterogeneous lamellar structure copper-zinc alloy consists of coarse-grain Cu phases and fine-grain CuZn alloy phases which are alternately arranged in a lamellar manner; the grain size of the coarse-grain Cu phase is 3-10 mu m; the grain size of the fine-grain CuZn alloy phase is 100 nm-2 mu m.
Further, the alternating layered thickness of the coarse-grain Cu phase and the fine-grain CuZn alloy phase is 5-10 mu m.
Further, the coarse-grain Cu phase comprises a fully recrystallized micro-coarse-grain structure; the fine-grain CuZn alloy phase contains an ultrafine grain structure generated by deformation.
Further, the ratio of the coarse-grain Cu phase to the fine-grain CuZn alloy phase is one of 1:1, 2:1, 3:1 and 4:1.
Further, the tensile strength of the heterogeneous lamellar structure copper-zinc alloy is 340 MPa-600 MPa, and the elongation is 15% -30%.
Further, the yield strength of the heterogeneous lamellar structure copper-zinc alloy is 290-500 MPa.
In addition, the application provides a preparation method of the heterogeneous lamellar structure copper-zinc alloy, which comprises the following steps:
step 1), raw material preparation: cutting pure Cu and CuZn alloy plates respectively; annealing and softening the cut Cu and the cut CuZn alloy respectively to obtain annealed Cu and annealed CuZn alloy;
step 2), surface treatment: respectively carrying out oil stain removal and oxide scale removal treatment on the surface of the annealed Cu and annealed CuZn alloy in the step 1);
step 3), rolling treatment: laminating the annealed Cu and annealed CuZn alloy obtained in the step 2) in the order of the annealed Cu, annealed CuZn alloy and annealed Cu, and cold-rolling and welding by using a slow rolling mill to obtain a first laminated structure;
step 4), accumulating and stitch welding: cutting edges and centrally cutting the head and tail of the first laminated structure along the long edge, carrying out surface treatment again on the cut first laminated structure, carrying out cold rolling welding by using a slow rolling machine after stacking, and repeating the steps for a plurality of times to obtain a second laminated structure;
step 5), annealing heat treatment: and (3) annealing the second laminated structure obtained in the step (4) to obtain the copper-zinc alloy with the heterogeneous lamellar structure.
Further, the purity of Cu in the step 1) is 99.99 weight percent, and the thickness is 0.5 mm-2 mm; the CuZn alloy has 58-64% of copper content, 36-42% of zinc content and 0.5-2 mm of thickness; the softening annealing temperature is 550-650 ℃, and the softening annealing time is 45-120 min.
Further, the cold rolling welding parameters in the step 3) are as follows: the rolling mill speed is 8 r/min-20 r/min, the rolling gap width is 0.7 mm-1.5 mm, and the rolling reduction is 55% -70%.
Further, the annealing parameters of the annealing heat treatment in step 5) are: the annealing temperature is 300-500 ℃ and the annealing time is 30-120 min.
In the scheme, the heterogeneous lamellar structure copper-zinc alloy consists of coarse-grain Cu phases and fine-grain CuZn alloy phases which are alternately arranged in a lamellar manner; the grain size of the coarse-grain Cu phase is 3-10 mu m; the grain size of the fine-grain CuZn alloy phase is 100 nm-2 mu m, and the heterogeneous lamellar structure copper-zinc alloy with alternately arranged coarse/fine grains is constructed, and the structure is alternately lamellar, so that the ratio of the coarse/fine grains is uniform, and the cooperative optimization of the strength and the ductility of the heterogeneous lamellar structure copper-zinc alloy is realized; in addition, the copper-zinc alloy with the heterogeneous lamellar structure is prepared by the preparation process of accumulated laminated rolling welding and post annealing heat treatment, the preparation process of the process is simple, the ratio of coarse crystals to fine crystals is easy to control, the performance of the produced alloy is uniform and stable, and the cooperative optimization of the strength and the ductility of the copper-zinc alloy with the heterogeneous lamellar structure is realized.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic diagram of a stacked rolling process of the present invention;
fig. 3 shows that the volume ratio of the raw materials of the invention is Cu: electron back scattering plot of the product prepared with cuzn=4:1;
fig. 4 shows that the volume ratio of the raw materials of the invention is Cu: electron back scattering map of cuzn=2:1 prepared product;
fig. 5 shows that the volume ratio of the raw materials of the invention is Cu: cuzn=1:1 electron back scattering plot of the prepared product.
Detailed Description
The present invention will be described in further detail with reference to the following examples thereof in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The copper-zinc alloy with the heterogeneous lamellar structure in one embodiment of the invention is formed by alternately and lamellar arrangement of coarse-grain Cu phases and fine-grain CuZn alloy phases; the grain size of the coarse-grain Cu phase is 3-10 mu m; the grain size of the fine-grain CuZn alloy phase is 100 nm-2 mu m.
In one embodiment, the alternating layered thickness of the coarse-grain Cu phase and the fine-grain CuZn alloy phase is 5-10 μm.
In one embodiment, the coarse-grain Cu phase comprises a fully recrystallized micron coarse-grain structure; the fine-grain CuZn alloy phase contains an ultrafine grain structure generated by deformation.
In one embodiment, the coarse-grain Cu-to-fine-grain CuZn ratio is one of 1:1, 2:1, 3:1, 4:1. Wherein the ratio corresponds to the ratio between the Cu added by the raw material and the CuZn alloy added by the raw material.
In one embodiment, the heterogeneous lamellar structure copper-zinc alloy has a tensile strength of 340 MPa-600 MPa and an elongation of 15% -30%.
In one embodiment, the yield strength of the heterogeneous lamellar structure copper-zinc alloy is 290-500 MPa.
In addition, the application provides a preparation method of the heterogeneous nano lamellar structure copper-zinc alloy, which comprises the following steps:
step 1), raw material preparation: cutting pure Cu and CuZn alloy plates respectively; annealing and softening the cut Cu and the cut CuZn alloy respectively to obtain annealed Cu and annealed CuZn alloy;
step 2), surface treatment: respectively carrying out oil stain removal and oxide scale removal treatment on the surface of the annealed Cu and annealed CuZn alloy in the step 1);
step 3), rolling treatment: laminating the annealed Cu and annealed CuZn alloy obtained in the step 2) in the order of the annealed Cu, annealed CuZn alloy and annealed Cu, and cold-rolling and welding by using a slow rolling mill to obtain a first laminated structure;
step 4), carrying out accumulated stitch welding, namely cutting edges and centrally cutting the head and the tail of the first laminated structure along the long edges, carrying out surface treatment on the cut first laminated structure again, carrying out cold rolling stitch welding by using a slow bundling machine after stacking, and repeating the steps for a plurality of times to obtain a second laminated structure;
step 5), annealing heat treatment: and (3) annealing the second laminated structure obtained in the step (4) to obtain the copper-zinc alloy with the heterogeneous lamellar structure.
In one embodiment, the Cu in step 1) has a purity of 99.99wt% and a thickness of 0.5mm to 2mm; the CuZn alloy has 58-64% of copper content, 36-42% of zinc content and 0.5-2 mm of thickness; the softening annealing temperature is 550-650 ℃, and the softening annealing time is 45-120 min.
In one embodiment, the cold rolling weld parameters in step 3) are: the rolling mill speed is 8 r/min-20 r/min, the rolling gap width is 0.7 mm-1.5 mm, and the rolling reduction is 55% -70%.
In one embodiment, the annealing parameters of the annealing heat treatment in step 5) are: the annealing temperature is 300-500 ℃ and the annealing time is 30-120 min.
In one embodiment, in the step 1), the pure copper Cu and CuZn alloy plates are cut by wire-cut electric discharge machining, wherein the length, width and height of the cut size are specifically 40mm by 30mm by 1mm.
In one embodiment, in step 1), the cut Cu and the cut CuZn alloy are respectively placed in a tube furnace to be subjected to softening annealing treatment under the condition of argon atmosphere, so as to obtain annealed Cu and annealed CuZn alloy;
in one embodiment, in the step 2), the annealed Cu and annealed CuZn alloys in the step 1) are respectively placed in an acetone solution, and ultrasonic cleaning is used to remove oil stains on the surfaces; removing oxide skin on the surface by ultrasonic wave in dilute sulfuric acid solution;
in one embodiment, in the step 2), the concentration of the dilute sulfuric acid is 0.8-2 mol/L, and the ultrasonic cleaning time is 8-15 min.
In one embodiment, the number of times described in step 4) is at least 9.
The structured coarse/fine grain heterogeneous lamellar structure not only comprises high-strength lamellar fine grains but also comprises high-ductility lamellar coarse grains, and the cooperative optimization of the strength and ductility of the copper-zinc alloy is realized through the mutual matching of soft/hard phases; in addition, the preparation method combines the accumulated stitch welding deformation with the subsequent annealing treatment, and the process not only can realize the fine regulation and optimization of the coarse/fine crystal heterogeneous lamellar structure, but also can prepare large-size high-strength high-plasticity copper zinc alloy blocks for practical lightweight application, and is hopeful to be popularized to the creation of other high-strength high-plasticity metal material systems
In the scheme, the heterogeneous lamellar structure copper-zinc alloy consists of coarse-grain Cu phases and fine-grain CuZn alloy phases which are alternately arranged in a lamellar manner; the grain size of the coarse-grain Cu phase is 3-10 mu m; the grain size of the fine-grain CuZn alloy phase is 100 nm-2 mu m, and the heterogeneous lamellar structure copper-zinc alloy with alternately arranged coarse/fine grains is constructed, and the structure is alternately lamellar, so that the ratio of the coarse/fine grains is uniform, and the cooperative optimization of the strength and the ductility of the heterogeneous lamellar structure copper-zinc alloy is realized; in addition, the copper-zinc alloy with the heterogeneous lamellar structure is prepared by the preparation process of accumulated laminated rolling welding and post annealing heat treatment, the preparation process is simple, the proportion of coarse crystals and fine crystals is easy to control, the performance of the produced alloy is uniform and stable, and the cooperative optimization of the strength and the ductility of the copper-zinc alloy with the heterogeneous lamellar structure is realized.
Embodiments of the present invention will be described in detail below with reference to specific examples and fig. 1 to 5.
Fig. 2 is described in conjunction with the above preparation method, specifically, the annealed Cu and annealed CuZn alloys are first surface treated, and the thickness of annealed Cu is 1mm. The thickness of the annealed CuZn alloy is 1mm, namely Cu: cuZn=2:1, the ratio is the volume ratio, the stack is carried out in a stack mode of annealed Cu-annealed CuZn alloy-annealed Cu to form a first stack structure, cold rolling treatment is carried out on the first stack structure, cutting operation is carried out on the first stack structure after cold rolling is finished, and after surface treatment is carried out on the cut first stack structure, the stack and cold rolling treatment are continuously repeated.
Examples 1-6 and comparative examples 1-2 differ in the ratio of Cu to CuZn alloy, the rolling parameters and the annealing heat treatment parameters, the specific parameters are shown in Table 1 below,
table 1:
| project | Raw material (volume ratio) | Rolling parameters | Annealing heat treatment parameters |
| Comparative example 1 | Cu | 95% deformation | 300℃，60min |
| Example 1 | Cu:CuZn＝4:1 | 10 passes of | 300℃，60min |
| Example 2 | Cu:CuZn＝2:1 | 10 passes of | 250℃，120min |
| Example 3 | Cu:CuZn＝2:1 | 10 passes of | 300℃，60min |
| Example 4 | Cu:CuZn＝2:1 | 10 passes of | 300℃，120min |
| Example 5 | Cu:CuZn＝2:1 | 10 passes of | 400℃，60min |
| Example 6 | Cu:CuZn＝1:1 | 10 passes of | 300℃，60min |
| Comparative example 2 | CuZn | 95% deformation | 300℃，60min |
The specific preparation processes of examples 1-6 and comparative examples 1-2 are as follows:
the preparation method of the heterogeneous lamellar structure copper-zinc alloy with controllable coarse/fine grain proportion comprises the following steps:
step 1): cutting pure Cu and CuZn alloy plates respectively by using a wire-cut electric discharge machine to form a specification with the length width of 40mm and the specification of 30mm, wherein the purity of the platy Cu is 99.9wt%, the specification of the CuZn alloy plates is 58-64% of Cu and 36-42% of Zn, the cut Cu and the cut CuZn alloy plates are respectively placed in a tube furnace to be annealed and softened under the condition of argon atmosphere, the reduction temperature is 550 ℃ and the time is 120min, and the annealed Cu and the annealed CuZn alloy are obtained by cooling the plates in the furnace under the argon atmosphere after annealing;
step 2): and (2) respectively placing the annealed Cu and annealed CuZn alloy obtained in the step (1) in a beaker containing 250ml of acetone solution, cleaning by using ultrasonic waves to remove substances remained on the surface, cleaning the acetone solution remained on the surfaces of the annealed Cu and annealed CuZn alloy by using deionized water, and drying at 49 ℃ for 15min. Respectively placing the annealed Cu and annealed CuZn alloy into a beaker containing 250ml of dilute sulfuric acid with the concentration of 1mol/L, performing ultrasonic cleaning to remove an oxide layer on the surface, and then removing residual dilute sulfuric acid by using deionized water, drying for standby, wherein the drying temperature is 49 ℃, the time is 15min, and the ultrasonic cleaning time is 8-15 min;
step 3): and (3) respectively pressing the annealed Cu and the annealed CuZn alloy obtained in the step (2) on a steel wire brush by hands to wipe back and forth for 10-15 times to enable the surface of the annealed Cu and the annealed CuZn alloy to show frosted texture, exposing the fresh surface of metal, stacking the annealed Cu, the annealed CuZn alloy and the annealed Cu, clamping the annealed Cu by using tweezers with the size of 30cm, putting the annealed Cu and the annealed Cu into a slow rolling mill to carry out cold rolling welding to obtain a first laminated structure, wherein the parameters of cold rolling are that the rolling mill speed is 15r/min, and the rolling gap width is 0.7mm. In order to obtain an interface with good welding quality, the rolling deformation of the pass must reach about 60%, and the pass is marked as the 0 th pass;
step 4): and cutting edges of the obtained first laminated structure with good interface combination by using wire-cut electric discharge machining along the 1.5mm positions of the two long edges, cutting the beginning and ending sections of the first laminated structure by 5mm respectively, and finally cutting the first laminated structure in half along the long edges to obtain two first laminated structures with the same size. Then the obtained first laminated structure is treated according to the annealing and softening treatment program in the step 1) and the surface treatment in the step 2), two first laminated structures are stacked for cold rolling and welding, the rolling deformation is more than 50%, the welding processing of the first pass is completed, a second laminated structure is obtained, the steps of cutting, surface treatment, stacking and rolling and welding are repeated, the second laminated structure is treated, two second laminated structures are stacked for cold rolling and welding, the rolling deformation is more than 50%, the operation is repeated, and the second laminated structure is obtained after 9 passes of cold rolling;
step 5): and (3) annealing the second laminated structure obtained in the step (4) to obtain the heterogeneous lamellar structure copper-zinc alloy with coarse-grain Cu phases and fine-grain CuZn alloy phases alternately arranged in a lamellar mode. The annealing treatment was performed under the conditions shown in table 1.
The metals prepared in examples 1 to 6 and comparative examples 1 to 2 were subjected to the relevant property test, and the results are shown in the following Table 1. The specific testing method comprises the following steps of cutting a test sample into a dog bone-shaped tensile sample with a length and width of 18mm x 9mm and a gauge length of 5mm by using a wire electric discharge machine, and carrying out a tensile experiment on the tensile sample by using a universal testing machine to obtain the yield strength, the tensile strength and the ductility of the material.
Table 1:
from the data analysis of table 2, it is clear that the heterogeneous lamellar structure copper-zinc alloy in the present application has excellent yield strength, tensile strength and ductility. Specifically, the difference between examples 1, 3 and 6 and comparative examples 1-2 is that the addition ratio of the raw materials is different, and the process manufacturing method is the same, which shows that under the process condition, the yield strength, the tensile strength and the ductility of Cu and CuZn alloy can be ensured under different addition ratios, and the heterogeneous lamellar structure copper-zinc alloy with alternately arranged coarse/fine crystals is constructed, and the structure is alternately lamellar, so that the ratio of the coarse/fine crystals is uniform, and the cooperative optimization of the strength and the ductility of the heterogeneous lamellar structure copper-zinc alloy is realized. In addition, the raw material ratios in examples 2, 4 and 5 are the same, the preparation process parameters are different, specifically the annealing temperature and the annealing time are different, under the precondition of different annealing temperatures and different annealing times, specifically under the condition of the same annealing for 120min, the temperature is raised from 250 ℃ to 300 ℃, and under the environment of 300 ℃, the yield strength, the tensile strength and the ductility of the heterogeneous lamellar structure copper-zinc alloy can be kept in cooperation; meanwhile, at 400 ℃, the yield strength and the tensile strength are reduced, but the balance among the yield strength, the tensile strength and the ductility of the copper-zinc alloy with the heterogeneous lamellar structure can be ensured; the heterogeneous lamellar structure copper-zinc alloy plate prepared by the technical scheme has the characteristics of sufficient strength and ductility, capability of precisely controlling the proportion of coarse crystals and fine crystals, and the strength of the annealing material after the accumulated lap welding is 450-600 MPa and the elongation is 15-30%; the copper-zinc alloy with the heterogeneous lamellar structure is prepared by the preparation process of accumulated laminated rolling welding and post annealing heat treatment, the preparation process of the process is simple, the ratio of coarse crystals to fine crystals is easy to control, the performance of the produced alloy is uniform and stable, and the cooperative optimization of the strength and the ductility of the copper-zinc alloy with the heterogeneous lamellar structure is realized. The copper-zinc alloy with the heterogeneous lamellar structure, which can precisely control the proportion, is developed through the accumulated stitch welding and the annealing after rolling. The heterogeneous lamellar structure copper-zinc alloy is simple to prepare and operate and stable in performance.
Further, as can be seen from the analysis in fig. 3 to 5: in different raw material adding proportions, the obtained coarse-grain Cu-phase and fine-grain CuZn alloy phase have larger difference, thus constructing the heterogeneous lamellar structure copper-zinc alloy with alternately arranged coarse/fine grains, and realizing the cooperative optimization of the strength and the ductility of the heterogeneous lamellar structure copper-zinc alloy.
The structure of the alloy consists of lamellar coarse-grain Cu phases and lamellar fine-grain CuZn alloy phases which are alternately arranged; the grain size of the coarse-grain Cu phase is 3-10 mu m; the grain size of the fine-grain CuZn alloy phase is 100 nm-2 mu m. The structured coarse/fine grain heterogeneous lamellar structure not only comprises high-strength lamellar fine grains but also comprises high-ductility lamellar coarse grains, and the cooperative optimization of the strength and ductility of the copper-zinc alloy is realized through the mutual matching of soft/hard phases; in addition, the preparation method combines the accumulated stitch welding deformation with the subsequent annealing treatment, and the process not only can realize the fine regulation and optimization of the coarse/fine crystal heterogeneous lamellar structure, but also can prepare the large-size high-strength high-plasticity copper zinc alloy block material for light weight engineering application, and is hopeful to be popularized to the creation of other high-strength high-plasticity metal material systems.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The heterogeneous lamellar structure copper-zinc alloy is characterized by comprising coarse-grain Cu phases and fine-grain CuZn alloy phases which are alternately arranged in a lamellar manner; the grain size of the coarse-grain Cu phase is 3-10 mu m; the grain size of the fine-grain CuZn alloy phase is 100 nm-2 mu m.
2. The heterogeneous lamellar structure copper-zinc alloy according to claim 1, characterized in that the alternating lamellar thickness of the coarse-grained Cu-phase and the fine-grained CuZn-alloy phase is 5 μm to 10 μm.
3. The heterogeneous lamellar structured copper-zinc alloy according to claim 1, characterized in that the coarse-grained Cu-phase comprises a fully recrystallized micro-coarse-grained structure; the fine-grain CuZn alloy phase contains an ultrafine grain structure generated by deformation.
4. The heterogeneous lamellar structure copper-zinc alloy according to claim 1, characterized in that the ratio of coarse-grain Cu-phase to fine-grain CuZn-alloy phase is one of 1:1, 2:1, 3:1, 4:1.
5. The heterogeneous lamellar structure copper-zinc alloy according to claim 1, characterized in that the tensile strength of the heterogeneous lamellar structure copper-zinc alloy is 340 MPa-600 MPa, the elongation is 15% -30%.
6. The heterogeneous lamellar structure copper-zinc alloy according to claim 1, characterized in that the yield strength of the heterogeneous lamellar structure copper-zinc alloy is 290MPa to 500MPa.
7. The preparation method of the heterogeneous lamellar structure copper-zinc alloy is characterized by comprising the following steps of:
step 1), raw material preparation: cutting pure Cu and CuZn alloy plates respectively; annealing and softening the cut Cu and the cut CuZn alloy respectively to obtain annealed Cu and annealed CuZn alloy;
step 2), surface treatment: respectively carrying out oil stain removal and oxide scale removal treatment on the surface of the annealed Cu and annealed CuZn alloy in the step 1);
step 3), rolling treatment: laminating the annealed Cu and annealed CuZn alloy obtained in the step 2) in the order of the annealed Cu, annealed CuZn alloy and annealed Cu, and cold-rolling and welding by using a slow rolling mill to obtain a first laminated structure;
step 4), accumulating and stitch welding: cutting edges and centrally cutting the head and tail of the first laminated structure along the long edge, carrying out surface treatment again on the cut first laminated structure, carrying out cold rolling welding by using a slow rolling machine after stacking, and repeating the steps for a plurality of times to obtain a second laminated structure;
step 5), annealing heat treatment: and (3) annealing the second laminated structure obtained in the step (4) to obtain the copper-zinc alloy with the heterogeneous lamellar structure.
8. The method for producing a heterogeneous lamellar structure copper-zinc alloy according to claim 7, characterized in that the Cu purity in step 1) is 99.99wt% and the thickness is 0.5 mm-2 mm; the CuZn alloy has 58-64% of copper content, 36-42% of zinc content and 0.5-2 mm of thickness; the softening annealing temperature is 550-650 ℃, and the softening annealing time is 45-120 min.
9. The method for producing a heterogeneous lamellar structure copper-zinc alloy according to claim 7, characterized in that the cold rolling welding parameters in step 3) are: the rolling mill speed is 8 r/min-20 r/min, the rolling gap width is 0.7 mm-1.5 mm, and the rolling reduction is 55% -70%.
10. The method for producing a heterogeneous lamellar structure copper-zinc alloy according to claim 7, characterized in that the annealing parameters of the annealing heat treatment in step 5) are: the annealing temperature is 300-500 ℃ and the annealing time is 30-120 min.
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