CN117505579A - Chromium zirconium copper flat prescription and preparation method thereof - Google Patents
Chromium zirconium copper flat prescription and preparation method thereof Download PDFInfo
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- CN117505579A CN117505579A CN202311590520.8A CN202311590520A CN117505579A CN 117505579 A CN117505579 A CN 117505579A CN 202311590520 A CN202311590520 A CN 202311590520A CN 117505579 A CN117505579 A CN 117505579A
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- QZLJNVMRJXHARQ-UHFFFAOYSA-N [Zr].[Cr].[Cu] Chemical compound [Zr].[Cr].[Cu] QZLJNVMRJXHARQ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000005096 rolling process Methods 0.000 claims abstract description 88
- 239000006104 solid solution Substances 0.000 claims abstract description 76
- 238000005482 strain hardening Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000000137 annealing Methods 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 39
- 230000032683 aging Effects 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000009749 continuous casting Methods 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims description 28
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 35
- 229910052802 copper Inorganic materials 0.000 description 35
- 230000008569 process Effects 0.000 description 34
- 239000013078 crystal Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 9
- 238000007790 scraping Methods 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 7
- 229910001093 Zr alloy Inorganic materials 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- 238000005728 strengthening Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910000599 Cr alloy Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000788 chromium alloy Substances 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 229910000906 Bronze Inorganic materials 0.000 description 5
- 239000010974 bronze Substances 0.000 description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 101100366060 Caenorhabditis elegans snap-29 gene Proteins 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001887 electron backscatter diffraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
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Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
-
- 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
- C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a preparation method of a chromium zirconium copper flat prescription, which comprises the following steps: batching, upward continuous casting, first cold working (drawing/peeling), solid solution, second cold working, rolling, third cold working, aging annealing and drawing of finished products; the chromium-zirconium-copper flat square comprises the following components in percentage by mass: 0.6-0.9, zr:0.03-0.06, the balance Cu and unavoidable impurities; the processing amount of the second cold working is 1% -2.5%. By using the preparation method, the key technological parameters can be obtained quickly by substituting the size of the chromium-zirconium-copper flat square to be prepared into an empirical formula, and the trial-and-error cost is saved. The method can be used for preparing the chromium-zirconium-copper flat square with higher width-thickness ratio and higher mechanical property.
Description
Technical Field
The invention belongs to the technical field of copper alloy, and particularly relates to a chromium-zirconium-copper flat square and a preparation method thereof.
Background
Along with the high-speed development of China high-voltage transmission, the voltage in a transmission line is continuously increased, the voltage born by a circuit is higher, and the generated electric arc is larger. The high-voltage switch is used as an important component for opening and closing a circuit, and needs to bear high temperature generated by an electric arc and impact caused by high voltage. Therefore, high-voltage transmission puts higher demands on the strength and high-temperature stability of materials used for the high-voltage switch.
The chromium-zirconium-copper is used as an aging strengthening alloy, and the solid solution element is precipitated while strengthening the alloy, so that the conductivity of the copper alloy is greatly reserved. The solute elements are dispersed and distributed in the matrix, so that the growth of crystal grains at high temperature can be effectively inhibited, and the alloy has better high-temperature-resistant stability, so that the chromium-zirconium-copper flat square is widely applied to the production of high-voltage switches.
The prior preparation of the chromium zirconium copper flat has two main processes: a preparation process of the chromium zirconium copper flat square comprises the following steps: ingot casting, extrusion flattening, multiple drawing, annealing and drawing; the manufacturing process of the chromium bronze contact finger section bar for the high-voltage switch comprises the steps of S1, preparing an upward chromium-leading bronze rod, S1-1, weighing 0.6-1.2% of Cr and the balance of Cu for proportioning according to the weight percentage; s1-2, adding the ingredients in the S1-1 into a graphite crucible of an upward continuous casting furnace for melting, and keeping the temperature of the solution at 1150-1350 ℃; s1-3, carrying out upward continuous casting on the solution obtained in the step S1-2 through a vertical continuous casting machine to obtain an upward cast chromium bronze rod, and then coiling the upward cast chromium bronze rod through a coiling machine to obtain a coiled chromium bronze rod; s2, continuous extrusion, S3, cold drawing, S4, fixed-length sawing, S5, ageing heat treatment, S6 and post treatment for standby.
The other preparation process of the chromium zirconium copper flat square comprises the following steps: blank up-continuous extrusion-solid solution- (multiple drawing-annealing-drawing). The process is generally only suitable for flat square production with the width-to-thickness ratio smaller than 2, and the production of flat square with larger width-to-thickness ratio can seriously increase the drawing times and even increase the solution treatment process, which can lead to the increase of processing cost to a certain extent.
Therefore, aiming at the problem of limitation of the prior art of the chromium-zirconium-copper flat square, a controllable preparation method of the chromium-zirconium-copper flat square is needed to be designed, key process parameters can be easily obtained based on the required size of the chromium-zirconium-copper flat square, the trial-and-error cost is reasonably controlled, and the chromium-zirconium-copper flat square with higher aspect ratio and higher mechanical property can be obtained.
Disclosure of Invention
The invention provides a preparation method of a chromium-zirconium-copper flat square, by using the preparation method, key technological parameters can be obtained quickly by substituting the size of the chromium-zirconium-copper flat square to be prepared into an empirical formula, trial-and-error cost is saved, and the chromium-zirconium-copper flat square with higher width-to-thickness ratio and higher mechanical property can be prepared.
The invention provides a preparation method of a chromium zirconium copper flat prescription, which comprises the following steps: batching, upward continuous casting, first cold working (drawing/peeling), solid solution, second cold working, rolling, third cold working, aging annealing and drawing of finished products;
the chromium-zirconium-copper flat square comprises the following components in percentage by mass: 0.6-0.9, zr:0.03-0.06, the balance Cu and unavoidable impurities;
the processing amount of the second cold working is 1% -2.5%.
The proper amount of Cr and Zr elements provided by the invention have stable solid solubility in the copper matrix at the solid solution temperature, and when the content of the Cr and Zr elements is higher, certain undissolved Cr/Zr particles still exist in the solid solution material, so that the deformation of the material is greatly hindered, and the undissolved Cr/Zr particles cannot be completely and uniformly distributed, so that the material is expanded uncontrollably in the rolling process, and the subsequent production process is influenced.
The Cr and the Zr provided by the invention have interaction, and a proper amount of Zr is precipitated around the Cr in the aging process, so that the growth of Cr precipitated phases is inhibited, the Cr precipitated phases are more dispersed, and the strength and high-temperature softening resistance of the material are improved.
The Cr and Zr elements provided by the invention can be separated out in the form of a second phase in the aging process of the chromium, zirconium and copper, so that aging strengthening is achieved, lattice distortion of the chromium, zirconium and copper is reduced, the chromium, zirconium and copper has higher conductivity, but the influence of excessive Cr and Zr elements on aging strengthening is not obviously improved, and the conductivity of the chromium, zirconium and copper is obviously reduced. Therefore, in summary, the content of Cr provided by the present invention is: 0.6 to 0.9, the Zr content is: 0.03-0.06.
The second cold working is carried out in the specific embodiment of the invention before rolling after solid solution blank, and the cold working is 1% -2.5%. Because the blank after solid solution is mainly Cube recrystallization structure, if rolling is directly carried out, the phenomenon similar to ear making appears at the edge part due to different transverse deformation in the rolling process, so that the rolled blank is partially widened and uneven and has no regularity. The specific embodiment of the invention carries out small-processing cold deformation on the blank after solid solution, and can form a goss texture in a certain direction with a depth of 0-0.15mm from the surface of the blank under the combination action of a proper amount of alloy components, so that metal preferentially flows along the rolling direction in the rolling process, and the phenomenon of 'lug making' at the edge of the rolling process is eliminated. If the Cr and Zr contents are too high, a large number of hard particles are likely to be formed, and the presence of a large number of hard particles does not easily form a goss texture in a certain direction under cold working of a relatively low working amount.
By utilizing the alloy components and the mass percentages thereof provided by the invention, and under the preparation process, the empirical formulas of rolling expansion, rolling thickness and blank size after solid solution can be obtained, and further, when the size of the flat square to be manufactured is obtained, the technological parameters such as rolling thickness, rolling expansion and blank size after solid solution can be rapidly obtained, so that a large number of trial errors are avoided, trial error cost is saved, and according to the width and thickness of the manufactured chromium zirconium copper flat square, the rolling expansion L after rolling the blank and the blank size D after solid solution are obtained:
L＝A*(D-d)+D
D＝(1.1a+2b+7.1)/3.11
wherein A is a constant, the value of A is 0.5-0.55, a is the thickness of the prepared chromium zirconium copper flat square, b is the width of the prepared chromium zirconium copper flat square, and d is the rolling thickness.
Further, a 350mm roller is adopted in rolling, the roller roughness is controlled at Ra1-2, so that the surface quality of a rolled blank is ensured, and the rolling speed is controlled at 10-20m/min.
Further, the rolling thickness is the thickness+ (1.2-1.5 mm) of the chromium zirconium copper flat square, and the rolling width is the width+ (2-3 mm) of the chromium zirconium copper flat square. If the rolling thickness is too thick, the rolling width is too wide, the flat square cold working cracking is easy to cause, if the rolling thickness is too thin, if the rolling size is smaller than the width of the chromium zirconium copper flat square, the flat square drawing process cannot fill the die cavity, and the required edge angle cannot be formed.
Further, the thickness of the blank after the third cold working is the thickness plus (0.45-0.55 mm) of the chromium-zirconium-copper flat square, and the width is the width plus (0.18-0.25 mm) of the chromium-zirconium-copper flat square. The rolled blank is pulled to a reserved bottom size (third cold working), the pressing amount in the width direction/the pressing amount in the thickness direction is more than 0.3, otherwise, the middle part of the rolled blank is concave after pulling, the finished product forming is affected, and meanwhile, the fact that the reserved bottom amount is too large can lead to a large amount of goss texture to generate bending property which is unfavorable for the flat square finished product to be parallel to the rolling direction is considered.
Further, the area ratio of Cube texture to goss texture in the tissue with the depth of 0-0.15mm from the surface of the blank after the second cold working is more than 60%.
Further, the ratio of the solid solution texture Cube area to the processing texture goss area is 1:1-0.5, wherein the processing texture comprises Cube texture and goss texture. The proper amount of solid solution Cube texture at the edge can enable dislocation to move easily, and the material is easy to spread in the rolling process.
Because obvious crystal lines exist on the surface of the upward-guiding blank, the upward-guiding blank needs to be removed in order to avoid the influence of the crystal lines on the surface quality of a product, but the upward-guiding blank belongs to a solid solution state and has low hardness, and the surface of the blank is extremely easy to be scratched by directly scraping the crystal lines, so that the blank needs to be subjected to work hardening, namely, the first cold working is performed. Meanwhile, large cold working amount is favorable for providing driving force for the recrystallization of subsequent crystal grains, large cold deformation is favorable for providing driving force for the recrystallization, and meanwhile, the nucleation position of the recrystallization is increased to play a role in refining the crystal grains, and equiaxed crystals generated by the recrystallization are favorable for the plastic deformation of blanks in the rolling process, so that the working amount of the first cold working after the up-draw continuous casting is more than or equal to 35%.
Furthermore, the temperature of solid solution is 930-950 ℃, the charging amount is less than 2 tons, the solid solution temperature is too low, which is not beneficial to the solid solution of solute elements, the solid solution effect is affected, meanwhile, the solute which is not solid solution into a matrix increases the rolling deformation resistance, the solid solution temperature is too high, the size of crystal grains in the solid solution process is difficult to control, the crystal grains at the edge of a solid solution blank are easy to grow, and orange peel even cracking occurs at the edge of the rolling process. The grain size after solid solution is 0.02-0.04mm. When the grain size is too large, the impurity content in the grain boundary is easy to increase, and the stress concentration at the edge of the rolling process is easy to cause cracking at the grain boundary with more defect content. However, if the grain size is too small, the grain boundary increases the blocking effect on dislocation slip, and thus increases the deformation resistance in the rolling process.
Further, the aging annealing temperature is 450-470 ℃, and the aging time is 4-7h.
The invention also provides the chromium zirconium copper flat square prepared by the preparation method of the chromium zirconium copper flat square, and the grain size of the chromium zirconium copper flat square structure is less than or equal to 0.005mm. The small crystal grains can effectively improve the strength and the shaping of the chromium-zirconium-copper flat square, and meanwhile, the small crystal grains mean that the number of crystal boundaries is increased, and the subsequent nucleation positions of the second phase are increased.
Further, the second phase in the chromium-zirconium-copper flat structure is a Cr phase and a Zr phase, and the distribution quantity of the second phase in the chromium-zirconium-copper flat structure is as follows: 50000 pieces/mm 2 . The fine dispersed secondary phase and a large number of grain boundaries can effectively inhibit the movement of dislocation, and the strength and high-temperature softening resistance of the material are improved.
Further, the thickness of the chromium zirconium copper flat square is more than 2mm, the width is more than 15mm, and the width-thickness ratio is 2-8.
Compared with the prior art, the invention has the beneficial effects that:
by controlling the Cr/Zr content and the solid solution process, the undissolved Cr/Zr particles are remained in the matrix as little as possible on the basis of controlling the grain size, the rolling resistance is reduced, and the risk of uncontrollable rolling expansion is reduced. Before rolling, a texture tissue with a certain depth is formed by small processing amount cold working, rolling expansion size is controlled, the dimensional relation between a rolled finished product and a solid solution blank and the relation between rolling expansion and rolling thickness can be obtained by controlling two points, and a reference is provided for preparing a flat square with the width-thickness ratio more than 2, so that key technological parameters can be obtained quickly, and trial-and-error cost is saved.
Meanwhile, the high-dispersion strengthening and fine-grain strengthening products are obtained by utilizing large-processing-amount rolling, crushing crystal grains and further increasing the nucleation position of Cr/Zr second phases in the annealing process while greatly improving the processing efficiency, so that the tensile strength of flat square products reaches more than 500MPa, the hardness reaches more than 145HB and the extension A100% reaches more than 15%. The high-voltage switch after processing can obtain higher strength and hardness while meeting the requirement of the subsequent cold processing of the flat square.
Drawings
FIG. 1 is a metallographic structure diagram of a chromium zirconium copper flat square prepared in example 1;
FIG. 2 is a second phase distribution diagram of the chromium zirconium copper flat prepared in example 2;
FIG. 3 is a graph showing the cold working cracking of chromium zirconium copper flat prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The specific embodiment of the invention provides a preparation method of the chromium zirconium copper flat square with short process flow, which is characterized in that the control of the components of the up-draw blank and the cold rolling are adopted to shorten the production process of the chromium zirconium copper flat square with large width-to-thickness ratio, and meanwhile, the relation between the size of a finished product and the rolling size and the rolling thickness and the expansion is obtained, so that the chromium zirconium copper flat square with short process flow is formed by solidification.
Specific examples of the invention 6 examples and 4 comparative examples are provided, with specific compositions shown in table 1.
The preparation method provided by the embodiment of the invention comprises the following process flows: raw material preparation, upward continuous casting, first cold working (drawing/peeling), solid solution, acid washing, second cold working, rolling, third cold working, aging annealing and finished product drawing. The raw materials are as follows: oxygen-free copper rod, copper-chromium cored wire and copper-zirconium cored wire; wherein the copper-chromium cored wire is prepared by wrapping pure chromium with T2 red copper, and the copper-zirconium cored wire is prepared by adopting T2 red copper and copper-zirconium alloy.
Example 1
The chromium-zirconium-copper flat square provided by the implementation comprises the following components in percentage by mass of 100 percent: cr 0.6%, zr:0.04%, the balance copper and unavoidable impurities, and the finished product size is 4mm by 20mm.
The preparation method provided by the implementation comprises the following specific steps:
s1, smelting: adding a proper amount of oxygen-free copper rod into an upward-drawing furnace according to the component mass percentage of the chromium-zirconium-copper flat square, introducing argon and heating until the oxygen-free rod is completely melted, starting automatic feeding of the oxygen-free rod, controlling the feeding speed at 220Kg/h, stopping feeding of the oxygen-free rod when the copper liquid is 20cm away from the edge of a crucible, adding copper-chromium alloy and copper-zirconium alloy which are prepared in proportion, keeping the final temperature at 1250 ℃, preserving heat for 20min, carrying out production of a phi 28mm upward-drawing blank after detecting components are qualified, carrying out automatic feeding of oxygen-free copper rod, copper-chromium-zirconium cored wires according to preset components in the subsequent drawing process, carrying out component testing on the furnace liquid every 30min, ensuring that the components of the upward-drawing blank are qualified, and cooling water pressure at 0.3MPa and drawing speed at 0.77mm/s to obtain the diameter phi 28mm upward-drawing chromium-zirconium-copper blank.
S2, cold working for the first time: rolling a 28mm blank to 23, carrying out a subsequent drawing process according to the reducing amount of 1-2mm in each pass, drawing to 19mm, finally peeling to 17.5mm to ensure that the surface crystal lines are completely peeled off, and then drawing to 16.5mm.
S3, solid solution: and (3) carrying out solid solution on a blank with the thickness of 16.5mm, controlling the solid solution temperature to 930 ℃, controlling the conductivity of the blank after solid solution to 35-45% IACS, and controlling the hardness HV5 after solid solution to 50-70.
S4, acid washing: and (3) pickling the solid solution blank, wherein the surface of the pickled blank is free from oxidation, collision, sand holes and the like.
S5, cold working for the second time: and (3) drawing the blank with the diameter of 16.5mm to 16.4mm, wherein the drawing processing rate is 1.2%.
S6, rolling: and rolling the drawn blank to a thickness of 5.5mm, wherein the roughness of a roller in the rolling process is Ra1-2, and the rolling speed is 15m/min.
S7, third cold working: and drawing the blank by adopting a polycrystalline die 4.5 mm-20.2 mm die, wherein the horn mouth angle of the die is 10 degrees (the drawing mouth angle is smaller and can cause the drawing process of the blank and the scraping of the die edge), and the length of the bearing is controlled to be 5-7mm (the bearing is too long, the friction is increased, and the bearing is too small and is difficult to ensure the size of a finished product).
S8, aging annealing: and (3) annealing the 4.5-20.2 mm blank by adopting a horizontal bright annealing furnace, wherein the annealing temperature is 450 ℃, and the annealing time is 5 hours.
S9, drawing a finished product: and (3) drawing out a finished product by using a 4 x 20 polycrystalline die by adopting a combined drawing machine, so as to ensure the size and straightness of the product: the length of the bearing of the drawing die is controlled to be 5-7mm, the R angle deviation is controlled to be +/-0.02 mm, and the angle of the drawing opening is 6 degrees. The obtained product is shown in figure 3, the crystal phase structure is shown in figure 1, and the crystal grains are finer.
Example 2
The chromium zirconium copper flat square provided by the embodiment comprises the following components in percentage by mass of 100 percent: cr:0.7%, zr:0.045%, the balance copper and unavoidable impurities, the finished product size is 3mm x 20mm.
The preparation method provided by the embodiment comprises the following steps:
s1, smelting: adding a proper amount of oxygen-free copper rod into an upward-pulling furnace according to required components, introducing argon and heating until the oxygen-free rod is completely melted, starting automatic feeding of the oxygen-free rod, controlling the feeding speed to be 220Kg/h, stopping feeding of the oxygen-free rod when the copper liquid is 20cm away from the edge of a crucible, adding copper-chromium alloy and copper-zirconium alloy which are prepared in proportion, keeping the final temperature at 1250 ℃, preserving heat for 20min, carrying out phi 28mm upward-pulling blank production after detecting components are qualified, carrying out automatic feeding of oxygen-free copper rod, copper-chromium and zirconium cored wires according to preset components in the follow-up pulling process, carrying out component test on the furnace liquid every 30min, ensuring that the components of the upward-pulling blank are qualified, cooling water pressure to be 0.3MPa, and pulling speed to be 0.77mm/s, and obtaining the upward-pulling chromium-zirconium-copper blank with the diameter phi 28 mm;
s2, cold working for the first time: rolling a 28mm blank to 23, carrying out a subsequent drawing process according to the reducing amount of 1-2mm in each pass, drawing to 19mm, finally peeling to 17.5mm to ensure that the surface crystal lines are completely peeled off, and then drawing to 16.2mm.
S3, solid solution: and (3) carrying out solid solution on a blank with the thickness of 16.2mm, controlling the solid solution temperature to 950 ℃, controlling the conductivity of the blank to be 35-45% IACS after solid solution, and controlling the hardness HV5 to be 50-70 after solid solution.
S4, acid washing: and (3) pickling the solid solution blank, wherein the surface of the pickled blank is free from oxidation, collision, sand holes and the like.
S5, cold working for the second time: and (3) drawing the blank with the diameter of 16.2mm to 16.1mm, wherein the drawing processing rate is 1.2%.
S6, rolling: the thickness of the drawn blank is 4.5mm, the roughness of the roller in the rolling process is Ra1-2, and the rolling speed is 15m/min.
S7, third cold working: drawing the blank by adopting a polycrystalline die 3.5mm x 20.2mm, wherein the horn mouth angle of the die is 10 degrees (the drawing mouth angle is smaller and can cause the drawing process of the blank and the scraping of the die edge), and the length of a bearing is controlled to be 5-7mm (the bearing is too long, the friction is increased, and the bearing is too small to ensure the size of a finished product).
S8, aging annealing: and (3) annealing the blank with the thickness of 3.5 x 20.2mm by adopting a horizontal bright annealing furnace, wherein the annealing temperature is 470 ℃ and the annealing time is 5 hours.
S9, drawing a finished product: and (3) drawing out a finished product by using a combined drawing machine through a 3 x 20 polycrystalline die, so as to ensure the size and straightness of the product: the length of the bearing of the drawing die is controlled to be 5-7mm, the R angle deviation is controlled to be +/-0.02 mm, and the angle of the drawing opening is 6 degrees. As shown in fig. 2, the second phase of the finished product is uniformly distributed in the matrix.
Example 3
The chromium zirconium copper flat square provided by the embodiment comprises the following components in percentage by mass of 100 percent: cr:0.8%, zr:0.05%, the balance copper and unavoidable impurities, and the finished product size is 5mm x 18mm.
The preparation method provided by the embodiment comprises the following steps:
s1, smelting: adding a proper amount of oxygen-free copper rod into an upward-pulling furnace according to required components, introducing argon and heating until the oxygen-free rod is completely melted, starting automatic feeding of the oxygen-free rod, controlling the feeding speed to be 220Kg/h, stopping feeding of the oxygen-free rod when the copper liquid is 20cm away from the edge of a crucible, adding copper-chromium alloy and copper-zirconium alloy which are prepared in proportion, keeping the final temperature at 1250 ℃, preserving heat for 20min, carrying out phi 28mm upward-pulling blank production after detecting components are qualified, carrying out automatic feeding of oxygen-free copper rod, copper-chromium and zirconium cored wires according to preset components in the follow-up pulling process, carrying out component test on the furnace liquid every 30min, ensuring that the components of the upward-pulling blank are qualified, cooling water pressure to be 0.3MPa, and pulling speed to be 0.77mm/s, and obtaining the upward-pulling chromium-zirconium-copper blank with the diameter phi 28 mm;
s2, cold working for the first time: rolling a 28mm blank to 23, carrying out a subsequent drawing process according to the reducing amount of 1-2mm in each pass, drawing to 18mm, finally peeling to 16.5mm to ensure that the surface crystal lines are completely peeled off, and then drawing to 15.6mm.
S3, solid solution: and (3) carrying out solid solution on a blank with the thickness of 15.6mm, controlling the solid solution temperature to 940 ℃, controlling the conductivity of the blank to be 35-45% IACS after solid solution, and controlling the hardness HV5 to be 50-70 after solid solution.
S4, acid washing: and (3) pickling the solid solution blank, wherein the surface of the pickled blank is free from oxidation, collision, sand holes and the like.
S5, cold working for the second time: and (3) drawing the blank with the thickness of 15.6mm to 15.45mm, wherein the drawing processing rate is 1.9%.
S6, rolling: and rolling the drawn blank to a thickness of 6.5mm, wherein the roughness of a roller in the rolling process is Ra1-2, and the rolling speed is 15m/min.
S7, third cold working: and drawing the blank by adopting a 5.5mm x 18.2mm die of the polycrystalline die, wherein the horn mouth angle of the die is 10 degrees (the drawing mouth angle is smaller and can cause scraping of the blank in the drawing process and the die edge part), and the length of the bearing is controlled to be 5-7mm (the bearing is too long, the friction is increased, and the bearing is too small and is difficult to ensure the size of a finished product).
S8, aging annealing: and (3) annealing the blank with the thickness of 5.5 x 18.2mm by adopting a horizontal bright annealing furnace, wherein the annealing temperature is 450 ℃, and the annealing time is 5 hours.
S9, drawing a finished product: and (3) drawing out a finished product by using a 5 x 18 polycrystalline die by adopting a combined drawing machine, so as to ensure the size and straightness of the product: the length of the bearing of the drawing die is controlled to be 5-7mm, the R angle deviation is controlled to be +/-0.02 mm, and the angle of the drawing opening is 6 degrees.
Example 4
The chromium zirconium copper flat square provided by the embodiment comprises the following components in percentage by mass of 100 percent: cr 0.9%, zr:0.06%, the balance copper and unavoidable impurities, and the finished product size is 7mm by 16mm.
The preparation method provided by the embodiment comprises the following steps:
s1, smelting: adding a proper amount of oxygen-free copper rod into an upward-pulling furnace according to required components, introducing argon and heating until the oxygen-free rod is completely melted, starting automatic feeding of the oxygen-free rod, controlling the feeding speed to be 220Kg/h, stopping feeding of the oxygen-free rod when the copper liquid is 20cm away from the edge of a crucible, adding the copper-chromium alloy and the copper-zirconium alloy which are prepared in proportion, keeping the final temperature at 1250 ℃, preserving heat for 20min, carrying out phi 28mm upward-pulling blank production after detecting that the components are qualified, carrying out automatic feeding according to preset components in the oxygen-free copper rod, copper-chromium and zirconium cored wires in the follow-up pulling process, carrying out component test on the furnace liquid every 30min, ensuring that the components of the upward-pulling blank are qualified, cooling water pressure to be 0.3MPa, and pulling speed to be 0.77mm/s, thereby obtaining the diameter phi 28mm upward-pulling chromium-zirconium-copper blank.
S2, cold working for the first time: rolling the 28mm blank to 23, carrying out the subsequent drawing process according to the reducing amount of 1-2mm per pass, drawing to 17.5mm, finally peeling to 16mm to ensure that the surface crystal lines are completely peeled off, and then drawing to 15.05mm.
S3, solid solution: and (3) carrying out solid solution on a blank with the thickness of 15.05mm, controlling the solid solution temperature to 940 ℃, controlling the conductivity of the blank to be 35-45% IACS after solid solution, and controlling the hardness HV5 to be 50-70 after solid solution.
S4, acid washing: and (3) pickling the solid solution blank, wherein the surface of the pickled blank is free from oxidation, collision, sand holes and the like.
S5, cold working for the second time: the 15.05mm blank was drawn to 14.9mm, and the drawing rate was 2.0%.
S6, rolling: the thickness of the drawn blank is 8.5mm, the roughness of the roller in the rolling process is Ra1-2, and the rolling speed is 15m/min.
S7, third cold working: and drawing the blank by adopting a die with a polycrystalline die of 7.5mm x 16.2mm, wherein the horn mouth angle of the die is 10 degrees (the drawing mouth angle is smaller and can cause the drawing process of the blank and the scraping of the edge part of the die), and the length of the bearing is controlled to be 5-7mm (the bearing is too long, the friction is increased, and the bearing is too small and is difficult to ensure the size of a finished product).
S8, aging annealing: and (3) annealing the blank with the thickness of 7.5 x 16.2mm by adopting a horizontal bright annealing furnace, wherein the annealing temperature is 450 ℃, and the annealing time is 5 hours.
S9, drawing a finished product: drawing out a finished product by using a 7 x 16 polycrystalline die by adopting a combined drawing machine, so as to ensure the size and straightness of the product: the length of the bearing of the drawing die is controlled to be 5-7mm, the R angle deviation is controlled to be +/-0.02 mm, and the angle of the drawing opening is 6 degrees.
Example 5
The chromium zirconium copper flat square provided by the embodiment comprises the following components in percentage by mass of 100 percent: cr 0.6%, zr:0.06%, the balance copper and unavoidable impurities, the finished product size is 4.8mm x 22mm.
The preparation method provided by the embodiment comprises the following steps:
s1, smelting: adding a proper amount of oxygen-free copper rod into an upward-pulling furnace according to required components, introducing argon and heating until the oxygen-free rod is completely melted, starting automatic feeding of the oxygen-free rod, controlling the feeding speed to be 220Kg/h, stopping feeding of the oxygen-free rod when the copper liquid is 20cm away from the edge of a crucible, adding copper-chromium alloy and copper-zirconium alloy which are prepared in proportion, keeping the final temperature at 1250 ℃, preserving heat for 20min, carrying out phi 28mm upward-pulling blank production after detecting components are qualified, carrying out automatic feeding of oxygen-free copper rod, copper-chromium and zirconium cored wires according to preset components in the follow-up pulling process, carrying out component test on the furnace liquid every 30min, ensuring that the components of the upward-pulling blank are qualified, cooling water pressure to be 0.3MPa, and pulling speed to be 0.77mm/s, and obtaining the upward-pulling chromium-zirconium-copper blank with the diameter phi 28 mm;
s2, cold working for the first time: rolling the 28mm blank to 23, carrying out the subsequent drawing process according to the reducing amount of 1-2mm per pass, drawing to 20.5mm, finally peeling to 19mm to ensure that the surface crystal lines are completely peeled off, and then drawing to 18.1mm.
S3, solid solution: and (3) carrying out solid solution on a blank with the thickness of 18.1mm, controlling the solid solution temperature to 950 ℃, controlling the conductivity of the blank to be 35-45% IACS after solid solution, and controlling the hardness HV5 to be 50-70 after solid solution.
S4, acid washing: and (3) pickling the solid solution blank, wherein the surface of the pickled blank is free from oxidation, collision, sand holes and the like.
S5, cold working for the second time: the 18.1mm blank was drawn to 18.0mm, and the drawing rate was 1.1%.
S6, rolling: and rolling the drawn blank to a thickness of 6.3mm, wherein the roughness of a roller in the rolling process is Ra1-2, and the rolling speed is 15m/min.
S7, third cold working: and drawing the blank by adopting a die with 5.3mm of a polycrystalline die and 22.2mm of the polycrystalline die, wherein the horn mouth angle of the die is 10 degrees (the drawing mouth angle is smaller and can cause the drawing process of the blank and the scraping of the edge part of the die), and the length of the bearing is controlled to be 5-7mm (the bearing is too long, the friction is increased, and the bearing is too small and is difficult to ensure the size of a finished product).
S8, aging annealing: and (3) annealing the blank with the thickness of 5.3 x 22.2mm by adopting a horizontal bright annealing furnace, wherein the annealing temperature is 450 ℃, and the annealing time is 5 hours.
S9, drawing a finished product: drawing out a finished product by using a combined drawing machine through a 4.8 x 22 polycrystalline die, so as to ensure the size and straightness of the product: the length of the bearing of the drawing die is controlled to be 5-7mm, the R angle deviation is controlled to be +/-0.02 mm, and the angle of the drawing opening is 6 degrees.
Example 6
The chromium zirconium copper flat square provided by the embodiment comprises the following components in percentage by mass of 100 percent: cr 0.9%, zr:0.03%, the balance copper and unavoidable impurities, the finished product size is 6mm by 21mm.
The preparation method provided by the embodiment comprises the following steps:
s1, smelting: adding a proper amount of oxygen-free copper rod into an upward-pulling furnace according to required components, introducing argon and heating until the oxygen-free rod is completely melted, starting automatic feeding of the oxygen-free rod, controlling the feeding speed to be 220Kg/h, stopping feeding of the oxygen-free rod when the copper liquid is 20cm away from the edge of a crucible, adding the copper-chromium alloy and the copper-zirconium alloy which are prepared in proportion, keeping the final temperature at 1250 ℃, preserving heat for 20min, carrying out phi 28mm upward-pulling blank production after detecting that the components are qualified, carrying out automatic feeding according to preset components in the oxygen-free copper rod, copper-chromium and zirconium cored wires in the follow-up pulling process, carrying out component test on the furnace liquid every 30min, ensuring that the components of the upward-pulling blank are qualified, cooling water pressure to be 0.3MPa, and pulling speed to be 0.77mm/s, thereby obtaining the diameter phi 28mm upward-pulling chromium-zirconium-copper blank.
S2, cold working for the first time: rolling a 28mm blank to 23, carrying out a subsequent drawing process according to the reducing amount of 1-2mm in each pass, drawing to 20.5mm, finally peeling to 19mm to ensure that the surface crystal lines are completely peeled off, and then drawing to 17.9mm.
S3, solid solution: and (3) carrying out solid solution on a blank with the thickness of 17.9mm, controlling the solid solution temperature to be 940 ℃, controlling the conductivity of the blank to be 35-45% IACS after solid solution, and controlling the hardness HV5 to be 50-70 after solid solution.
S4, acid washing: and (3) pickling the solid solution blank, wherein the surface of the pickled blank is free from oxidation, collision, sand holes and the like.
S5, cold working for the second time: the 17.9mm blank was drawn to 17.75mm, and the drawing rate was 1.7%.
S6, rolling: and rolling the drawn blank to a thickness of 7.5mm, wherein the roughness of a roller in the rolling process is Ra1-2, and the rolling speed is 15m/min.
S7, third cold working: and drawing the blank by adopting a polycrystalline die 6.5mm x 21.2mm die, wherein the horn mouth angle of the die is 10 degrees (the drawing mouth angle is smaller and can cause the drawing process of the blank and the scraping of the die edge), and the length of the bearing is controlled to be 5-7mm (the bearing is too long, the friction is increased, and the bearing is too small and is difficult to ensure the size of a finished product).
S8, aging annealing: and (3) annealing the blank with the thickness of 6.5 x 21.2mm by adopting a horizontal bright annealing furnace, wherein the annealing temperature is 450 ℃, and the annealing time is 5 hours.
S9, drawing a finished product: and (3) drawing out a finished product by using a combined drawing machine through a 6 x 21 polycrystalline die, so as to ensure the size and straightness of the product: the length of the bearing of the drawing die is controlled to be 5-7mm, the R angle deviation is controlled to be +/-0.02 mm, and the angle of the drawing opening is 6 degrees.
Comparative example 1
The chromium zirconium copper flat prescription comprises the following components in percentage by mass of 100 percent: cr 1.2%, zr:0.08%, the balance copper and unavoidable impurities, and the finished product size is 4mm by 20mm. The procedure is as in example 1.
Comparative example 2
The preparation process is the same as in example 2, with the main difference that no secondary cold working direct rolling is performed after solid solution.
Comparative example 3
The preparation process is the same as in example 3, with the main difference that the secondary cold working is S5: drawing a blank with the thickness of 15.6mm to 15.3mm, wherein the drawing processing rate is 3.8%;
comparative example 4
The main differences between the composition and the smelting are as in example 4: the finished product is directly pulled out after the blank is in solid solution, and the following concrete steps are as follows:
s2, cold working for the first time: rolling the 28mm blank to 23, carrying out the subsequent drawing process according to the reducing amount of 1-2mm per pass, drawing to 21.5mm, finally peeling to 20mm to ensure that the surface crystal lines are completely peeled off, and then drawing to 19mm.
S3, solid solution: and (3) carrying out solid solution on a blank with the thickness of 19mm, controlling the solid solution temperature to be 940 ℃, controlling the conductivity of the blank to be 35-45% IACS after solid solution, and controlling the hardness HV5 to be 50-70 after solid solution.
S4, acid washing: the solid solution blank is subjected to acid washing, and the surface of the blank after acid washing is free of oxidation, collision, sand holes and the like;
s5, secondary cold working: directly drawing the 19mm solid solution blank through a die, wherein the thickness direction of each drawing is reduced by 2mm, the width direction is reduced by 0.4-0.5mm (the specific drawing process is 19-17 x 18.5-15 x 18-13 x 17.6-11 x 17.2-9 x 16.8), and drawing is carried out until the thickness direction is 9 x 16.8;
s7, third cold working: drawing the 9 x 16.8 blank by adopting a polycrystalline die 7.5mm x 16.2mm die, wherein the horn mouth angle of the die is 10 degrees (the small drawing mouth angle can cause the blank drawing process and the scraping of the die edge part), and the length of a bearing is controlled to be 5-7mm (the bearing is too long, the friction is increased, and the bearing is too small to ensure the size of a finished product);
s8, aging annealing: annealing the blank with the thickness of 7.5 x 16.2mm by adopting a horizontal bright annealing furnace, wherein the annealing temperature is 450 ℃, and the annealing time is 5 hours;
s9, drawing a finished product: drawing out a finished product by using a 7 x 16 polycrystalline die by adopting a combined drawing machine, so as to ensure the size and straightness of the product: the length of the bearing of the drawing die is controlled to be 5-7mm, the R angle deviation is controlled to be +/-0.02 mm, and the angle of the drawing opening is 6 degrees.
Performance analysis:
the chemical compositions of the examples and comparative examples are summarized in table 1; the rolling thickness, the broadening theoretical results and the actual measurement results of the examples and the comparative examples are summarized in Table 2; the feasibility of the empirical formula was verified and the texture types and texture areas after secondary cold working of examples and comparative examples are summarized in table 3; the qualification rates of the products of the comparative example and the example are shown in Table 4; the copper alloys prepared in examples and comparative examples were subjected to performance tests of grain size, tensile strength, conductivity, hardness, etc., and the test methods were specifically as follows:
and (3) detecting the grain size: the grain size and the comparative example are tested according to GB/T6394-2017 method for measuring average grain size of metals, wherein the grain size test method is a cut-off method, and the comparative example test method is an area method.
Detection of second phase deposition and texture: the second phase size is obtained by observing the structure of the sample under a scanning electron microscope and a transmission electron microscope, calculating the average particle size and the number of the second phase precipitated from the alloy according to the observation result, and calculating the number density and the precipitated phase area ratio respectively. Texture test the electropolished chromium zirconium copper samples were tested using EBSD, and the texture type and area number were calculated from the reflection-derived chrysanthemum pool pattern.
Tensile strength, yield strength: according to GB/T228.1-2021 section 1 Metal tensile test: room temperature test method detection;
conductivity of: the method is tested according to GB/T32791-2016 copper and copper alloy conductivity vortex test method.
Hardness: the detection standard is GB/T4340.1-2009 metal Vickers hardness test part 1; test methods.
Tolerance dimensions: the detection standard is GB/T5584.1-2009 copper, aluminum and the first part of the alloy flat wire for electrician: general regulations
Yield is as follows:
according to the requirements of customers and labels, the elongation rate of the product is more than 10 percent, the tensile strength is more than 500MPa, the hardness HB is more than 145, and the conductivity is more than 85 percent IACS; the tolerance size of the product meets the standard requirement.
Table 1 comparison of chemical compositions of inventive examples and comparative examples
TABLE 2 examination of solution size and broad empirical formula in the Rolling Process of the invention
TABLE 3 surface depth occupied by goss texture after the second cold working and the ratio of goss to Cube texture in that depth
Table 4 yield of example and comparative example
TABLE 5 comparison of the properties of the inventive and comparative examples
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From the above data, i.e., tables 1 to 5, it can be seen that the actual expansion and theoretical expansion differ less in examples 1 to 6, so that the solution size and finished product empirical formulas and the rolling expansion and rolling thickness empirical formulas are viable; as can be seen from comparative examples 1, 2 and 3, the change of the composition and the secondary small amount of cold deformation all lead to a wide deviation from the empirical formula, leading to uncontrollability of the rolling width, and leading to the inability of the process to solidify; meanwhile, the two rolling deformations can sufficiently refine grains, which is beneficial to the second fine dispersion distribution in the aging process, and the rolling is not performed, as can be seen in comparative example 4, the proportion of fine grains is obviously reduced, and the subsequent aging strengthening is not facilitated. Therefore, the product percent of pass can be controlled to be more than 90 percent in the embodiment, while the rolling expansion can not meet the requirement due to the change of the components in the comparative example 1, and meanwhile, the plasticity of the product is reduced due to the increase of the Cr content, so that the product is cracked; in comparative example 2, the rolling blank was not subjected to secondary cold working, so that the rolling blank was not uniformly widened, and most of finished products were scrapped due to poor tolerance; in comparative example 3, the rolling expansion cannot meet the requirement of the subsequent finished product drawing due to the overlarge secondary cold working, so that the products are all scrapped; in comparative example 4, the process route is insufficient in grain refinement, so that the tensile strength and the extension of the finished product cannot meet the requirements and are completely scrapped.
Claims (10)
1. The preparation method of the chromium-zirconium-copper flat prescription is characterized by comprising the following steps of: batching, upward continuous casting, first cold working, solid solution, second cold working, rolling, third cold working, aging annealing and drawing of a finished product;
the chromium-zirconium-copper flat square comprises the following components in percentage by mass: 0.6-0.9, zr:0.03-0.06, the balance Cu and unavoidable impurities;
the processing amount of the second cold working is 1% -2.5%.
2. The method for preparing the chromium zirconium copper flat according to claim 1, wherein the rolling width L after rolling the blank and the blank size D after solid solution are obtained according to the width and the thickness of the chromium zirconium copper flat:
L＝A*(D-d)+D
D＝(1.1a+2b+7.1)/3.11
wherein A is a constant, the value of A is 0.5-0.55, a is the thickness of the chromium zirconium copper flat square, b is the width of the chromium zirconium copper flat square, D is the rolling thickness, and D is the size of the blank after solid solution.
3. The method for preparing the chromium zirconium copper flat according to claim 1, wherein the rolling thickness is + (1.2-1.5 mm) of the chromium zirconium copper flat, and the rolling width is + (2-3 mm) of the chromium zirconium copper flat.
4. The method for preparing the chromium zirconium copper flat according to claim 1, wherein the thickness of the blank after the third cold working is the thickness+ (0.45-0.55 mm) of the chromium zirconium copper flat and the width is the width+ (0.18-0.25 mm) of the chromium zirconium copper flat.
5. The method for producing a chromium zirconium copper flat according to claim 1, wherein the ratio of the area of Cube texture to the area of goss texture in the texture of 0-0.15mm depth from the surface of the blank after the second cold working is 60% or more.
6. The method for preparing a chromium zirconium copper flat according to claim 1, wherein the processing amount of the first cold processing is not less than 35%.
7. The method for preparing a chromium zirconium copper flat according to claim 1, wherein the solid solution temperature is 930-950 ℃, and the grain size after solid solution is 0.02-0.04mm.
8. The method for preparing the chromium-zirconium-copper flat according to claim 1, wherein the aging annealing temperature is 450-470 ℃ and the aging time is 4-7h.
9. A chromium-zirconium-copper flat square prepared by the preparation method of any one of claims 1-8, characterized in that the second phase in the chromium-zirconium-copper flat square structure is Cr and Zr phase, and the distribution number of the second phase in the chromium-zirconium-copper flat square structure is 50000/mm 2 。
10. The method for preparing the chromium zirconium copper flat square according to claim 9, wherein the thickness of the chromium zirconium copper flat square is more than 2mm, the width is more than 15mm, and the width-to-thickness ratio is 2-8.
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