CN104451487A - Method for preparing copper alloy nanometer gradient material - Google Patents
Method for preparing copper alloy nanometer gradient material Download PDFInfo
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- CN104451487A CN104451487A CN201410656185.1A CN201410656185A CN104451487A CN 104451487 A CN104451487 A CN 104451487A CN 201410656185 A CN201410656185 A CN 201410656185A CN 104451487 A CN104451487 A CN 104451487A
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- copper alloy
- gradient material
- nanometer gradient
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- copper
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910017777 Cu—Al—Zn Inorganic materials 0.000 claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000012360 testing method Methods 0.000 claims abstract description 8
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 6
- 239000010959 steel Substances 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims description 13
- 241000863032 Trieres Species 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 10
- 239000000956 alloy Substances 0.000 abstract description 9
- 239000007769 metal material Substances 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract 1
- 230000003116 impacting effect Effects 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 238000007709 nanocrystallization Methods 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005480 shot peening Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
Abstract
The invention discloses a method for preparing a copper alloy nanometer gradient material, and belongs to the technical field of metal material machining. The method comprises the following steps: carrying out vacuum homogenizing annealing on a Cu-Al-Zn ternary copper alloy ingot at the temperature of 800-840 DEG C for 2-3 hours, and rolling into a thin plate at room temperature; then carrying out destressing and homogenizing annealing at the temperature of 550-600 DEG C for 2-3 hours, and cooling with a furnace; impacting an annealed copper plate of the Cu-Al-Zn ternary copper alloy at a high speed by using a steel ball on a surface nanocrystallization testing machine with liquid nitrogen introduced to prepare the nanometer gradient copper alloy material, wherein the testing frequency of the testing machine is 20-50 HZ, and the time is 5-30 minutes. The method disclosed by the invention is simple in preparation process and can obtain the copper alloy gradient material which is obviously enhanced in strength and less reduced in property and has good toughness matching.
Description
Technical field
The present invention relates to the preparation method of an Albatra metal-nanometer gradient material, belong to metal material processing technical field.
Background technology
Materials microstructure structure directly affects the use properties of material, in order to meet the specific demand of Service Environment to material property (as intensity, hardness, frictional wear, corrosion and fatigue life-span and stress distribution etc.), people propose kinds of surface modification technology in succession, such as shot-peening, plating, spraying, vapour deposition (PVD, CVD), ion implantation, surface laser process and chemical conversion treatment etc.These technology, by improving the weave construction of material surface and drastically increasing the military service behavior of material, therefore industrially achieve and apply widely.Along with deepening continuously of nano material and nanotechnology research, traditional process for modifying surface is combined with nano fabrication technique likely for the nanometer realizing engineering metal material provides a new developing direction.
Two more than ten years in the past; the research Showed Very Brisk of nano material and nanotechnology; this is mainly because nano material has unique structure and excellent performance; research nano material has not only deepened the understanding of people to solid material essential structure feature further, is also that design, the exploitation of high performance material of new generation provides material and technical foundation simultaneously.Up to now, people have developed multiple preparation method of nano material, as evaporation of metal condensation-original position coldmoulding method, Amorphous Crystallization method, mechanical milling method and intense plastic strain method etc.But due to the restriction of the factors such as complicated process of preparation, production cost are high and limited, the inner Presence of an interface of material profile size pollutes, hole class defect is many, existing technology of preparing also fails to obtain practical application on engineering metal material.
Under arms under environment, the unstability of metallic substance starts from surface more, as long as therefore prepare certain thickness nanostructured surface laye on material, form gradient material with the gradual change of heart portion, just can be arrived overall performance and the military service behavior of the complementation optimization raising material of core structure and performance by surface.Making Nano surface technology and nano surface formed material have many unique distinctions: first, making Nano surface adopts Conventional surface treatment (or improving Conventional surface treatment) to realize, and industrially applies and there is not obvious technology barrier; Secondly, there is not obvious interface between nano surface crystalline substance tissue and matrix, delamination can not occur and be separated; 3rd, making Nano surface be not only applicable to material entirety, but also can be used for the surface modification of local.Due to making Nano surface be not only conceived to current scientific and technological level, but also towards practical engineering application, the performance and used life therefore likely for utilizing nanotechnology to improve Traditional project metallic substance significantly provides a practicable approach.
Copper has excellent characteristic, is industrially used widely, but the intensity of copper and hardness are all very low, and some important occasions are difficult to use, and after adding other alloying element solution strengthening or second-phase strength, can improve its intensity; Prepare super fine crystal material by the method for large plastometric set, super fine crystal material hinders the motion of dislocation effectively owing to having a large amount of crystal boundaries, can improve intensity; But the block body ultrafine grain prepare large plasticity or nanocrystalline material, plasticity is lower, becomes the obstacle that it is industrially applied.
In order to solve the shortcoming of above prior art, obtain intensity and all good Cu alloy material of plasticity, the present invention utilizes high speed small ball to clash into specimen surface under adopting the vacuum environment of logical liquid nitrogen on making Nano surface of metal material trier, at reasonable offer Ultra-fine Grained nanometer gradient material, top layer has high intensity, hardness, and heart portion has higher toughness.The change of grain structure and stress gradient, makes this material have excellent plasticity and intensity.
Summary of the invention
The present invention is under the vacuum low-temperature environment of logical liquid nitrogen, copper alloy plate is carried out to the surperficial high energy impact process of high strain rate, the stable Ultra-fine Grained nanometer gradient material of one deck is formed on copper alloy plate surface, thus prepare the method for the copper alloy gradient material of high-strong toughness, specifically comprise the following steps:
(1) by casting Cu-Al-Zn ternary copper-alloy ingot casting out vacuum homogenizing annealing 2 ~ 3 hours at the temperature of 800 ~ 840 DEG C, being then rolled into thickness is 3mm ~ 4.5mm thin plate, then at the temperature of 550 ~ 600 DEG C stress relief annealing 2 ~ 3 hours;
(2) under the vacuum environment of logical liquid nitrogen, the thin plate processed in step (1) is carried out high-speed impact deformation process 5 ~ 30min with the steel ball that 160 ~ 200 diameters are 6 ~ 8mm on making Nano surface trier and prepare copper alloy nanometer gradient material.
Collision deformation treating processes described in step of the present invention (2) uses making Nano surface trier to complete, and the operating frequency of trier is 20Hz ~ 50Hz.
The invention has the beneficial effects as follows:
(1) the present invention is in conjunction with the copper alloy nanometer gradient material of the method acquisition high-strong toughness of the fierce viscous deformation of traditional annealing process and surface, and preparation method is simple;
(2) the copper alloy gradient material that the method for the invention obtains has from surface to core structure and the feature of Gradient distribution of stress, and the high strength on top layer and the high-ductility in heart portion realize the good combination of obdurability;
(3) fund input cost of the present invention is low, easily realizes industrialization and produces, constant product quality.
Accompanying drawing explanation
Fig. 1 is the stress strain curve of the Cu-Al-Zn ternary copper-alloy that embodiment 1 ~ 2 prepares;
Fig. 2 is the stress strain curve of the Cu-Al-Zn ternary copper-alloy that embodiment 3 ~ 4 prepares;
Fig. 3 is the microhardness curve of the Cu-Al-Zn ternary copper-alloy that embodiment 1 ~ 2 prepares.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, but protection scope of the present invention is not limited to described content.
Embodiment 1(simultaneous test)
The mass percent of the concrete composition of Cu-Al-Zn described in the present embodiment to be the mass percent of Cu be 81.20%, Al is the mass percent of 4.50%, Zn is 14.30%.
It is the ingot casting of 30mm vacuum homogenizing annealing 2 hours at the temperature of 840 DEG C by casting Cu-Al-Zn ternary copper-alloy diameter out, then at room temperature thin plate is rolled into, then the Cu-Al-Zn ternary copper-alloy material that stress relief annealing prepares for 2 hours at the temperature of 600 DEG C.
The Cu-Al-Zn ternary copper-alloy material that this example prepares does not carry out making Nano surface, and tensile yield strength is 106.6MPa, and tensile strength is 378.4 MPa, and maximum strain is 67.7%.
Embodiment 2
The mass percent of the concrete composition of Cu-Al-Zn described in the present embodiment to be the mass percent of Cu be 81.20%, Al is the mass percent of 4.50%, Zn is 14.30%.
(1) be the ingot casting of 30mm vacuum homogenizing annealing 2 hours at the temperature of 840 DEG C by casting Cu-Al-Zn ternary copper-alloy diameter out, be then at room temperature rolled into thin plate, then at the temperature of 600 DEG C stress relief annealing 2 hours;
(2) on making Nano surface trier, the vacuum environment of liquid nitrogen (logical under) carries out to copper coin two surfaces the Cu-Al-Zn ternary copper-alloy material that collision deformation process prepares respectively with 180 steel balls (6mm), trier frequency is 20 ~ 50HZ, and test period is 5 ~ 30min.
The tensile yield strength being the sample of 5min when the making Nano surface time is 247.6MPa, and tensile strength is 391.3MPa, and maximum strain is 62.6%; The making Nano surface time is the tensile yield strength of the sample of 15min is 290.4MPa, and tensile strength is 411.2MPa, and maximum strain is 54.8%; The making Nano surface time is the tensile yield strength of the sample of 30min is 290.4MPa, and tensile yield strength is 266.2MPa, and tensile strength is 338.0MPa, and maximum strain is 52.8%.
Embodiment 3
The mass percent of the concrete composition of Cu-Al-Zn described in the present embodiment to be the mass percent of Cu be 74.25%, Al is the mass percent of 1.86%, Zn is 23.89%.
(1) be the ingot casting of 30mm vacuum homogenizing annealing 3 hours at the temperature of 800 DEG C by casting Cu-Al-Zn ternary copper-alloy diameter out, be then at room temperature rolled into thin plate, then at the temperature of 550 DEG C stress relief annealing 3 hours;
(2) on making Nano surface trier, the vacuum environment of liquid nitrogen (logical under) carries out to copper coin two surfaces the Cu-Al-Zn ternary copper-alloy material that collision deformation process prepares respectively with 200 steel balls (8mm), trier frequency is 50HZ, and test period is 30min.
The tensile yield strength of the Cu-Al-Zn ternary copper-alloy material that the present embodiment of the Cu-Al-Zn ternary copper-alloy material that the present embodiment prepares prepares is 266.2MPa, and tensile strength is 338.0MPa, and maximum strain is 52.8%.
Embodiment 4
The mass percent of the concrete composition of Cu-Al-Zn described in the present embodiment to be the mass percent of Cu be 74.25%, Al is the mass percent of 1.86%, Zn is 23.89%.
(1) be the ingot casting of 30mm vacuum homogenizing annealing 1.5 hours at the temperature of 820 DEG C by casting Cu-Al-Zn ternary copper-alloy diameter out, be then at room temperature rolled into thin plate, then at the temperature of 580 DEG C stress relief annealing 2.5 hours;
(2) on making Nano surface trier, the vacuum environment of liquid nitrogen (logical under) carries out to copper coin two surfaces the Cu-Al-Zn ternary copper-alloy material that collision deformation process prepares respectively with 180 steel balls (7mm), trier frequency is 30HZ, and test period is 5 ~ 30min.
The making Nano surface time is the tensile yield strength of the sample of 5min is 226.7MPa, and tensile strength is 357.5MPa, and maximum strain is 57.6%; The making Nano surface time is the tensile yield strength of the sample of 15min is 280.9MPa, and tensile strength is 364.6MPa, and maximum strain is 43.7%; The making Nano surface time is the tensile yield strength of the sample of 30min is 319.5MPa, and tensile strength is 385.8MPa, and maximum strain is 40.3%.
The stress strain curve of Fig. 1 to be composition that embodiment 1 ~ 2 prepares be Cu-Al-Zn ternary copper-alloy of 81.20%Cu-4.50%Al-14.30%Zn (wt.%); The plasticity of annealed state sample is best as seen from the figure, intensity is the poorest, and after Surface Nanocrystalline, intensity significantly improves, plasticity slightly reduces, and increase with the making Nano surface time, intensity continuous increases, and plasticity continues to reduce, but to certain hour, the change of plasticity is just little, and the sample of making Nano surface 30min and the sample maximum strain value of making Nano surface 15min differ very little, and intensity is also improved space.
The stress strain curve of Fig. 2 to be composition that embodiment 3 ~ 4 prepares be Cu-Al-Zn ternary copper-alloy of 74.25%Cu-1.86%Al-23.89%Zn (wt.%), contrasts with Fig. 1 and also has identical rule.
Can find out that this preparation method can significantly improve the intensity of Cu-Al-Zn ternary copper-alloy by Fig. 1 and Fig. 2, and keep high plasticity.
Fig. 3 is the microhardness curve of the Cu-Al-Zn ternary copper-alloy that embodiment 1 ~ 2 prepares, as seen from the figure anneal sample from top layer to heart portion microhardness difference less than, the Cu-Al-Zn ternary copper-alloy sample surface layer microhardness crossed through Surface Nanocrystalline is the highest, walk toward material heart portion, hardness reduces gradually, is minimum to heart portion; Increase with the making Nano surface time, the degree of grain refining and the degree of depth increase, and hardness improves; Annealing Cu-Al-Zn ternary copper-alloy microhardness value is 1.1GPa, and the sample surface layer microhardness value after Surface Nanocrystalline 30min can reach 2.2GPa, doubles.
Claims (6)
1. the preparation method of an Albatra metal-nanometer gradient material, is characterized in that, specifically comprise the following steps:
(1) by casting copper alloy casting ingot homogenizing annealing under vacuo out, be then rolled into thin plate, then destressing, homogenizing annealing carried out to thin plate;
(2) thin plate processed in step (1) is carried out high-speed impact deformation process 5 ~ 30min with the steel ball that 160 ~ 200 diameters are 6 ~ 8mm on making Nano surface trier and prepare copper alloy nanometer gradient material.
2. the preparation method of copper alloy nanometer gradient material according to claim 1, it is characterized in that: described in step (1), the annealing temperature of ingot casting anneal is 800 ~ 840 DEG C, annealing time is 2 ~ 3h, the annealing temperature of described thin plate anneal is 550 ~ 600 DEG C, and annealing time is 2 ~ 3h.
3. the preparation method of copper alloy nanometer gradient material according to claim 1, is characterized in that: described in step (1), gauge of sheet is 3mm ~ 4.5mm.
4. the preparation method of copper alloy nanometer gradient material according to claim 1, is characterized in that: described in step (1), copper alloy is Cu-Al-Zn ternary copper-alloy.
5. the preparation method of copper alloy nanometer gradient material according to claim 1, is characterized in that: described in step (2), high-speed impact deformation process is carried out under the vacuum environment of logical liquid nitrogen.
6. the preparation method of copper alloy nanometer gradient material according to claim 1, is characterized in that: described in step (2), the test frequency of making Nano surface trier is 20 ~ 50HZ.
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| CN201410656185.1A CN104451487B (en) | 2014-11-18 | 2014-11-18 | Method for preparing copper alloy nanometer gradient material |
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| CN201410656185.1A CN104451487B (en) | 2014-11-18 | 2014-11-18 | Method for preparing copper alloy nanometer gradient material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947013A (en) * | 2015-05-26 | 2015-09-30 | 昆明理工大学 | Preparation method of double-layer gradient ball-milled surface nano copper rod |
| CN105177645A (en) * | 2015-07-27 | 2015-12-23 | 昆明理工大学 | Preparation method of multi-layer composite gradient nano pure copper materials |
| CN107299302A (en) * | 2016-04-15 | 2017-10-27 | 南京理工大学 | A kind of method for improving metal gradient structural strength and plasticity matching degree |
| CN108517477A (en) * | 2018-04-16 | 2018-09-11 | 中国兵器工业第五九研究所 | A kind of ultra-fine crystallization gradient control method of depth taper copper conic liner tissue |
| CN115627378A (en) * | 2022-10-19 | 2023-01-20 | 昆明理工大学 | Preparation method of Cu-Al-Zn alloy material |
| CN116213751A (en) * | 2022-12-13 | 2023-06-06 | 浙江大学 | 316L stainless steel surface treatment method |
| CN116516268A (en) * | 2023-04-14 | 2023-08-01 | 常熟市普华电工材料有限公司 | Alloy copper wire annealing process |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947013A (en) * | 2015-05-26 | 2015-09-30 | 昆明理工大学 | Preparation method of double-layer gradient ball-milled surface nano copper rod |
| CN104947013B (en) * | 2015-05-26 | 2016-12-07 | 昆明理工大学 | A kind of preparation method of double-deck gradient sphere grinding making Nano surface copper rod |
| CN105177645A (en) * | 2015-07-27 | 2015-12-23 | 昆明理工大学 | Preparation method of multi-layer composite gradient nano pure copper materials |
| CN107299302A (en) * | 2016-04-15 | 2017-10-27 | 南京理工大学 | A kind of method for improving metal gradient structural strength and plasticity matching degree |
| CN107299302B (en) * | 2016-04-15 | 2020-02-28 | 南京理工大学 | Method for improving metal gradient structure strength and plasticity matching degree |
| CN108517477A (en) * | 2018-04-16 | 2018-09-11 | 中国兵器工业第五九研究所 | A kind of ultra-fine crystallization gradient control method of depth taper copper conic liner tissue |
| CN115627378A (en) * | 2022-10-19 | 2023-01-20 | 昆明理工大学 | Preparation method of Cu-Al-Zn alloy material |
| CN116213751A (en) * | 2022-12-13 | 2023-06-06 | 浙江大学 | 316L stainless steel surface treatment method |
| CN116516268A (en) * | 2023-04-14 | 2023-08-01 | 常熟市普华电工材料有限公司 | Alloy copper wire annealing process |
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| CN104451487B (en) | 2017-04-12 |
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