CN102776409B - Technology for preparing corrosion-resistant copper alloy - Google Patents
Technology for preparing corrosion-resistant copper alloy Download PDFInfo
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- CN102776409B CN102776409B CN201210305706.XA CN201210305706A CN102776409B CN 102776409 B CN102776409 B CN 102776409B CN 201210305706 A CN201210305706 A CN 201210305706A CN 102776409 B CN102776409 B CN 102776409B
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- 238000005516 engineering process Methods 0.000 title claims abstract description 18
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 12
- 230000007797 corrosion Effects 0.000 title abstract description 9
- 238000005260 corrosion Methods 0.000 title abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 21
- 238000007670 refining Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000001953 recrystallisation Methods 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000005096 rolling process Methods 0.000 abstract description 2
- 229910001122 Mischmetal Inorganic materials 0.000 abstract 3
- 238000003723 Smelting Methods 0.000 abstract 1
- 238000005266 casting Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000011572 manganese Substances 0.000 description 7
- 229910001369 Brass Inorganic materials 0.000 description 6
- 239000010951 brass Substances 0.000 description 6
- -1 compound rare-earth Chemical class 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005479 sherardizing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Abstract
The invention discloses a technology for preparing a corrosion-resistant copper alloy, which comprises the following compositions by weight percent:1.0-1.2% of Mn, 0.5-0.7% of Si, 0.05-0.15% of Fe, 0.8-1.2% of Mg, 2-4% of Zn, 11-13% of Al, 1.2-1.4% of Ti, 0.3-0.5% of Sc, 5.5-6.5% of Ni and 0.2-0.3% of composite mischmetal, wherein the mischmetal contains La and Ce mischmetal elements, the percentage of Ce is 30-50%, and the balance is Cu. The technology comprises the following steps: 1. smelting, refining and casting to form a bar; 2. heating the bar which is obtained in the step 1 to the temperature of 870-920 DEG C; then carrying out hot extruding on the bar to form a pipe billet; 3. heating the pipe billet which is obtained in the step 2 to be 850-900 DEG C, and rolling the pipe billet to form a pipe; 4. carrying out recrystallization annealing, annealing at the temperature of 800-820 DEG C, and thermally insulating for 3-5 hours; 5. drawing until a finished product specification is formed; and 6. finally, carrying out bright annealing, annealing at the temperature of 760-780 DEG C, and thermally insulating for 4-6 hours.
Description
Technical field
The present invention relates to copper alloy technical field, particularly a kind of preparation technology of Vulcan metal.
Background technology
The tube bank material using in briny environment at present mainly contains aluminum brass, and (Typical Representative is: C68700, its composition is 76～79wt%Cu, 1.8～2.5wt%Al, surplus is Zn), (Typical Representative is one-ton brass: C44300, its composition is 70～73wt%Cu, 0.8～1.2wt%Sn, 0.06wt%Fe, 0.02～0.06As, surplus is Zn), and Alpaka (Typical Representative is: C70600, and its composition is 9.0～11wt%Ni, 1.0～1.8wt%Fe, 1.0wt%Mn, 1.0wt%Zn, surplus is Cu; C71500, its composition is 29～33wt%Ni, 0.4～0.7wt%Fe, 1.0wt%Mn, 1.0wt%Zn, surplus is Cu), stainless steel (Typical Representative is 1Cr18Ni9Ti, 0Cr18Ni9Ti, 00Cr19Ni10 and 00Cr18Ni12Mo2) and titanium alloy (Typical Representative is TA2) etc.
Limitation and deficiency that above-mentioned tube bank material is used in corrosive environment of sea water are: aluminum brass and one-ton brass exist low strength, dealloying (dezincify, dealuminzation) and erosion corrosion seriously etc. not enough; There is the defects such as cost is high, processing is comparatively difficult in Alpaka; There is the problems such as cost is higher, marine biological polution is serious in titanium alloy and stainless steel.
Application number is CN200610039282.1, name is called in the patent of " seamless copper alloy tube for heat exchanger of fine corrosion resistance and preparation method thereof " provides a kind of seamless copper alloy tube for heat exchanger, on the basis of arsenic one-ton brass, the elements such as boron, nickel, manganese have been added again, improve the corrosion resistance of tubing, but cupronickel easily produces galvanic corrosion, and one-ton brass exists the problem of sherardizing steel ability always, limited under the condition that sea water desalinating plant is can only flow velocity lower and used.
The production technique of a kind of McGill metals pipe, rod is provided in the patent that and for example application number is CN200710106263.0, the most laggard extrusion molding of alloy cast ingot that contains copper, aluminium, nickel, iron, this alloy is used corrosion resistance nature also very unexcellent through reality, and this copper alloy can not be drawn into tubing, limited its application.
Summary of the invention
For the deficiencies in the prior art, one of object of the present invention is to provide a kind of preparation technology of Vulcan metal, the copper alloy seawater corrosion resistance of preparing by this technique and performance of flushing, high-wearing feature, high strength, and good processability.
For achieving the above object, the present invention adopts following technical scheme:
A preparation technology for Vulcan metal, this copper alloy is comprised of following component by weight percentage: Mn 1.0-1.2%, Si 0.5-0.7%, Fe 0.05-0.15%, Mg 0.8-1.2%, Zn 2-4%, Al 11-13%, Ti 1.2-1.4%, Sc 0.3-0.5%, Ni 5.5-6.5%, compound rare-earth 0.2-0.3%, wherein mishmetal is La, Ce mixed rare-earth elements, and the per-cent of Ce is 30-50%, and surplus is Cu.Described preparation technology comprises the steps:
1) select the master alloy of electrolytic copper, fine aluminium ingot, pure magnesium ingot, pure zinc ingot, all the other elements selections and copper, according to mentioned component, carry out proportioning, except aluminium and magnesium, all the other raw materials first carry out melting, until it, all after fusing, add fine aluminium ingot, pure magnesium ingot refining, refining temperature is 1170-1190 ℃, after refining 20-30 minute, is cast into bar.
2) by step 1) bar that obtains is heated to temperature 870-920 ℃; Then be hot extruded into pipe.
3) by step 2) heating of pipe blank that obtains is to 850-900 ℃, is rolled into pipe.
4) carry out recrystallization annealing, annealing temperature is 800-820 ℃, insulation 3-5 hour.
5) then carry out drawing, be drawn to the finished product specification.
6) finally carry out clean annealing, annealing temperature is 760-780 ℃, and soaking time is 4-6 hour.
Preparation method of the present invention has following beneficial effect:
1) on the basis of a large amount of orthogonal tests, adopt multicomponent alloy element, make these elements reach coordination technique effect, put forward heavy alloyed corrosion resisting property and mechanical property; By adding rare earth element, put forward heavy alloyed over-all properties;
2) for designed alloying element component, improve preparation technology, control refining temperature and time, make the content of element keep preset blending ratio, and make liquation pure; Adjust the temperature of extruding, rolling, recrystallization annealing and clean annealing, the above-mentioned actual temperature of using is all to consider on the basis of alloying constituent, through what determine after great many of experiments, after continuous like this processing, guaranteed the microtexture of alloy, and then determined that it has suitable performance.
Embodiment
Embodiment mono-
A preparation technology for Vulcan metal, this copper alloy is comprised of following component by weight percentage: Mn 1.0%, and Si 0.7%, Fe 0.05%, and Mg 1.2%, and Zn 2%, Al 13%, Ti1.2%, Sc 0.5%, and Ni 5.5%, compound rare-earth 0.3%, wherein mishmetal is La, Ce mixed rare-earth elements, and the per-cent of Ce is 30%, and surplus is Cu.Described preparation technology comprises the steps:
1) select the master alloy of electrolytic copper, fine aluminium ingot, pure magnesium ingot, pure zinc ingot, all the other elements selections and copper, according to mentioned component, carry out proportioning, except aluminium and magnesium, all the other raw materials first carry out melting, until it, all after fusing, add fine aluminium ingot, pure magnesium ingot refining, refining temperature is 1170 ℃, and refining was cast into bar after 30 minutes.
2) by step 1) bar that obtains is heated to temperature 870-920 ℃; Then be hot extruded into pipe.
3) by step 2) heating of pipe blank that obtains is to 850-900 ℃, is rolled into pipe.
4) carry out recrystallization annealing, annealing temperature is 800 ℃, is incubated 5 hours.
5) then carry out drawing, be drawn to the finished product specification.
6) finally carry out clean annealing, annealing temperature is 760 ℃, and soaking time is 6 hours.
Embodiment bis-
A preparation technology for Vulcan metal, this copper alloy is comprised of following component by weight percentage: Mn 1.2%, and Si 0.5%, Fe 0.15%, and Mg 0.8%, and Zn 4%, Al 11%, Ti 1.4%, and Sc 0.3%, and Ni 6.5%, compound rare-earth 0.2%, wherein mishmetal is La, Ce mixed rare-earth elements, and the per-cent of Ce is 50%, and surplus is Cu.Described preparation technology comprises the steps:
1) select the master alloy of electrolytic copper, fine aluminium ingot, pure magnesium ingot, pure zinc ingot, all the other elements selections and copper, according to mentioned component, carry out proportioning, except aluminium and magnesium, all the other raw materials first carry out melting, until it, all after fusing, add fine aluminium ingot, pure magnesium ingot refining, refining temperature is 1190 ℃, and refining was cast into bar after 20 minutes.
2) by step 1) bar that obtains is heated to temperature 870-920 ℃; Then be hot extruded into pipe.
3) by step 2) heating of pipe blank that obtains is to 850-900 ℃, is rolled into pipe.
4) carry out recrystallization annealing, annealing temperature is 820 ℃, is incubated 3 hours.
5) then carry out drawing, be drawn to the finished product specification.
6) finally carry out clean annealing, annealing temperature is 780 ℃, and soaking time is 4 hours.
Embodiment tri-
A preparation technology for Vulcan metal, this copper alloy is comprised of following component by weight percentage: Mn 1.1%, and Si 0.6%, Fe 0.010%, and Mg 1.0%, and Zn 3%, Al 12%, Ti 1.3%, and Sc 0.4%, and Ni 6.0%, compound rare-earth 0.25%, wherein mishmetal is La, Ce mixed rare-earth elements, and the per-cent of Ce is 40%, and surplus is Cu.Described preparation technology comprises the steps:
1) select the master alloy of electrolytic copper, fine aluminium ingot, pure magnesium ingot, pure zinc ingot, all the other elements selections and copper, according to mentioned component, carry out proportioning, except aluminium and magnesium, all the other raw materials first carry out melting, until it, all after fusing, add fine aluminium ingot, pure magnesium ingot refining, refining temperature is 1180 ℃, and refining was cast into bar after 25 minutes.
2) by step 1) bar that obtains is heated to temperature 870-920 ℃; Then be hot extruded into pipe.
3) by step 2) heating of pipe blank that obtains is to 850-900 ℃, is rolled into pipe.
4) carry out recrystallization annealing, annealing temperature is 810 ℃, is incubated 4 hours.
5) then carry out drawing, be drawn to the finished product specification.
6) finally carry out clean annealing, annealing temperature is 770 ℃, and soaking time is 5 hours.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (1)
1. a preparation technology for Vulcan metal, is characterized in that, this copper alloy is comprised of following component by weight percentage: Mn 1.0-1.2%, Si 0.5-0.7%, Fe 0.05-0.15%, Mg 0.8-1.2%, Zn 2-4%, Al 11-13%, Ti 1.2-1.4%, Sc 0.3-0.5%, Ni 5.5-6.5%, mishmetal 0.2-0.3%, wherein mishmetal is La, Ce mixed rare-earth elements, the per-cent of Ce is 30-50%, and surplus is Cu; Described preparation technology comprises the steps:
1) select the master alloy of electrolytic copper, fine aluminium ingot, pure magnesium ingot, pure zinc ingot, all the other elements selections and copper, according to mentioned component, carry out proportioning, except aluminium and magnesium, all the other raw materials first carry out melting, until it, all after fusing, add fine aluminium ingot, pure magnesium ingot refining, refining temperature is 1170-1190 ℃, after refining 20-30 minute, is cast into bar;
2) by step 1) bar that obtains is heated to temperature 870-920 ℃; Then be hot extruded into pipe;
3) by step 2) heating of pipe blank that obtains is to 850-900 ℃, is rolled into pipe;
4) carry out recrystallization annealing, annealing temperature is 800-820 ℃, insulation 3-5 hour;
5) then carry out drawing, be drawn to the finished product specification;
6) finally carry out clean annealing, annealing temperature is 760-780 ℃, and soaking time is 4-6 hour.
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| CN201210305706.XA CN102776409B (en) | 2012-08-24 | 2012-08-24 | Technology for preparing corrosion-resistant copper alloy |
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| CN201210305706.XA CN102776409B (en) | 2012-08-24 | 2012-08-24 | Technology for preparing corrosion-resistant copper alloy |
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| CN102776409A CN102776409A (en) | 2012-11-14 |
| CN102776409B true CN102776409B (en) | 2014-05-07 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103103589B (en) * | 2013-01-16 | 2015-06-10 | 南京工业大学 | Preparation method of manganese copper alloy material |
| CN103194640B (en) * | 2013-04-07 | 2015-08-26 | 宁波博威合金材料股份有限公司 | Xantal and preparation method thereof |
| CN103230961B (en) * | 2013-05-03 | 2015-09-09 | 江苏兴荣高新科技股份有限公司 | The manufacture method of copper alloy tube and copper alloy tube |
| CN103421978B (en) * | 2013-08-23 | 2015-05-27 | 苏州长盛机电有限公司 | Copper-magnesium alloy material |
| CN104060121B (en) * | 2014-06-05 | 2016-05-18 | 锐展(铜陵)科技有限公司 | The preparation method of wear-resistant copper alloy wire for a kind of automobile |
| CN104630555A (en) * | 2015-03-10 | 2015-05-20 | 济南大学 | High-strength corrosion resisting brass material and preparation method thereof |
| CN107794404B (en) * | 2017-07-24 | 2019-02-15 | 湖南大学 | A kind of Cu-Al-Mg alloy and its strain ageing treatment process |
| CN108941241A (en) * | 2018-07-06 | 2018-12-07 | 苏州市金翔钛设备有限公司 | A kind of processing method of copper-titanium alloy tubing |
| CN114015907B (en) * | 2021-11-12 | 2022-07-12 | 江西省科学院应用物理研究所 | Rare earth-containing Cu-Mg-Si alloy and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732731A (en) * | 1985-08-29 | 1988-03-22 | The Furukawa Electric Co., Ltd. | Copper alloy for electronic instruments and method of manufacturing the same |
| CN101008056A (en) * | 2007-01-19 | 2007-08-01 | 华东理工大学 | Alloy material used for circuit lead frame and its manufacture method |
| CN101050494A (en) * | 2007-05-16 | 2007-10-10 | 赵景财 | Material of spring brass alloy, and production method |
| CN101696476A (en) * | 2009-10-14 | 2010-04-21 | 苏州有色金属研究院有限公司 | Corrosion-resistant multicomponent aluminum-bronze alloy material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6089536A (en) * | 1983-10-22 | 1985-05-20 | Kobe Steel Ltd | Corrosion resistant copper alloy and its manufacture |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732731A (en) * | 1985-08-29 | 1988-03-22 | The Furukawa Electric Co., Ltd. | Copper alloy for electronic instruments and method of manufacturing the same |
| CN101008056A (en) * | 2007-01-19 | 2007-08-01 | 华东理工大学 | Alloy material used for circuit lead frame and its manufacture method |
| CN101050494A (en) * | 2007-05-16 | 2007-10-10 | 赵景财 | Material of spring brass alloy, and production method |
| CN101696476A (en) * | 2009-10-14 | 2010-04-21 | 苏州有色金属研究院有限公司 | Corrosion-resistant multicomponent aluminum-bronze alloy material |
Non-Patent Citations (1)
| Title |
|---|
| JP昭60-89536A 1985.05.20 |
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