CN105177344B - Cu-Fe alloy wire and preparing method thereof - Google Patents
Cu-Fe alloy wire and preparing method thereof Download PDFInfo
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- CN105177344B CN105177344B CN201510459015.9A CN201510459015A CN105177344B CN 105177344 B CN105177344 B CN 105177344B CN 201510459015 A CN201510459015 A CN 201510459015A CN 105177344 B CN105177344 B CN 105177344B
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- 239000000956 alloy Substances 0.000 title claims abstract description 100
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910017827 Cu—Fe Inorganic materials 0.000 title abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 86
- 239000010949 copper Substances 0.000 claims abstract description 58
- 238000005266 casting Methods 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 238000005242 forging Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 87
- 238000000137 annealing Methods 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 50
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 45
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims description 45
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005098 hot rolling Methods 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000007499 fusion processing Methods 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 102000002151 Microfilament Proteins Human genes 0.000 claims description 5
- 108010040897 Microfilament Proteins Proteins 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 210000003632 microfilament Anatomy 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000005482 strain hardening Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 230000009286 beneficial effect Effects 0.000 claims description 3
- 238000010622 cold drawing Methods 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims 2
- 239000000686 essence Substances 0.000 claims 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims 1
- 239000011538 cleaning material Substances 0.000 claims 1
- 238000005204 segregation Methods 0.000 abstract description 11
- 239000006104 solid solution Substances 0.000 abstract description 6
- 229910002549 Fe–Cu Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910021652 non-ferrous alloy Inorganic materials 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 2
- 238000013461 design Methods 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 210000001787 dendrite Anatomy 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
The invention discloses a Cu-Fe alloy wire and a preparing method thereof, and belongs to the technical field of non-ferrous alloy. The preparing method includes the steps that an intermediate alloy with even ingredients is used as parent materials, wherein the ingredients of the parent materials comprise 45% to 60% of Fe, 0.20% to 0.35% of Ni, not smaller than 0% of RE and the balance Cu; and then cathode copper and the intermediate alloy parent materials serve as raw materials, and a casting-state alloy ingot is obtained through vacuum melting and further machined into the Cu-Fe alloy wire, wherein the wire is prepared from 8.0% to 13.0% of Fe and the balance Cu and unavoidable impurities. When the prepared Cu-Fe alloy is in the casting state and the forging state, Fe-Cu solid solution is good, Fe elements are evenly distributed without segregation, and good machinability is achieved. The diameter phi of the further-machined finished wire ranges from 0.05 mm to 0.1 mm, the tensile strength of the finished wire is larger than or equal to 440 N/mm<2>, and the elongation of the finished wire is larger than or equal to 10%. The Cu-Fe alloy further has the excellent electromagnetic shielding effect.
Description
Technical field
The present invention relates to non-ferrous alloy technical field, be specifically related to a kind of copper-iron alloy silk material and preparation method thereof.
Background technology
Metal material has a wide range of applications scope, but few, by metal material to the report of copper-iron alloy both at home and abroad
The knowledge learned can predict the Some features of Cu-Fe alloy: (1) fusing point should be higher than that Cu is less than Fe, if being used as vacuum
Electrical contact material substitutes Cu alloy, then can improve its arc ablation resistance ability；(2) fine copper and pure iron all have good extension
Property, therefore Cu-Fe alloy should also possess this performance；(3) cost of Cu material can be reduced with Fe Substitute For Partial Cu；(4) tool
There is effectiveness.
Fig. 1 show Cu-Fe binary alloy phase diagram, and primary solid solution theory is thought: the atomic radius of two kinds of elements and electrification
Learning character the most similar, the most easily form solid solution, but Fe-Cu system is exception, their atomic radius is almost equal, chemistry
Affinity or electronegativity and other chemical property are the most much like, but the dissolubility below fusing point is the least, from metal phase diagram
On see Fe only 2.5% unlimited solid solution in Cu.Along with the increase of Fe content, Cu-Fe alloy is easily formed in process of setting
The microscopic structure of the tissue that segregation is serious, i.e. alloy is mainly present in Cu matrix with nascent rich Fe dendritic form, Fe content
The highest, α-Fe dendrite is the thickest, because this characteristic of this alloy, significantly hinders production and the application of Cu-Fe alloy.
Alloy is in smelting process, and some elements are to add in the way of intermediate alloy.Utilize the side that intermediate alloy adds
Formula, on the one hand can reduce the melting loss of alloying element, thus realize the accurate control to alloy composition；The opposing party
Face, also shortens smelting time while reducing smelting temperature, is conducive to improving the life-span of smelting equipment, and saves the energy.
Separately there are some researches show, the factor such as the composition of intermediate alloy, structure also can produce material impact to the performance of prepared alloy.
Therefore, by using specific intermediate alloy masterbatch during producing Cu-Fe bianry alloy, made to changing
The solid solubility of standby Cu-Fe bianry alloy, optimizes its performance and expansive approach scope, becomes a kind of new Research Thinking.
Summary of the invention
It is an object of the invention to provide a kind of copper-iron alloy silk material and preparation method thereof, use the middle conjunction of specific composition
Gold masterbatch, good with Cu solid solution in conjunction with Fe when specific technique, the CuFe alloy casting state of preparation and forging state, Fe Elemental redistribution is equal
Even, not segregation, has good processability.After being processed further filamentation material, there is mechanical strength and the elongation percentage of excellence.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of copper-iron alloy silk material, weight percentage, this copper-iron alloy silk material chemical composition is: Fe be 8.0～
13.0%, surplus is Cu and inevitable impurity；The preferred chemical composition of this material is: Fe is 8.5～11.5%, and surplus is
Cu and inevitably impurity；In its chemical composition: C≤0.03%, S≤0.01%, P≤0.01%.
This copper-iron alloy silk material finished size tolerance grade is high, its diameter Ф 0.05～0.1mm, tensile strength >=440N/
mm2；Elongation percentage >=10%；This material also has the effectiveness of excellence.
Described copper-iron alloy silk material is prepared in accordance with the following steps:
(1) raw material prepares and dispensing
By tough cathode and intermediate alloy masterbatch surface successively through pickling, washing and drying and processing, it is ensured that all raw materials clean,
Then in required ratio correct amount；Described pickling refers to: tough cathode uses the sulfuric acid cleaned of concentration 30vol.%, ingot iron
The hydrochloric acid using concentration 30vol.% cleans, and electrolytic nickel uses the nitric acid of concentration 40vol.% to clean；Described intermediate alloy masterbatch
For strip-like copper ferrum intermediate alloy, weight percentage, this master alloy chemistries is: Fe 45～60%, Ni 0.20
～0.35%, RE > 0, Cu are surplus；Wherein: RE is lanthanide-indueed shift；This master alloy chemistries is preferably: Fe 48
～52%, Ni 0.20～0.30%, La < 0.02%, Ce < 0.04%, Cu are surplus.
Described intermediate alloy masterbatch is as ferrum element and the source of part copper element, and described tough cathode is as remainder copper
The source of element；The preparation of described intermediate alloy masterbatch includes following (a)-(e) step:
A () raw material prepares: material choice tough cathode, ingot iron and electrolytic nickel, successively through pickling, washing before raw material use
And drying and processing, to ensure that all raw materials clean；Described pickling refers to: tough cathode uses the sulfuric acid cleaned of concentration 30vol.%,
Ingot iron uses the hydrochloric acid of concentration 30vol.% to clean, and electrolytic nickel uses the nitric acid of concentration 40vol.% to clean.By weight hundred
Dividing content meter, in raw material, each element percentage composition is: Fe 45～60%, Ni 0.20～0.35%, RE 0.05～0.1%, Cu
For surplus；Wherein: RE is lanthanide-indueed shift；In raw material, each element percentage composition is preferably: Fe 48～52%, Ni 0.25
～0.30%, La 0.02～0.025%, Ce 0.04～0.045%, Cu are surplus.
(b) vacuum induction melting:
According to element ratio dispensing each in raw material, then carrying out vacuum induction melting, fusion process is particularly as follows: by negative electrode
Copper, ingot iron load in crucible by proportioning, and in stove, after evacuation, power transmission melts, 1300～1550 DEG C of refine 20-30min；Add
Enter after Ni and CaF refine 20-30min again；It is eventually adding La and Ce, after 40～50 seconds, starts charged casting；In fusion process,
Vacuum≤8Pa, refining temperature controls at 1300～1550 DEG C；Casting obtains alloy cast ingot；
(c) ingot mill surface:
Remove the thick top layer of ingot casting surface 2-3mm with vertical knee-type milling machine, its objective is to remove the part that impurity content is high, simultaneously
It is beneficial to following process；
(d) hot rolling cogging:
Rolling temperature 1000～1015 DEG C, be incubated 90～100 minutes, roll 6-7 passage, is hot-rolled down to 10～12mm, so
After be cold working to 5～6mm；
E the sheet material after () hot rolling cogging is carried out, cleaning process is: first wash away sheet material with the sulphuric acid of concentration 30vol.%
The oxide skin on surface, then with clear water, the residual acid on surface is rinsed well；Cut into after cleaning in the middle of the strip-like copper ferrum of required specification
Alloy material.
(2) vacuum melting
Tough cathode, intermediate alloy masterbatch are loaded in crucible, refine 20-30min after power transmission fusing, it is subsequently adding CaF, then
Secondary refine 20-30min, then start charged casting after being filled with noble gas Ar in stove, i.e. obtain described copper-iron alloy ingot casting；Very
In empty fusion process: refining temperature controls at 1200～1500 DEG C；Vacuum≤2Pa；In prepared copper-iron alloy (ingot casting)
Fe Elemental redistribution uniformly, not segregation.
(3) alloy cast ingot car light:
By copper-iron alloy ingot casting surface car light.
(4) forge hot and forging rear car light:
Flat-die forging on 750Kg pneumatic hammer, heating by electric cooker temperature 850～875 DEG C, after being incubated 60～100 minutes, carry out
Two upsettings two are forged after pulling out to Ф 42～50mm bar；Then car light is to Ф 40～45mm bar.
(5) hot rolling:
Heating by electric cooker temperature 845～855 DEG C, after being incubated 70～80 minutes, roll (stalk on Ф 250 × 350 pass milling train
Pressure) to Ф 10～15mm bar.
(6) cold working and pilot process vacuum annealing:
Step (3) gained Ф 10～15mm bar carries out dish circle, annealing and cold drawing successively process, repeat this process 3
～5 times, it is thus achieved that make annealing treatment again after Ф 1.2～2.0mm silk material, annealing temperature 550～730 DEG C.
(7) microfilament drawing:
After vacuum annealing, soft state Ф 1.2～2.0mm silk material carries out repeatedly drawing process, it is thus achieved that diameter Ф 0.05～0.1mm
Copper-iron alloy silk material, detailed process is:
Ф 1.2～2.0mm silk material is drawn to Ф 0.8～1.2mm, every time working modulus 15%；Hydrogen annealing furnace continuously
Annealing: furnace temperature 740 DEG C, draws and takes between (machine) speed 70～80, silk material elongation percentage >=25% after annealing；By Ф 0.8～
1.2mm silk material is drawn to Ф 0.3～0.5mm, every time working modulus 15%；Hydrogen annealing furnace annealing continuously: furnace temperature 740
DEG C, draw and take between (machine) speed 70～80, silk material elongation percentage >=25% after annealing；Ф 0.3～0.5mm silk material is drawn to Ф
0.15～0.2mm, every time working modulus 13%；Hydrogen annealing furnace annealing continuously: furnace temperature 740 DEG C, draws and takes (machine) speed 70
～between 80, silk material elongation percentage >=20% after annealing；Ф 0.15～0.2mm silk material is drawn to Ф 0.05～0.1mm, every time
Working modulus 12%；Hydrogen annealing furnace annealing continuously: furnace temperature 740 DEG C, draws and takes between (machine) speed 70～80, silk material after annealing
Elongation percentage >=10%.
Advantages of the present invention and having the beneficial effect that:
1, for producing high-strength high-tractility Cu-Fe alloy wire, CuFe intermediate alloy masterbatch is used.On masterbatch ingot casting,
In, lower composition uniform, Fe Elemental redistribution uniformly, not segregation；Use this masterbatch and coordinate the preparation technology of feature can reduce Gao Yan
The fusing point of malleability Cu-Fe alloy, reduces oxidation and the scaling loss of Fe, and by secondary vacuum remelting, makes high ductibility Cu-Fe alloy
Being evenly distributed of middle Fe, not segregation.
2, for making composition uniform CuFe intermediate alloy masterbatch, rare-earth elements La (lanthanum) and the Ce of specific proportioning is added
(cerium), lanthanide-indueed shift has purification, a roguing effect, and under specific process conditions with other element synergism, from
And fully refine the crystal grain of Cu-Fe As-cast Microstructure, reduce the generation of segregation.
3, prepared high-strength high ductibility copper-iron alloy silk material chemical composition stability, the distribution in the alloy of Fe element is equal
Even, not segregation.
4, prepared high-strength, high ductibility copper-iron alloy silk material finished size tolerance grade high, microfilament diameter Ф up to
0.05～0.1mm；Good mechanical performance, silk material tensile strength >=440N/mm2, elongation percentage >=10%；Copper-iron alloy silk material also has
Having the effectiveness of excellence, stable performance, cost performance is high, has the most wide market prospect.
Accompanying drawing explanation
Fig. 1 is CuFe binary alloy phase diagram.
Fig. 2 is the CuFe intermediate alloy metallographic microscopic appearance figure of embodiment 1 preparation.
Fig. 3 is metallographic microscopic appearance figure under CuFe alloy as-cast condition prepared by embodiment 1.
Fig. 4 is metallographic microscopic appearance figure under CuFe alloy forging state prepared by embodiment 1.
Fig. 5 is that the CuFe alloy tensile of embodiment 1 preparation is to metallographic microscopic appearance figure during Ф 8.4mm.
Detailed description of the invention
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
The masterbatch that the present invention is prepared using copper ferrum intermediate alloy as Cu-Fe alloy wire, the preparation of this intermediate alloy
Cheng Wei: raw material preparation → dispensing → vacuum melting → masterbatch component analysis → ingot mill surface → hot rolling → pickling, washing → shearing；
Following example are prepared in accordance with the following steps:
(1) raw material prepares
In raw material, each element proportioning is (wt.%): Fe 45～60%, Ni 0.20～0.35%, RE 0.05～0.1%,
Cu is surplus；Wherein: RE is lanthanide-indueed shift；Preferably proportioning raw materials is: Fe 48～52%, Ni 0.25～
0.30%, La 0.02～0.025%, Ce 0.04～0.045%, Cu are surplus.
(2) dispensing: weigh by element proportion speed each in raw material.By tough cathode, ingot iron, electrolytic nickel surface through acid
Wash, wash, drying and processing, it is ensured that all raw materials clean.Acid cleaning process is: the sulphuric acid of tough cathode employing concentration 30vol.% is clear
Washing, ingot iron uses the hydrochloric acid of concentration 30vol.% to clean, and electrolytic nickel uses the nitric acid of concentration 40vol.% to clean.
(3) vacuum melting
Loading in crucible by tough cathode, ingot iron, electrolytic nickel and CaF load in loading hopper, and lanthanide-indueed shift fills
Enter in feeder；Banking evacuation, vacuum≤8Pa (i.e. 6 × 10-2mmHg)；Refine 25min after power transmission fusing, then Ni (electricity
Solve nickel) and CaF refine 25min again, it is eventually adding La and Ce, starts charged casting after 45 seconds, it is thus achieved that alloy cast ingot.Vacuum melts
The vacuum induction furnace model that refining uses: ZG-0.025；Refining temperature controls at 1300～1550 DEG C.
(4) masterbatch component analysis
Use ammonium acid fluoride to cover Fe, then with the content of the chemistry titration detection upper and lower Cu of masterbatch ingot casting, precisely determine mother
In material, Cu, Fe composition is particularly significant to the production of next step CuFe system alloy.
(5) ingot mill surface
Remove the high part of ingot surface impurity content (removing 2mm thickness top layer) with vertical knee-type milling machine, follow-up add
Work.
(6) hot rolling cogging
Heating by electric cooker: temperature 1010 DEG C, is incubated 90～100 minutes, is hot-rolled down to 12mm, is cold working to 5～6mm.Used by set
Standby: Φ 250 × 450 2 roller hot-rolling mill.
(7) pickling, washing: wash away the oxide skin on masterbatch surface and with clear water by the residual acid on surface with sulphuric acid (30vol.%)
Rinse well.
(8) shear: masterbatch plate shears is cut into required specification strip intermediate alloy stand-by.
Using the strip intermediate alloy of above-mentioned preparation as the masterbatch of the high-strength high ductibility copper-iron alloy silk material of required preparation,
As follows for preparing the process of high-strength high ductibility copper-iron alloy silk material:
(1) raw material prepares and dispensing
By tough cathode and strip intermediate alloy masterbatch surface successively through pickling, washing and drying and processing, it is ensured that all raw materials
Cleaning, described pickling refers to: tough cathode uses the sulfuric acid cleaned of concentration 30vol.%, and ingot iron uses concentration 30vol.%
Hydrochloric acid cleans, and electrolytic nickel uses the nitric acid of concentration 40vol.% to clean；
Copper-iron alloy silk material chemical composition to be prepared is 8.0～13.0% for (wt.%): Fe, and surplus is Cu and not
Evitable impurity；Preferably chemical composition is 8.5～11.5% for (wt.%): Fe, and surplus is Cu and the most miscellaneous
Matter；In alloy: C≤0.03%, S≤0.01%, P≤0.01%.
Raw material after cleaning is by required alloy proportion correct amount；Described intermediate alloy masterbatch is as required preparation Gao Yan
Ferrum element and the source of part copper element in malleability copper-iron alloy, described tough cathode is as the source of remainder copper；
(2) vacuum melting
In Vacuum Melting: refining temperature controls at 1200～1500 DEG C；Vacuum≤2Pa (i.e. 1.5 × 10- 2mmHg)；Vacuum melting device therefor: ZG-0.025 vacuum induction furnace, fusion process is:
Loading in crucible by tough cathode, strip intermediate alloy masterbatch, CaF loads in loading hopper, banking evacuation, and power transmission melts
Refine 20min after change, is subsequently adding CaF, again refine 20min, then starts charged casting after being filled with noble gas Ar in stove,
I.e. obtain copper-iron alloy ingot casting.
(3) using plasma Atomic Emission Spectrometer AES (ICP-1000) detection prepared by copper-iron alloy ingot casting on, in,
The composition of lower Fe.
(4) alloy cast ingot car light:
By copper-iron alloy ingot casting qualified for composition at CA6140 lathe upper surface car light.
(5) forge hot and forging rear car light:
Flat-die forging on 750Kg pneumatic hammer, heating by electric cooker temperature 860 DEG C, after being incubated 90 minutes, carry out after two upsettings two pull out
Forging is to Ф 45mm bar；Then car light is to Ф 42mm bar.
(6) hot rolling:
Heating by electric cooker temperature 850 DEG C, after being incubated 70 minutes, rolling on Ф 250 × 350 pass milling train (stalk pressure) to Ф
13mm bar.
(7) cold working and pilot process vacuum annealing:
Step (3) gained Ф 13mm bar is carried out successively dish circle, annealing (annealing temperature 550～730 DEG C) and cold drawing
Process, repeat this process 4 times, it is thus achieved that after Ф 1.5mm silk material, carry out the annealing under the conditions of 550～730 DEG C again；In this step
Device therefor LS-20 ton chain drawbench；1/560,1/350,1/250 upright stretching machine；Ф 800 pit type annealing furnace etc..
(8) microfilament drawing:
After vacuum annealing, soft state Ф 1.5mm silk material carries out multi pass drawing process, and every time working modulus 15% is drawn to Ф
0.9mm；Continuous annealing furnace annealing (hydrogen): furnace temperature 740 DEG C, draws and takes (machine) speed 80, and silk material elongation percentage after annealing >=
25%；Ф 0.9mm silk material is carried out multi pass drawing process, every time working modulus 15%, it is drawn to Ф 0.4mm；Continuous annealing
Furnace annealing processes (hydrogen): furnace temperature 740 DEG C, draws and takes (machine) speed 70, silk material elongation percentage >=25% after annealing；By Ф 0.4mm silk
Material is drawn to Ф 0.18mm, every time working modulus 13%；Hydrogen annealing furnace annealing continuously: furnace temperature 740 DEG C, draws and takes (machine) speed
Degree 70, silk material elongation percentage >=20% after annealing；Ф 0.18mm silk material is drawn to Ф 0.06mm, every time working modulus 12%；Even
Continuous hydrogen annealing furnace annealing: furnace temperature 740 DEG C, draws and takes (machine) speed 70, silk material elongation percentage >=10% after annealing.
Embodiment 1
1, the present embodiment prepares the concrete consumption of the copper ferrum each raw material of intermediate alloy masterbatch is (wt.%): Fe=48%；Ni=
0.25%；La=0.02%；Ce=0.04%；Cu=51.69%；Gained intermediate alloy masterbatch (1#) composition is shown in Table 1, in the middle of this
Microstructure of the alloy microscopic appearance figure such as Fig. 2, by Fig. 2 with Biao 1 data it can be seen that copper ferrum intermediate alloy chemistry prepared by the present invention becomes
Dividing stable, ingot casting upper, middle and lower composition is uniform；Fe element is evenly distributed in intermediate alloy, not segregation.
2, preparing high-strength high ductibility CuFe alloy, Design of Chemical Composition is (wt.%): Fe=8.8%, Cu=
91.2%.Prepared copper-iron alloy ingot casting composition is as shown in table 2, and ingot chemistry is stable, and ingot casting upper, middle and lower composition is equal
Even；Metallographic microscopic appearance figure under as-cast condition, fig. 3, it is shown that Cu, Fe solid solution is good, still has part free state
Rich Fe exist.As shown in Figure 4, rich Fe free under as cast condition is through heating and forges for metallographic microscopic appearance after ingot casting is forged
Obtain partial crushing.
3, CuFe alloy bar material is processed filamentation material, be stretched to metallographic microscopic appearance such as Fig. 5 during Ф 8.4mm silk material, from
It can be seen that through heating repeatedly, heat treatment and after repeatedly obstructing pressure, stretch process in figure, the distribution of Fe more uniformly, refine.
Finally it is prepared as Ф 0.06mm silk material, after tested, this Ф 0.06mm silk material tensile strength 440N/mm2；Elongation percentage is 12.5%；
This copper-iron alloy also has the effectiveness of excellence.
Embodiment 2
1, the present embodiment prepares copper ferrum intermediate alloy masterbatch process with embodiment 1.
2, preparing high-strength high ductibility CuFe alloy, Design of Chemical Composition is (wt.%): Fe=9.0%, Cu=
91.0%.Prepared copper-iron alloy ingot casting composition is as shown in table 2, and ingot chemistry is stable, and ingot casting upper, middle and lower composition is equal
Even；
3, CuFe alloy cast ingot is processed into Ф 0.06mm silk material, after tested, this Ф 0.06mm silk material tensile strength 443N/
mm2；Elongation percentage is 12%；This copper-iron alloy also has the effectiveness of excellence.
Embodiment 3
1, the present embodiment prepares copper ferrum intermediate alloy masterbatch process with embodiment 1.
2, preparing high-strength high ductibility CuFe alloy, Design of Chemical Composition is (wt.%): Fe=9.5%, Cu=
90.5%.Prepared copper-iron alloy ingot casting composition is as shown in table 2, and ingot chemistry is stable, and ingot casting upper, middle and lower composition is equal
Even；
3, CuFe alloy cast ingot is processed into Ф 0.06mm silk material, after tested, this Ф 0.06mm silk material tensile strength 445N/
mm2；Elongation percentage is 11.2%；This copper-iron alloy also has the effectiveness of excellence.
Embodiment 4
1, the present embodiment prepares copper ferrum intermediate alloy masterbatch process with embodiment 1.
2, preparing high-strength high ductibility CuFe alloy, Design of Chemical Composition is (wt.%): Fe=10.2%, Cu=
89.8%.Prepared copper-iron alloy ingot casting composition is as shown in table 2, and ingot chemistry is stable, and ingot casting upper, middle and lower composition is equal
Even；
3, CuFe alloy cast ingot is processed into Ф 0.06mm silk material, after tested, this Ф 0.06mm silk material tensile strength 448N/
mm2；Elongation percentage is 11%；This copper-iron alloy also has the effectiveness of excellence.
Embodiment 5
1, the present embodiment prepares the concrete consumption of the copper ferrum each raw material of intermediate alloy masterbatch is (wt.%): Fe=49%；Ni=
0.26%；La=0.02%；Ce=0.04%；Cu=51.68%；Gained intermediate alloy masterbatch (2#) composition is shown in Table 1, by table 1
Data are it can be seen that copper ferrum master alloy chemistries prepared by the present invention is stablized, and ingot casting upper, middle and lower composition is uniform；Fe element
Intermediate alloy is evenly distributed, not segregation.
2, preparing high-strength high ductibility CuFe alloy, Design of Chemical Composition is (wt.%): Fe=10.8%, Cu=
89.2%.Prepared copper-iron alloy ingot casting composition is as shown in table 2, and ingot chemistry is stable, and ingot casting upper, middle and lower composition is equal
Even；
3, CuFe alloy cast ingot is processed into Ф 0.06mm silk material, after tested, this Ф 0.06mm silk material tensile strength 452N/
mm2；Elongation percentage is 10.3%；This copper-iron alloy also has the effectiveness of excellence.
Embodiment 6
1, the present embodiment prepares the concrete consumption of the copper ferrum each raw material of intermediate alloy masterbatch is (wt.%): Fe=50%；Ni=
0.27%；La=0.02%；Ce=0.04%；Cu=49.67%；Gained intermediate alloy masterbatch (3#) composition is shown in Table 1, by table 1
Data are it can be seen that copper ferrum master alloy chemistries prepared by the present invention is stablized, and ingot casting upper, middle and lower composition is uniform；Fe element
Intermediate alloy is evenly distributed, not segregation.
2, preparing high-strength high ductibility CuFe alloy, Design of Chemical Composition is (wt.%): Fe=11.2%, Cu=
88.8%.Prepared copper-iron alloy ingot casting composition is as shown in table 2, and ingot chemistry is stable, and ingot casting upper, middle and lower composition is equal
Even；
3, CuFe alloy cast ingot is processed into Ф 0.06mm silk material, after tested, this Ф 0.06mm silk material tensile strength 455N/
mm2；Elongation percentage is 10%；This copper-iron alloy also has the effectiveness of excellence.
In above-described embodiment, CuFe intermediate alloy masterbatch (ingot casting) chemical composition measured value (analyzes method: use as shown in table 1
Ammonium acid fluoride covers Fe, and then titrimetry surveys Cu content, surveys other constituent contents in conjunction with other elemental analysis method).Prepared
Copper-iron alloy ingot chemistry measured value as shown in table 2, using plasma Atomic Emission Spectrometer AES (ICP-1000) is examined
The composition of the ingot casting upper, middle and lower Fe prepared by survey.
Table 1 CuFe intermediate alloy masterbatch (ingot casting) chemical composition (wt.%)
Table 2 CuFe alloy (ingot casting) chemical composition measured value (wt.%)
Claims (7)
1. the preparation method of a copper-iron alloy silk material, it is characterised in that: weight percentage, this material chemical composition
For: Fe is 8.0～13.0%, and surplus is Cu and inevitable impurity；The preparation method of this material comprises the steps:
(1) raw material prepares and dispensing:
By tough cathode and intermediate alloy masterbatch surface successively through pickling, washing and drying and processing, it is ensured that all raw materials clean, then
In required ratio correct amount；
(2) vacuum melting:
Tough cathode, intermediate alloy masterbatch are loaded in crucible, refine 20-30min after power transmission fusing, it is subsequently adding CaF2, essence again
Refining 20-30min, then start charged casting after being filled with noble gas Ar in stove, i.e. obtain copper-iron alloy ingot casting；Vacuum melting
Cheng Zhong: refining temperature controls at 1200～1500 DEG C, vacuum≤2Pa；
(3) alloy cast ingot car light:
Is got on the bus light at lathe in copper-iron alloy ingot casting surface；
(4) forge hot and forging rear car light:
Flat-die forging on 750Kg pneumatic hammer, heating by electric cooker temperature 850～875 DEG C, after being incubated 60～100 minutes, carry out two upsettings
Two pull out after forge to Ф 42～50mm bar；Then car light is to Ф 40～45mm bar；
(5) hot rolling:
Heating by electric cooker temperature 845～855 DEG C, after being incubated 70～80 minutes, be rolling to Ф 10 on Ф 250 × 350 pass milling train
～15mm bar；
(6) cold working and pilot process vacuum annealing:
Step (5) gained Ф 10～15mm bar carries out dish circle, annealing and cold drawing successively process, repeat this process 3～5
Secondary, it is thus achieved that to make annealing treatment again after Ф 1.2～2.0mm silk material, annealing temperature 550～730 DEG C；
(7) microfilament drawing:
After vacuum annealing, soft state Ф 1.2～2.0mm silk material carries out repeatedly drawing process, it is thus achieved that diameter Ф 0.05～0.1mm copper ferrum
Alloy wire；
In step (1), described intermediate alloy masterbatch is strip-like copper ferrum intermediate alloy, weight percentage, this intermediate alloy
Chemical composition is: Fe 45～60%, Ni 0.20～0.35%, and RE > 0, Cu are surplus；
In step (1), described intermediate alloy masterbatch is as ferrum element and the source of part copper element, and described tough cathode is as residue
The source of part copper element；The preparation of described intermediate alloy masterbatch comprises the steps:
(a) raw material prepare: weight percentage, in raw material, each element percentage composition is: Fe 45～60%, Ni 0.20～
0.35%, RE 0.05～0.1%, Cu are surplus；Wherein: RE is lanthanide-indueed shift；
(b) vacuum induction melting:
According to element ratio dispensing each in raw material, then carry out vacuum induction melting, in fusion process, vacuum≤8Pa, refine
Temperature controls at 1300～1550 DEG C；Casting obtains alloy cast ingot；
(c) ingot mill surface:
Remove the thick top layer of ingot casting surface 2-3mm with vertical knee-type milling machine, its objective is to remove the part that impurity content is high, be beneficial to simultaneously
Following process；
(d) hot rolling cogging:
Rolling temperature 1000～1015 DEG C, be incubated 90～100 minutes, roll 6-7 passage, is hot-rolled down to 10～12mm, the coldest
It is machined to 5～6mm；
E the sheet material after () hot rolling cogging is carried out, cleaning process is: first wash away plate surface with the sulphuric acid of concentration 30vol.%
Oxide skin, then with clear water, the residual acid on surface is rinsed well；The strip-like copper ferrum intermediate alloy of required specification is cut into after cleaning
Material.
The preparation method of copper-iron alloy silk material the most according to claim 1, it is characterised in that: fusion process in step (b)
Particularly as follows: load in crucible by tough cathode, ingot iron by proportioning, in stove, after evacuation, power transmission melts, 1300～1550 DEG C of essences
Refining 20-30min；Add Ni and CaF2After refine 20-30min again；It is eventually adding La and Ce, after 40～50 seconds, starts charged watering
Casting obtains alloy cast ingot.
The preparation method of copper-iron alloy silk material the most according to claim 2, it is characterised in that: tough cathode, industry in raw material
Successively through pickling, washing and drying and processing before pure iron and electrolytic nickel surface use, to ensure that all raw materials clean；Described pickling is
Referring to: tough cathode uses the sulfuric acid cleaned of concentration 30vol.%, ingot iron uses the hydrochloric acid of concentration 30vol.% to clean, electrolytic nickel
The nitric acid using concentration 40vol.% cleans.
The preparation method of copper-iron alloy silk material the most according to claim 1, it is characterised in that: microfilament drawing in step (7)
Process is specific as follows:
Ф 1.2～2.0mm silk material is drawn to Ф 0.8～1.2mm, every time working modulus 15%；Hydrogen annealing furnace annealing continuously
Process: furnace temperature 740 DEG C, silk material elongation percentage >=25% after annealing；Ф 0.8～1.2mm silk material is drawn to Ф 0.3～0.5mm, often
Pass reduction 15%；Hydrogen annealing furnace annealing continuously: furnace temperature 740 DEG C, silk material elongation percentage >=25% after annealing；By Ф
0.3～0.5mm silk material is drawn to Ф 0.15～0.2mm, every time working modulus 13%；Hydrogen annealing furnace annealing continuously: stove
Temperature 740 DEG C, silk material elongation percentage >=20% after annealing；Ф 0.15～0.2mm silk material is drawn to Ф 0.05～0.1mm, every time
Working modulus 12%；Hydrogen annealing furnace annealing continuously: furnace temperature 740 DEG C, silk material elongation percentage >=10% after annealing.
The preparation method of copper-iron alloy silk material the most according to claim 1, it is characterised in that: weight percentage,
In this material chemical composition: Fe is 8.5～11.5%, surplus is Cu and inevitable impurity.
The preparation method of copper-iron alloy silk material the most according to claim 1 or 5, it is characterised in that: percentage composition by weight
Meter, in this material chemical composition: C≤0.03%, S≤0.01%, P≤0.01%.
The preparation method of copper-iron alloy silk material the most according to claim 1 or 5, it is characterised in that: this material diameter Ф
0.05～0.1mm, tensile strength >=440N/mm2, elongation percentage >=10%；This copper-iron alloy silk material has effectiveness.
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