CN110205652A - A kind of preparation method and application of copper bearing master alloy - Google Patents
A kind of preparation method and application of copper bearing master alloy Download PDFInfo
- Publication number
- CN110205652A CN110205652A CN201910407398.3A CN201910407398A CN110205652A CN 110205652 A CN110205652 A CN 110205652A CN 201910407398 A CN201910407398 A CN 201910407398A CN 110205652 A CN110205652 A CN 110205652A
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- preparation
- scandium
- alloy
- crucible
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
Abstract
The invention discloses a kind of preparation methods of copper bearing master alloy, in the molten salt electrolyte containing scandium, are that can consume cathode with metal copper electrode, using graphite as anode, prepare copper bearing master alloy by molten-salt electrolysis；The copper bearing master alloy of above method preparation is used to prepare Mo-bearing granitoid or other containing scandium alloy.Preparation method provided by the invention, simple process, pollution-free, production cost is low, and the content of the copper bearing master alloy scandium of preparation can be used for a variety of preparations containing scandium alloy up to 10~75%.
Description
Technical field
The present invention relates to field of alloy preparation technology, and in particular to a kind of preparation method and application of copper bearing master alloy.
Background technique
The atomic number of scandium is 21, belongs to III subgroup with lanthanide rare metal in periodic table, is equal with titanium, vanadium, chromium
Belong to 3d type transition metal.Metal scandium is that the excellent alterant of cast aluminium alloy gold and the excellent of iron change agent.Metal scandium at present
It is widely used in and prepares aluminium-scandium alloy, micro metal scandium (0.1~0.4%) is added in aluminium alloy, alloy grain can be made thin
Change, significantly improves intensity, plasticity and toughness, high temperature resistance, corrosion resistance of aluminium alloy etc..Mo-bearing granitoid comprehensive performance is obvious
Better than traditional aluminium alloy, it is widely used in the hard-core technologies such as space flight, war industry field.
Since simple substance scandium chemical property is active, and fusing point is high (1541 DEG C), differs larger with aluminium fusing point (660 DEG C), it is difficult to
Mo-bearing granitoid is prepared by the method for direct founding.In the industry in the production process of aluminium-scandium alloy, usually with intermediate alloy
Form scandium is added into alloy.Currently, the preparation method of scandium bearing master alloy mainly has to the method for mixing, metallothermic processes and melts
Salt electrolysis method.
It is using High Purity Scandium Metal and fine aluminium as raw material, in argon atmosphere, by the metal scandium of special ratios to the method for mixing
It is added in aluminum melt, is sufficiently stirred after being wrapped up with aluminium foil, cast after keeping the temperature enough time, can be prepared by closing among aluminium scandium
Gold.Scandium bearing master alloy of the scandium content 2~4%, simple process can be made using to the method for mixing, but the method for mixing is needed to use
High Purity Scandium Metal is raw material, higher cost；Alloy loss is more, and the rate of recovery is low；And scandium, aluminium fusing point differ greatly, ingredient point in alloy
Cloth is uneven, inferior quality.
Metallothermic processes uses scandium fluoride for raw material based on scandium fluoride vacuum thermit reduction, is also with metallic aluminium
Former agent carries out reduction under vacuum and prepares scandium bearing master alloy.Scandium content is up to 30% in intermediate alloy made from the method, but fluorine
It is complicated to change scandium stock preparation process, and the technique can not continuous production, yield is lower.
Fused salt electrolysis process mainly using scandium oxide or scandium chloride as raw material, is electrolysed in chloride system or fluoric-salt system.
When wherein using scandium chloride as raw material, NaCl-KCl-ScCl is mostly used3With LiCl-KCl-ScCl3For electrolyte, with liquid metal aluminium
Make cathode, by using suitable electrolytic parameter, scandium ion deposits on liquid aluminium cathode and formed alloy, on anode
Cl-It is oxidized generation chlorine.It is to be noted that the easy moisture absorption of scandium chloride, it is difficult to transport and storage, and have chlorine in electrolytic process
Gas generation has pollution to environment, therefore less use in industrial production.And when using scandium oxide as raw material, the electrolyte that uses for
NaF·AlF3–Sc2O3–ScF3- NaCl, NaF-Sc2O3–ScF3、CaCl2–Sc2O3Or LiF-Sc2O3–ScF3, mostly use liquid golden
Belong to aluminium to make cathode or add Al in fused salt2O3Liquid aluminium is generated in cathode when to be electrolysed, scandium ion is in cathode in electrolytic process
It deposits and forms intermediate alloy with aluminium.Compared with to the method for mixing and metallothermic processes, closed among the aluminium scandium of fused salt electrolysis process preparation
Fitting has that ingredient is uniform, production cost is low, is easy to continuous production, is not required to advantages such as reducing agents.About fused salt electrolysis process
It prepares in the research of bearing master alloy, is substantially using aluminium-scandium alloy as target product, with liquid aluminium come collecting scandium, but aluminium,
Scandium fusing point differs greatly, and during electrolytic preparation aluminium-scandium alloy, aluminum melt needs the very high degree of superheat, and scandium is in aluminium
Diffusion is slower, is hardly formed the uniform high concentration ingredient containing scandium alloy of ingredient, the content of scandium is lower in intermediate alloy.
Summary of the invention
The technical problem to be solved by the present invention is to there is a problem of that scandium content is low, mentions when molten-salt electrolysis prepares bearing master alloy
The method that cathode carries out the copper bearing master alloy of the high scandium content of electrolytic preparation can be consumed using copper for a kind of.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of preparation method of copper bearing master alloy is that can disappear with metal copper electrode in the molten salt electrolyte containing scandium
It consumes cathode and copper bearing master alloy is prepared by molten-salt electrolysis using graphite as anode.
Further, the molten salt electrolyte includes: 20~70 parts of LiF, 5~60 parts of ScF by mass fraction3, 0~55 part
MCl or/and MF, wherein M is one or more of alkali metal element and alkali earth metal.
Further, raw material Sc is added in the molten salt electrolyte2O3, Sc2O3Addition quality be fused salt quality 0
~30%.
Further, the molten-salt electrolysis temperature is 875~1100 DEG C.
Further, the molten-salt electrolysis, control cathode-current density are 0.5~40A/cm2。
Further, access crucible is placed below cathode to collect copper bearing master alloy product, the access crucible
For molybdenum crucible, tungsten crucible, tantalum crucible or graphite crucible.
The copper bearing master alloy of above method preparation be used to prepare other metals containing scandium alloy.
A kind of preparation method of copper bearing master alloy provided by the invention, simple process, pollution-free, raw material sources are wide, raw
It produces at low cost；In the copper bearing master alloy of preparation, impurity content is lower, the content of scandium by the mass ratio of the material up to 10~75%,
It can be used for a variety of preparations containing scandium alloy, be remarkably improved the mechanical performance of alloy, intensity, plasticity and toughness, high temperature resistant, corrosion-resistant etc.
Performance.
Specific embodiment
A kind of preparation method of copper bearing master alloy is that can disappear with metal copper electrode in the molten salt electrolyte containing scandium
It consumes cathode and copper bearing master alloy is prepared by molten-salt electrolysis using graphite as anode.
Wherein, molten salt electrolyte ingredient is LiF-ScF3- MCl/MF, M are in alkali metal element and alkali earth metal
One or more, the molten salt electrolyte include: 20~70 parts of LiF, 5~60 parts of ScF by mass fraction3, 0~55 part of MCl
Or/and MF.Raw material Sc is added in the molten salt electrolyte2O3, Sc2O3Addition quality be fused salt quality 0~30%.
Specifically, a kind of preparation method of copper bearing master alloy, by Sc2O3It is uniformly mixed with molten salt electrolyte, with graphite earthenware
Crucible contains, and using graphite crucible as anode, will be used as cathode in the fused salt of copper rod insertion fusing, is placed with access earthenware below copper rod
Crucible is separated to collect cathode product product, access crucible with graphite crucible insulation, and molten-salt electrolysis prepares copper bearing master alloy.
The molten-salt electrolysis temperature is 875~1100 DEG C, and control cathode-current density is 0.5~40A/cm2
The access crucible is molybdenum crucible, tungsten crucible, tantalum crucible or graphite crucible.
The copper bearing master alloy of above method preparation is used to prepare containing scandium alloy.It is added in the form of intermediate alloy other
Preparation contains scandium alloy inside metal.
Copper, the opposite aluminium of fusing point difference, the scandium of scandium are smaller, according to Cu-Sc phasor it is found that liquidus curve is more gentle, scandium and copper
Respectively can be in 865 DEG C of formation (the mass ratio of the materiaies) containing scandium 13%, 875 DEG C of formation (the mass ratio of the materiaies) containing scandium 30% or 71%, 890
DEG C formed contain scandium 36.5% (the mass ratio of the material) Cu-Sc alloy.Therefore the present invention is proposed using scandium fluoride or scandium oxide as raw material,
Cathode can be consumed using copper in fluoride or electrolysis of fused chloride salt matter, carry out the high scandium content of electrolytic preparation by anode of graphite
Copper bearing master alloy product.In electrolytic process, scandium ion Sc3+Metal scandium is reduced to cathodic migration and on cathode, gold
Belong to scandium and copper forms Cu-Sc alloy, electrolysis temperature is lower than the fusing point of copper, but is higher than the fusing point of Cu-Sc alloy, and obtained liquid is closed
Gold is separated with cathode to be sunk to entering in the access crucible below cathode, and cathode exposes new surface and continues to be electrolysed.With
The progress of electrolysis, cathode constantly consumes and forms alloy.By adjusting electrolysis temperature and current density, different scandiums can be obtained and contain
The copper bearing master alloy of amount, the Cu-Sc alloy in access crucible obtain Cu-Sc alloy pig after casting is cooling.
Creativeness of the invention is summarized as follows:
1, cathode of the present invention is that can consume cathode, and cathode product is liquid, and relative to solid product, impurity content is low, after
Continuous processing convenience；
2, aluminium-scandium alloy is produced relative to using the molten-salt electrolysis of liquid cathode aluminium, scandium content of the invention dramatically increases, and makees
For the intermediate alloy of aluminium-scandium alloy allotment, not only application is convenient, but also scandium alloy production scale can be greatly reduced, and saves equipment and throws
Money and scandium alloy production cost；
3, the rare earth-iron alloys such as dysprosium iron, terbium iron production equipment and mode can be used for reference, is set without developing special scandium alloy electrolysis
Standby, technical maturity is high.
A kind of preparation method of the copper bearing master alloy of embodiment 1
By 500g fused salt and 150g Sc2O3It is put into the graphite crucible that diameter is 80mm after mixing, wherein according to matter
Measure percentage, the ScF that molten-salt electrolysis plastidome is 60 parts3, 20 parts of LiF and 10 part of NaF；Graphite crucible bottom centre places
Having the diameter crossed with graphite insulation processing is the molybdenum crucible of 50mm as access crucible；Then graphite crucible is put into stove and is added
Heat is to 875 DEG C, and after fused salt dissolves, the copper rod of a diameter 20mm is inserted into fused salt, immersion depth 30mm；With graphite crucible
It for anode, is electrolysed by cathode of copper rod, current density 40A/cm2；The molybdenum earthenware of access is taken out after electrolysis 2h with crucible tongs
The copper bearing master alloy liquid being wherein collected into is cast in mold, copper bearing master alloy ingot is made by crucible.Through detecting, alloy at
Divide and press the mass ratio of the material are as follows: copper 25%, scandium 75%.
A kind of preparation method of the copper bearing master alloy of embodiment 2
By 500g fused salt and 100g Sc2O3It is put into the graphite crucible that diameter is 80mm after mixing, wherein according to matter
Measure percentage, the ScF that molten-salt electrolysis plastidome is 5 parts3With 70 parts of LiF；Graphite crucible bottom centre is placed with exhausted with graphite
The processed diameter of edge is the molybdenum crucible of 50mm as access crucible；Then graphite crucible is put into stove and is heated to 1100
DEG C, after fused salt dissolves, the copper rod of a diameter 20mm is inserted into fused salt, immersion depth 30mm；Using graphite crucible as anode,
It is electrolysed by cathode of copper rod, current density 10A/cm2；The molybdenum crucible for taking out access after electrolysis 2h with crucible tongs, by it
In the copper bearing master alloy liquid that is collected into be cast in mold, copper bearing master alloy ingot is made.Through detecting, alloying component presses substance
Amount ratio are as follows: copper 80%, scandium 20%.
A kind of preparation method of the copper bearing master alloy of embodiment 3
500g fused salt is put into the graphite crucible that diameter is 80mm, wherein according to mass percent, molten-salt electrolysis plastid
The ScF that system is 5 parts3, 70 parts of LiF and 55 part of MgCl；Graphite crucible bottom centre, which is placed with, to be crossed with graphite insulation processing
Diameter is the molybdenum crucible of 50mm as access crucible；Then graphite crucible is put into stove and is heated to 1000 DEG C, it is molten to fused salt
After change, the copper rod of a diameter 20mm is inserted into fused salt, immersion depth 30mm；It is yin with copper rod using graphite crucible as anode
Pole is electrolysed, current density 0.5A/cm2；The molybdenum crucible for taking out access after electrolysis 2h with crucible tongs, by what is be wherein collected into
Copper bearing master alloy liquid is cast in mold, and copper bearing master alloy ingot is made.Through detecting, alloying component presses the mass ratio of the material are as follows:
Copper 90%, scandium 10%.
It should be noted last that the above specific embodiment is only used to illustrate the technical scheme of the present invention and not to limit it,
Although being described the invention in detail referring to example, those skilled in the art should understand that, it can be to the present invention
Technical solution be modified or replaced equivalently, without departing from the spirit and scope of the technical solution of the present invention, should all cover
In the scope of the claims of the present invention.
Claims (7)
1. a kind of preparation method of copper bearing master alloy, it is characterised in that: in the molten salt electrolyte containing scandium, with metallic copper electricity
Cathode can be extremely consumed, using graphite as anode, copper bearing master alloy is prepared by molten-salt electrolysis.
2. preparation method as described in claim 1, it is characterised in that: the molten salt electrolyte by mass fraction include: 20~
70 parts of LiF, 5~60 parts of ScF3, 0~55 part of MCl or/and MF, wherein M is one of alkali metal element and alkali earth metal
Or it is a variety of.
3. preparation method as described in claim 1, it is characterised in that: raw material Sc is added in the molten salt electrolyte2O3,
Sc2O3Addition quality be fused salt quality 0~30%.
4. preparation method as described in claim 1, it is characterised in that: the molten-salt electrolysis temperature is 875~1100 DEG C.
5. preparation method as described in claim 1, it is characterised in that: the molten-salt electrolysis, control cathode-current density are 0.5
~40A/cm2。
6. preparation method as described in claim 1, it is characterised in that: place access crucible below cathode to collect copper scandium
Intermediate alloy product, the access crucible are molybdenum crucible, tungsten crucible, tantalum crucible or graphite crucible.
7. the copper bearing master alloy of any preparation of claim 1~6 be used to prepare other metals containing scandium alloy.
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| CN201910407398.3A CN110205652B (en) | 2019-05-16 | 2019-05-16 | Preparation method and application of copper-scandium intermediate alloy |
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| CN114672851A (en) * | 2022-04-26 | 2022-06-28 | 江西理工大学 | Method for preparing aluminum-scandium-transition metal alloy through consumable cathode molten salt electrolysis |
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| CN114635162A (en) * | 2022-04-26 | 2022-06-17 | 江西理工大学 | Method for preparing aluminum rare earth multicomponent alloy by consumable cathode molten salt electrolysis |
| CN114672851A (en) * | 2022-04-26 | 2022-06-28 | 江西理工大学 | Method for preparing aluminum-scandium-transition metal alloy through consumable cathode molten salt electrolysis |
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