CN100588732C - Process for preparing magnesium-lithium-dysprosium alloy by fused salt electrolysis - Google Patents
Process for preparing magnesium-lithium-dysprosium alloy by fused salt electrolysis Download PDFInfo
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- CN100588732C CN100588732C CN200810064626A CN200810064626A CN100588732C CN 100588732 C CN100588732 C CN 100588732C CN 200810064626 A CN200810064626 A CN 200810064626A CN 200810064626 A CN200810064626 A CN 200810064626A CN 100588732 C CN100588732 C CN 100588732C
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Abstract
The invention provides a Mg Li -Dysprosium alloy and a method for preparing the same through fusion electrolysis. The method uses MgCl2+LiCl+KCl+KF as an electrolyte system in an electrolytic furnace,then adds anhydrous Dy2O3powders to heat up to a melting temperature of 630 DEG C, using metal molybdenum (Mo) as a cathode and graphite as an anode at an electrolysis temperature of between 660 and760 DEG C, and adopts a sinking cathode method, in which a cathodic current density is 10-15A/cm<2>, an anodic current density is 0.4-0.6A/cm<2> and a cell voltage is 7-8V, so as to deposit a Mg-Li-Dyalloy nearby the cathode in a fused-salt electrolysis cell after electrolyzing for 1 to 2 hours. The method does not use metallic magnesium, metal lithium, or metallic dysprosium, but uses metal compound as raw materials to directly prepare the Mg-Li-Dy alloy through the fusion electrolysis method, thereby having the advantages of greatly shortened production flow, simple process so as to reducethe production cost.
Description
(1) technical field
What the present invention relates to is a kind of alloy, specifically a kind of magnesium-lithium-dysprosium alloy.The invention still further relates to a kind of preparation method of magnesium-lithium-dysprosium alloy.
(2) background technology
Magnesium alloy is because the characteristic of its light weight is subjected to the favor of all trades and professions, yet magnesium alloy has shortcomings such as intensity is lower, toughness is relatively poor, high thermal resistance is poor, solidity to corrosion difference; Rare earth metal has purification, refinement and alloying action in black and Non-ferrous Metallurgy process, in magnesium alloy, has certain solid solubility, in magnesium alloy, add simultaneously the compound that rare earth can form the intergranular good thermal stability, so magnesium rare earth based alloy possess higher intensity and resistance to elevated temperatures preferably simultaneously.
Little, the good moldability of magnesium lithium alloy density, but rolled sheet metal, be suitable for most seeking the requirement of lightweight and high tenacity, but it is low that it has intensity, be difficult to application on structural part, corrosion-resistant, cost height, element lithium and easily separate out shortcomings such as causing the alloy instability, caused present magnesium lithium alloy research to stay cool substantially.Therefore, comprehensive utilization rare earth and the effect of lithium in magnesium alloy can be maximized favourable factors and minimized unfavourable ones, and realize high-strength, high-ductility, the magnesium alloy that resistance to elevated temperatures is good and solidity to corrosion is good.
Traditional magnesium lithium alloy manufacture method is as to the method for mixing, exist such as long flow path, energy consumption height, a series of problems such as metal loss is big, environmental pollution is serious, power on lithium deposition to form the method for alloy at liquid magnesium (or solid-state magnesium) at negative electrode and document proposes, though the comparison method of mixing has had certain improvement, but still need preparation MAGNESIUM METAL (or magnesium alloy) earlier, fundamentally do not solve the drawback of long flow path.
Need at first produce each single metal to the method for mixing, be mixed in proportion then, fusion, stirring, ingot casting, operation is many, the energy consumption height.The method of mixing is mainly contained following some deficiency:
A. Zhi Bei magnesium lithium alloy will produce the macrosegregation of metallic lithium and rare earth inevitably, because magnesium, lithium, rare earth differ greatly on proportion, lithium and rare earth can not be distributed in the magnesium well;
B. in molten process,, therefore must cause the serious scaling loss of active element such as magnesium, lithium, cause composition to be difficult to control because the fusing point of rare earth metal is high more a lot of than the fusing point of magnesium, lithium to blending;
C. must be before this method through single magnesium, the preparation of lithium and the preparation process of other metallic elements.
The consumable cathode method that proposes in the prior art prepares alloy, for example the patent No. is 200510054067.4, name is called in the patent application document of " producing Dy-Fe alloy by molten salt electrolysis method Processes and apparatus ", and disclosing a kind of is electrolysis cathode with the pure iron, at fused binary villiaumite (DyF
3, LiF) prepare Dy-Fe alloy with consumable pure iron catholyte dysprosium oxide in the system, it is the consumable negative electrode that this method still needs pure iron.The high Faradaic current electrolysis of the high electrolysis temperature rare earth fluorine that proposes in the prior art prepares the patent of alloy, for example application number is 03133598.5, name is called in the patent " a kind of dysprosium metal alloy and preparation method thereof ", disclosing a kind of is the method for a kind of dysprosium metal alloy of ionogen electrolysis production with dysprosium fluoride, lithium fluoride, neodymium fluoride, but the electrolysis temperature that this method needs is that 1180 ℃ of energy consumption scaling loss are bigger.Also produce the report of magnesium-rare earth alloy in addition relevant for the method that adopts the fused salt electrolysis coelectrodeposition, for example number of patent application is 200510017209.X, and name is called the technical scheme of record in " the coelectrodeposition preparation method of magnesium-lanthanum-praseodymium-cerium master alloy " etc.But preparing magnesium lithium-rare earth alloy by the magnesium-lanthanum-praseodymium-cerium master alloy still needs to adopt to mixing method interpolation metallic lithium.
(3) summary of the invention
The object of the present invention is to provide a kind of magnesium-lithium-dysprosium alloy that is suitable for industrial application that has.The present invention also aims to provide a kind of fused salt electrolysis preparation method thereof that can save the energy, reduce production costs, be easy to industrialized magnesium-lithium-dysprosium alloy.
The object of the present invention is achieved like this: magnesium-lithium-dysprosium alloy of the present invention by weight ratio is: the magnesium of lithium 0.5～42.6%, dysprosium 0.8～20.1% and surplus is formed.
Magnesium-lithium-dysprosium alloy of the present invention adopts following method to prepare:
300 ℃, 600 ℃ drying treatment 24 hours, KF was by KF2H respectively for LiCl and KCl
2O is through the dehydration preparation, and dehydration conditions is: with KF2H
2O places vacuum drying oven, and dehydration temperaturre is more than 130 ℃, in electrolytic furnace, is negative electrode and places the electrolyzer lower curtate that graphite is anode with inert metal electrode molybdenum (Mo), and pole span is 4cm, adds the MgCl through dehydration in corundum crucible
2, LiCl, KCl and KF, the mass percent of each composition respectively 5～13%, 40～45%, 40～45% and 5% is pressed MgCl again
21～7% of weight adds Dy
2O
3, controlled temperature is treated in the crucible to feed the direct current electrolysis, control cathode current density 10～15A/cm after the material fusion under 660～760 ℃ condition
2, reach or near Mg
2+Limiting diffusion current density; Anodic current density is 0.4～0.6A/cm
2, bath voltage 7～8V through 1～2 hour electrolysis, deposits liquid Mg-Li-Dy alloy at the fused salt electrolysis trench bottom near negative electrode, get solid-state Mg-Li-Dy alloy after the condensation.
According to reported in literature, in magnesium alloy, add Dy, mainly play three effects: the first, can improve the machining property and the physicals of magnesium alloy; The second, have cleaning action; The 3rd, generate intermetallic compound with the metal that is the solute state in the alloy, improved alloy flowability, processing characteristics, improved performances such as magnesium alloy strength, plasticity, solidity to corrosion, wear resistance, heat-resisting, high temperature creep-resisting.
Because the proportion of the alloy middle-weight rare earths of preparation is bigger, the proportion of alloy is greater than electrolytical proportion, so adopt the sunk type negative electrode.
It is simple to the invention provides a kind of technology, the magnesium-lithium-dysprosium alloy preparation method that production cost is low.Characteristics of the present invention are (1) promptly without MAGNESIUM METAL and lithium, also without rare earth metal, are raw material but all adopt metallic compound, adopt fused salt electrolysis directly to prepare magnesium-lithium-dysprosium alloy, therefore Production Flow Chart are shortened greatly, and technology is simpler; (2) electrolysis temperature of the present invention low (660～760 ℃) is well below Dy
2O
3Fusing point (2352 ℃) and the fusing point of metal Dy (1407 ℃), therefore, can prolong the work-ing life of equipment, save the energy, reduce production costs.
(4) description of drawings
Fig. 1 to Fig. 3 is electronic scanning Electronic Speculum (SEM) photo by the prepared magnesium-lithium-dysprosium alloy of fused salt electrolysis.Wherein Fig. 1 is the line sweep of the alloying element content surveyed of the incidental power spectrum of SEM; Fig. 2 and Fig. 3 are the face scanning of the alloying elements distribution surveyed of SEM and the incidental power spectrum of SEM.
Fig. 4 is the quality percentage composition table of the alloy compositions each point of EDS analysis.
(5) embodiment
For example the present invention is done in more detail below and describes:
Embodiment 1: with MgCl
2+ LiCl+KCl+KF is an electrolyte system, and the mass percent of each composition is respectively 13%, 41%, 41%, 5%, presses MgCl again
23% of weight adds rich dysprosium rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, under 680 ℃ of the electrolysis temperatures, takes cathode method, and pole span is 4cm, and cathode current density is 10A/cm
2, anodic current density 0.4A/cm
2, bath voltage 7.7～8V, the electrolysis through 2 hours deposits the Mg-Li-Dy alloy near fused-salt bath and negative electrode, and the content of magnesium, lithium, dysprosium is respectively: 87.3%, 3.9%, 8.8%.
Embodiment 2: with MgCl
2+ LiCl+KCl+KF is an electrolyte system, and the mass percent of each composition is respectively 13%, 41%, 41%, 5%, presses MgCl again
23% of weight adds rich dysprosium rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, under 680 ℃ of the electrolysis temperatures, takes cathode method, and pole span is 4cm, and cathode current density is 15A/cm
2, anodic current density 0.5A/cm
2, bath voltage 8.7～9.3V, the electrolysis through 1 hour deposits the Mg-Li-Dy alloy near fused-salt bath and negative electrode, and the content of magnesium, lithium, dysprosium is respectively: 98.7%, 0.5%, 0.8%.
Embodiment 3: with MgCl
2+ LiCl+KCl+KF is an electrolyte system, and the mass percent of each composition is respectively 13%, 41%, 41%, 5%, presses MgCl again
23% of weight adds rich dysprosium rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, under 680 ℃ of the electrolysis temperatures, takes cathode method, and pole span is 4cm, and cathode current density is 10A/cm
2, anodic current density 0.5A/cm
2, bath voltage 6.5～7.1V, the electrolysis through 1 hour deposits the Mg-Li-Dy alloy near fused-salt bath and negative electrode, and the content of magnesium, lithium, dysprosium is respectively: 97.6%, 1.4%, 1%.
Embodiment 4: with MgCl
2+ LiCl+KCl+KF is an electrolyte system, and the mass percent of each composition is respectively 13%, 41%, 41%, 5%, presses MgCl again
23% of weight adds rich dysprosium rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, under 660 ℃ of the electrolysis temperatures, takes cathode method, and pole span is 4cm, and cathode current density is 10A/cm
2, anodic current density 0.4A/cm
2, bath voltage 7.6～8.1V, the electrolysis through 1 hour deposits the Mg-Li-Dy alloy near fused-salt bath and negative electrode, and the content of magnesium, lithium, dysprosium is respectively: 89.9%, 5.4%, 4.7%.
Embodiment 5: with MgCl
2+ LiCl+KCl+KF is an electrolyte system, and the mass percent of each composition is respectively 13%, 41%, 41%, 5%, presses MgCl again
23% of weight adds rich dysprosium rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, under 760 ℃ of the electrolysis temperatures, takes cathode method, and pole span is 4cm, and cathode current density is 10A/cm
2, anodic current density 0.5A/cm
2, bath voltage 7.5～8V, the electrolysis through 1 hour deposits the Mg-Li-Dy alloy near fused-salt bath and negative electrode, and the content of magnesium, lithium, dysprosium is respectively: 95.4%, 0.8%, 3.8%.
Embodiment 6: with MgCl
2+ LiCl+KCl+KF is an electrolyte system, and the mass percent of each composition is respectively 13%, 41%, 41%, 5%, presses MgCl again
21% of weight adds rich dysprosium rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, under 680 ℃ of the electrolysis temperatures, takes cathode method, and pole span is 4cm, and cathode current density is 10A/cm
2, anodic current density 0.5A/cm
2, bath voltage 7.6～8.1V, the electrolysis through 1 hour deposits the Mg-Li-Dy alloy near fused-salt bath and negative electrode, and the content of magnesium, lithium, dysprosium is respectively: 97.1%, 1.3%, 1.6%.
Embodiment 7: with MgCl
2+ LiCl+KCl+KF is an electrolyte system, and the mass percent of each composition is respectively 13%, 41%, 41%, 5%, presses MgCl again
27% of weight adds rich dysprosium rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, under 680 ℃ of the electrolysis temperatures, takes cathode method, and pole span is 4cm, and cathode current density is 10A/cm
2, anodic current density 0.5Mcm
2, bath voltage 7.9～8.1V, the electrolysis through 2 hours deposits the Mg-Li-Dy alloy near fused-salt bath and negative electrode, and the content of magnesium, lithium, dysprosium is respectively: 75.1%, 4.8%, 20.1%.
Embodiment 8: with MgCl
2+ LiCl+KCl+KF is an electrolyte system, and the mass percent of each composition is respectively 5%, 45%, 45%, 5%, presses MgCl again
23% of weight adds rich dysprosium rare earth oxide, is negative electrode with inert metal molybdenum (Mo), and graphite is anode, under 680 ℃ of the electrolysis temperatures, takes cathode method, and pole span is 4cm, and cathode current density is 15A/cm
2, anodic current density 0.6A/cm
2, bath voltage 7.6～8V, the electrolysis through 1 hour deposits the Mg-Li-Dy alloy near fused-salt bath and negative electrode, and the content of magnesium, lithium, dysprosium is respectively: 52.8%, 42.6%, 4.6%.
In the Figure of description, Fig. 1 to Fig. 3 is electronic scanning Electronic Speculum (SEM) photo by the prepared magnesium-lithium-dysprosium alloy of fused salt electrolysis, and wherein Fig. 1 is the line sweep of the alloying element content surveyed of the incidental power spectrum of SEM, and each point data is seen the table 1 of Fig. 4.Fig. 2 and Fig. 3 are the face scanning of the alloying elements distribution surveyed of SEM and the incidental power spectrum of SEM.Fig. 1 to Fig. 3 illustrates, is more even by the prepared magnesium-lithium-dysprosium alloy of fused salt electrolysis, the segregation-free phenomenon.
Claims (3)
1, a kind of method of preparing magnesium-lithium-dysprosium alloy by fused salt electrolysis is characterized in that: 300 ℃, 600 ℃ drying treatment 24 hours, KF was by KF2H respectively for LiCl and KCl
2O is through the dehydration preparation, and dehydration conditions is: with KF2H
2O places vacuum drying oven, and dehydration temperaturre is 130 ℃, in electrolytic furnace, is negative electrode and places the electrolyzer lower curtate that graphite is anode with the inert metal molybdenum, and pole span is 4cm, adds the MgCl through dehydration in corundum crucible
2, LiCl, KCl and KF, the mass percent of each composition is respectively 5～13%, 41～45%, 41～45% and 5%, presses MgCl again
21～7% of weight adds Dy
2O
3, controlled temperature is treated in the crucible to feed the direct current electrolysis, control cathode current density 10～15A/cm after the material fusion under 660～760 ℃ condition
2, reach or near Mg
2+Limiting diffusion current density; Anodic current density is 0.4～0.6A/cm
2, bath voltage 7～8V through 1～2 hour electrolysis, deposits liquid Mg-Li-Dy alloy at the fused salt electrolysis trench bottom near negative electrode, get solid-state Mg-Li-Dy alloy after the condensation.
2, the method for preparing magnesium-lithium-dysprosium alloy by fused salt electrolysis according to claim 1 is characterized in that: under 760 ℃ of the described electrolysis temperatures, pole span is 4cm, and cathode current density is 10A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 7.5～8V through 1 hour electrolysis, deposits the Mg-Li-Dy alloy at fused-salt bath near negative electrode, and the content of magnesium, lithium, dysprosium is respectively 95.4%, 0.8%, 3.8%.
3, the method for preparing magnesium-lithium-dysprosium alloy by fused salt electrolysis according to claim 1 is characterized in that: under 680 ℃ of the described electrolysis temperatures, pole span is 4cm, and cathode current density is 15A/cm
2, anodic current density is 0.6A/cm
2, bath voltage 7.6～8V through 1 hour electrolysis, deposits the Mg-Li-Dy alloy at fused-salt bath near negative electrode, and the content of magnesium, lithium, dysprosium is respectively 52.8%, 42.6%, 4.6%.
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| CN101914706B (en) * | 2010-07-23 | 2012-02-01 | 哈尔滨工程大学 | Zinc-aluminum-neodymium alloy and fused salt electrolysis preparation method thereof |
| CN102134728A (en) * | 2011-03-01 | 2011-07-27 | 哈尔滨工程大学 | Method for separating praseodymium oxide and dysprosium oxide through fused salt electrolytic deposition |
| CN102644094B (en) * | 2012-04-24 | 2014-08-06 | 哈尔滨工程大学 | Method for preparing Al-Mg-Tb ternary alloy by means of fused salt electrolysis |
| GB2566035B (en) * | 2017-08-30 | 2019-11-27 | Medalliance Ltd | Metal alloy and medical device containing same |
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