CN103060851A - Method for preparing erbium-thulium alloy containing reinforced aluminum-lithium through molten salt electrolysis co-reduction - Google Patents
Method for preparing erbium-thulium alloy containing reinforced aluminum-lithium through molten salt electrolysis co-reduction Download PDFInfo
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- CN103060851A CN103060851A CN2013100202564A CN201310020256A CN103060851A CN 103060851 A CN103060851 A CN 103060851A CN 2013100202564 A CN2013100202564 A CN 2013100202564A CN 201310020256 A CN201310020256 A CN 201310020256A CN 103060851 A CN103060851 A CN 103060851A
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Abstract
The invention provides a method for preparing an erbium-thulium alloy containing reinforced aluminum-lithium through molten salt electrolysis co-reduction. The method comprises the following steps of: by taking insert metal tungsten as a cathode and a spectral purity graphite rod as an anode in an electrolysis furnace, adding AlF3, ErCl3 and TmCl3 as electrolytes into the KCl-LiCl molten salt in equal mass ratio, wherein the adding quantity of the AlF3 is controlled within 8.0-11.5wt%, and the adding quantities of ErCl3 and TmCl3 are respectively controlled with 0.96-1.0wt%; carrying out electrolysis by using a sinking cathode method at 650 DEG C, wherein the cathode current density is 3.18-7.96Acm<-2>; and carrying out electrolysis for 120 minutes, and carrying out co-reduction to separate out the Al-Li-Er-Tm four-element alloy containing the reinforced Al3Er and Al3Tm near the cathode of a molten salt electrolysis groove. The method can be used for directly preparing the erbium-thulium alloy containing reinforced aluminum-lithium by using the molten salt electrolysis co-reduction method, with simple process and low production cost.
Description
Technical field
That the present invention relates to is a kind of preparation method of aluminium lithium rare earth alloy.
Background technology
Al-Li alloy has low density, high specific strength, high specific stiffness, good low-temperature performance, good corrosion resistance nature and remarkable superplastic forming performance, replace conventional aluminium alloy with it, can make component quality alleviate 10%～15%, rigidity improves 15%～20%, is considered to the optimal high-strength light structured material of 21 century aerospace industry.
But Al-Li alloy also exists poor toughness, and anisotropy obviously reaches the problems such as insufficient strength height.For addressing this problem, various countries scholar formation Al-RE sosoloid or the method for strengthening phase some performance of improving alloy by adding trace rare-earth element La, the elements such as Ce, Sc.And in the Al alloy, add rare earth element er, formation has L1
2The Al of type crystal structure
3Er.Al
3The lattice parameter of Er and aluminium are very approaching, with matrix preferably interface coherency are arranged, and are effective strengthening phases.Simultaneously, because Al
3The fusing point of Er very high (1067 ℃), the growing up and Grain Boundary Sliding of the migration of crystal boundary, crystal grain in the time of can stoping high temperature, thus be conducive to put forward heavy alloyed mechanical property.Therefore, contain L1 in the Al-Li alloy
2The Al of type crystal structure
3The lifting of the relative alloy property of Er is highly profitable.
Be the report of alloy about adopting fused salt electrolysis process direct production aluminium lithium in the prior art, be CN101368281 at publication number for example, name is called in the patent document of " method of aluminum lithium alloy preparation by fused salt electrolysis process ", disclosing a kind of is in the electrolyzer of aluminium in the negative electrode material, add the carbonate or the nitrate that contain lithium, control current density 0.05 ~ 0.3A cm
-2, make lithium content and be 1 ~ 15% Al-Li alloy.Publication number CN101643921, name is called in the patent document of " a kind of method of producing aluminium-lithium alloy with high lithium content by low-temperature molten salt electrolysis ", disclose a kind of in the LiCl-KCl of eutectic system, 380 ~ 450 ℃ of electrolysis temperatures, cathodic current current density 1.0 ~ 3.0Acm
-2Lower, through electrolysis in 1 ~ 4 hour, obtain the Al-Li alloy that alloying constituent is evenly distributed at the aluminium negative electrode.Name is called in the patent document of " a kind of aluminum-lithium-samarium alloy and fused salt electrolysis preparation method thereof " (publication number CN101886197A) for another example, in chloride system, adds Samarium trioxide, at 630 ~ 720 ℃, and cathode current density 6.4Acm
-2, through electrolysis in 2 ~ 6 hours, on inertia Mo electrode, make respectively the Al-Li-Sm alloy that alloying constituent is evenly distributed.
Summary of the invention
The object of the present invention is to provide a kind of production process simple, the fused salt electrolysis coreduction preparation that alloy composition can be controlled in process of production contains the method for strengthening phase aluminium lithium erbium thulium alloy.
The object of the present invention is achieved like this: in electrolytic furnace, take inert metal tungsten as negative electrode, the spectroscopically pure graphite rod is anode, adds AlF in waiting KCl-LiCl fused salt of mass ratio
3, ErCl
3And TmCl
3As ionogen, AlF wherein
3Addition be controlled at 8.0 ~ 11.5wt.%, ErCl
3And TmCl
3Addition be controlled at respectively 0.96 ~ 1.0wt.%, under 650 ℃, adopt the sinking cathode method to carry out electrolysis, cathode current density is 3.18 ~ 7.96A cm
-2, through electrolysis in 120 minutes, coreduction was separated out and is contained strengthening phase Al near the negative electrode of fused-salt bath
3Er and Al
3The Al-Li-Er-Tm quad alloy of Tm.
LiCl among the present invention and KCl are respectively 300 ℃, 600 ℃ drying treatment 24 hours.
The present invention adopts is that the method for aluminium lithium erbium thulium coreduction is produced aluminium lithium erbium thulium alloy.Compare with background technology, without metallic aluminium, metallic lithium and rare earth metal, also without element reduction heavy rare earths erbium and changeable valence rare earth thuliums such as other element such as calcium, lanthanum, ceriums, but direct preparation aluminium lithium erbium thulium alloy of one step of method that all to adopt metallic compound be raw material by fused salt electrolysis.And obtain containing the Al-Li-Er-Tm alloy of strengthening phase by control ionogen proportioning and cathode current density.
It is simple to the invention provides a kind of technique, and the coreduction that production cost is low prepares aluminium lithium erbium thulium alloy preparation method.Characteristics of the present invention are: (1) adopts co-reducing process directly to prepare aluminium lithium erbium thulium alloy.Adopt the method for coreduction to prepare liquid alloy in fused salt, not segregation of alloy can be avoided the restriction of intermetallic compound diffusion and the loss of electrode materials, than using active electrode more to have superiority.Coreduction can be controlled by the electrolytic parameter in the control electrolytic process composition of alloy simultaneously, and technical process is simply controlled.(2) in prepared Al-Li-Tm-Er alloy, contain strengthening phase Al
3Er and Al
3The Tm phase.Al
3Er and Al
3Tm has L1
2The type structure, lattice parameter and matrix Al approach, separate out with matrix coherence or half coherence when solidifying, effective crystal grain thinning, the ageing strengthening effect of raising Al-Li alloy is improved the thermostability of alloy.(3) the Tm element is the changeable valence rare earth element, and in electrolytic process, Tm (III)/Tm (II) existence is repeatedly appraised at the current rate, be difficult to become metal in cathodic reduction, so the electrolytic preparation changeable valence rare earth is the difficult problem in electrolysis field always.The present invention adopts the method for coreduction, and successful electrolysis makes thulium content at 1.60～16.88% Al-Li-Er-Tm alloy on noble electrode, has solved the difficult problem of electrolytic preparation changeable valence rare earth element.
Description of drawings
Accompanying drawing 1 be embodiment 1 preparation contain strengthening phase Al
3Er and Al
3The XRD analysis of the Al-Li-Er-Tm quad alloy of Tm.
Accompanying drawing 2 ~ 4th, scanning electronic microscope (SEM) photo, face scanned photograph and the spot scan photo of the alloy sample of example 4 preparations.Wherein: Fig. 2 is the SEM photo; Fig. 3 a-Fig. 3 c is respectively the EDS face scintigram that Al in the alloy, Er and Tm element distribute; Fig. 4 is the EDS energy spectrum analysis figure that A is ordered in the SEM photo.
Embodiment
The below is described in more detail the present invention for example:
Embodiment 1, in waiting KCl-LiCl fused salt of mass ratio, AlF
3, ErCl
3And TmCl
3Addition be respectively 8.0wt.%, 1.0wt.% and 1.0wt.%, take inert metal tungsten (W) as negative electrode, graphite is anode, electrolysis temperature is under 650 ℃, adopts the sinking cathode method, pole span is 4cm, cathode current density is 7.96A cm
-2, through electrolysis in 2 hours, coreduction was separated out and is contained strengthening phase Al near electric tank cathode
3Er and Al
3The Al-Li-Er-Tm alloy of Tm, the content of the Al in the alloy, Li, Er and Tm is respectively 54.69%, 4.50%, 23.93% and 16.88%.
Embodiment 2, in waiting KCl-LiCl fused salt of mass ratio, AlF
3, ErCl
3And TmCl
3Addition be respectively 9.8wt.%, 0.98wt.% and 0.98wt.%, take inert metal tungsten (W) as negative electrode, graphite is anode, electrolysis temperature is under 650 ℃, adopts the sinking cathode method, pole span is 4cm, cathode current density is 7.96A cm
-2, through electrolysis in 2 hours, coreduction was separated out and is contained strengthening phase Al near electric tank cathode
3Er and Al
3The Al-Li-Er-Tm alloy of Tm, the content of the Al in the alloy, Li, Er and Tm is respectively 79.52%, 2.19%, 11.36% and 6.93%.
Embodiment 3, in waiting KCl-LiCl fused salt of mass ratio, AlF
3, ErCl
3And TmCl
3Addition be respectively 11.5wt.%, 0.96wt.% and 0.96wt.%, take inert metal tungsten (W) as negative electrode, graphite is anode, electrolysis temperature is under 650 ℃, adopts the sinking cathode method, pole span is 4cm, cathode current density is 7.96A cm
-2, through electrolysis in 2 hours, coreduction was separated out and is contained strengthening phase Al near electric tank cathode
3Er and Al
3The Al-Li-Er-Tm alloy of Tm, the content of the Al in the alloy, Li, Er and Tm is respectively 80.94%, 2.18%, 9.83% and 7.05%.
Embodiment 4, in waiting KCl-LiCl fused salt of mass ratio, AlF
3, ErCl
3And TmCl
3Addition be respectively 11.5wt.%, 0.96wt.% and 0.96wt.%, take inert metal tungsten (W) as negative electrode, graphite is anode, electrolysis temperature is under 650 ℃, adopts the sinking cathode method, pole span is 4cm, cathode current density is 6.37A cm
-2, through electrolysis in 2 hours, coreduction was separated out and is contained strengthening phase Al near electric tank cathode
3Er and Al
3The Al-Li-Er-Tm alloy of Tm, the content of the Al in the alloy, Li, Er and Tm is respectively 87.67%, 1.79%, 6.67% and 3.87%.
Embodiment 5, in waiting KCl-LiCl fused salt of mass ratio, AlF
3, ErCl
3And TmCl
3Addition be respectively 11.5wt.%, 0.96wt.% and 0.96wt.%, take inert metal tungsten (W) as negative electrode, graphite is anode, electrolysis temperature is under 650 ℃, adopts the sinking cathode method, pole span is 4cm, cathode current density is 4.78A cm
-2, through electrolysis in 2 hours, coreduction was separated out and is contained strengthening phase Al near electric tank cathode
3Er and Al
3The Al-Li-Er-Tm alloy of Tm, the content of the Al in the alloy, Li, Er and Tm is respectively 91.13%, 1.24%, 4.62% and 3.01%.
Embodiment 6, in waiting KCl-LiCl fused salt of mass ratio, AlF
3, ErCl
3And TmCl
3Addition be respectively 11.5wt.%, 0.96wt.% and 0.96wt.%, take inert metal tungsten (W) as negative electrode, graphite is anode, electrolysis temperature is under 650 ℃, adopts the sinking cathode method, pole span is 4cm, cathode current density is 3.18A cm
-2, through electrolysis in 2 hours, coreduction was separated out and is contained strengthening phase Al near electric tank cathode
3Er and Al
3The Al-Li-Er-Tm alloy of Tm, the content of the Al in the alloy, Li, Er and Tm is respectively 93.96%, 1.87%, 2.57% and 1.60%.
Claims (2)
1. a fused salt electrolysis coreduction prepares the method that contains strengthening phase aluminium lithium erbium thulium alloy, and it is characterized in that: in electrolytic furnace, take inert metal tungsten as negative electrode, the spectroscopically pure graphite rod is anode, adds AlF in waiting KCl-LiCl fused salt of mass ratio
3, ErCl
3And TmCl
3As ionogen, AlF wherein
3Addition be controlled at 8.0～11.5wt.%, ErCl
3And TmCl
3Addition be controlled at respectively 0.96～1.0wt.%, under 650 ℃, adopt the sinking cathode method to carry out electrolysis, cathode current density is 3.18 ~ 7.96A cm
-2, through electrolysis in 120 minutes, coreduction was separated out and is contained strengthening phase Al near the negative electrode of fused-salt bath
3Er and Al
3The Al-Li-Er-Tm quad alloy of Tm.
2. fused salt electrolysis coreduction according to claim 1 preparation contains the method for strengthening phase aluminium lithium erbium thulium alloy, it is characterized in that: described LiCl and KCl are respectively 300 ℃, 600 ℃ drying treatment 24 hours.
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Cited By (1)
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|---|---|---|---|---|
| CN112760515A (en) * | 2020-12-23 | 2021-05-07 | 西南铝业（集团）有限责任公司 | Covering agent and preparation method and application thereof |
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| EP0142829A2 (en) * | 1983-11-18 | 1985-05-29 | Sumitomo Light Metal Industries, Ltd. | Method of producing a high purity aluminum-lithium mother alloy |
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Cited By (1)
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| CN112760515A (en) * | 2020-12-23 | 2021-05-07 | 西南铝业（集团）有限责任公司 | Covering agent and preparation method and application thereof |
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Application publication date: 20130424 |