CN109628764A - A kind of method that calcium original position distillation-deoxidation prepares high-purity hafnium - Google Patents
A kind of method that calcium original position distillation-deoxidation prepares high-purity hafnium Download PDFInfo
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- CN109628764A CN109628764A CN201811569165.5A CN201811569165A CN109628764A CN 109628764 A CN109628764 A CN 109628764A CN 201811569165 A CN201811569165 A CN 201811569165A CN 109628764 A CN109628764 A CN 109628764A
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- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
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Abstract
The invention discloses the methods that a kind of calcium original position distillation-deoxidation for belonging to metal smelt technical field prepares high-purity hafnium.This method is that material system A, calcium reduction agent separation are placed in closed reaction vessel, it heats in an inert atmosphere, calcium is entered in material system A in fused salt in calcium reduction agent with the dissolution of high-purity calcium gas form, realizes to hafnium raw material deoxidation, high-purity hafnium of oxygen content≤0.10wt% is made；The material system A is the mixture of hafnium raw material and anhydrous calcium chloride, and one or both of alkali halide, alkaline-earth halide are contained or not contain in material system A, and the hafnium raw material is metal hafnium, hafnium alloy or hafnium oxide；The calcium reduction agent is calcium metal or calcium alloy；The separated region placed that separates is mutually isolated simultaneously gas phase connection.The method of the present invention is simple and easy, good to the removal effect of oxygen, can satisfy the requirement in the fields such as high pure metal hafnium Coating Materials, dielectric material, high temperature alloy, atomic energy industry.
Description
Technical field
The invention belongs to metal smelt technical field, in particular to a kind of calcium original position distillation-deoxidation prepares the side of high-purity hafnium
Method.
Background technique
Metal hafnium is a kind of silvery white non-ferrous metal, it has the excellent properties such as high temperature resistant, anticorrosive, easy processing, is atomic energy
The important materials in the fields such as industry, aerospace, military science, biological medicine, petrochemical industry.Hafnium thermal neutron capture area compared with
(115b) greatly is easy to capture nuclear reactor neutron and controls reaction speed, can be used for control rod and the protection of atomic pile
Device；Hafnium can manufacture the cathode of X-ray tube in electrical equipment industry, can be used as the getter in electric lamp filament and electron tube；The conjunction of hafnium
Gold can be used as the protective layer that rocket nozzle material and gliding type aircraft are reentried；Further, since hafnium has good lead
Hot, electric conductivity and lower electron work functon, it can also be used to the plasma emitter of plasma cutting electrode.
But the physical and chemical performance of metal hafnium is very sensitive to the interstitial atom in metal such as oxygen, carbon, nitrogen etc..Due to hafnium
The property of itself has very strong affinity to these gaseous impurities especially oxygen, therefore, is especially in smelting, the processing of hafnium
In the hot and cold processing of hafnium and welding process, oxygen is very easy to enter in hafnium to significantly reduce its physical and chemical performance.Although iodine
The oxygen in hafnium can be effectively removed by changing purifying technique, but that there are metal recovery rates is low, processing capacity is small, energy consumption is high, Wu Faying
The problems such as molded material.In addition, the pollution of other impurities such as carbon, nitrogen how is avoided while metal hafnium deoxidation,
And hafnium deoxidation process has to the problem of considering.And oxygen in hafnium can be removed by being rarely reported in existing patent and document
Simple and easy method.Therefore, find a kind of simple, the economic method that can effectively remove oxygen in metal hafnium to hafnium and its
The production and application of alloy are of great significance.In recent years, had metallurgy, material worker carried out positive spy in this respect
Rope and trial, and have made some progress:
Chinese patent 201010590603.3 discloses a kind of preparation method and application of superfine high-purity hafnium powder, and this method will
Oxidation hafnium powder and the mixing of reducing agent powder are put into crucible, issue raw reduction reaction in the protection of argon gas, reduzate passes through
Pickling, washing, drying, screening obtain oxygen content less than 0.2wt%, and metal impurities total content is less than 100ppm, and granularity is less than 1 μm
Ultra-fine hafnium powder.This method is mainly characterized by reduzate through overpickling, and obtained hafnium powder metals content impurity is few, although instead
The oxide for answering process to generate can protect hafnium powder to prevent hafnium powder from exploding, but calcium oxide is in the reaction system with the shape of pure solid
Formula exists, thermodynamic activity 1, therefore is unfavorable for the oxygen being removed in depth in hafnium, is not suitable for the hafnium plate after processing is become a useful person, hafnium
The deoxidation of line and other abnormity components, application range are narrow；In addition, the hafnium powder of surface attachment calcium oxide can occur at the reaction temperatures
Sintering, is mixed in the slight gap position in hafnium powder, only is difficult to completely remove with pickling, therefore its oxygen content is only lowered to
0.2%, it is unsatisfactory for the standard requirements (YS/T399-2013) that oxygen content in hafnium is lower than 0.12wt%.Less it is able to satisfy high-purity hafnium matter
Amount requires (O≤100ppm).Therefore the patent difficulty has practical application value.
To avoid the impurity in calcium from polluting in metal hafnium deoxidation process to metal hafnium bring impurity, conventional method is first
Calcium metal is distilled, obtain silicon, oxygen, nitrogen content qualification high-purity calcium, then with high-purity calcium to metal hafnium deoxidation.The of this technique
One problem is to be distilled high-purity calcium of acquisition in packaging, storage, transport, high-purity calcium can because absorb the oxygen in environment, nitrogen,
Water and introduce nitrogen, oxygen impurities, nitrogen, oxygen impurities can pollute hafnium product；Second Problem is the distillation and deoxidation difference of traditional handicraft
It is completed in two equipment, energy consumption is high.
Summary of the invention
The purpose of the present invention is to provide a kind of method that calcium original position distillation-deoxidation prepares high-purity hafnium, specific technical solutions
It is as follows:
A kind of method that calcium original position distillation-deoxidation prepares high-purity hafnium is to be placed in material system A, calcium reduction agent separation
It in closed reaction vessel, heats in an inert atmosphere, calcium enters material system A with the dissolution of high-purity calcium gas form in calcium reduction agent
In middle fused salt, the deoxidation to hafnium raw material is realized, high-purity hafnium of oxygen content≤0.10wt% is made；
The material system A is the mixture of hafnium raw material and anhydrous calcium chloride, and alkali gold is contained or not contain in material system A
Belong to one or both of halide, alkaline-earth halide, the hafnium raw material is metal hafnium, hafnium alloy or hafnium oxide；It is described
Calcium reduction agent is calcium metal or calcium alloy；
The separated region placed that separates is mutually isolated simultaneously gas phase connection.
Further, the hafnium raw material is metal hafnium, hafnium alloy, and the oxygen content < 100ppm of high-purity hafnium is made.
Preferably, the closed reaction vessel includes metal hafnium crucible, stainless steel crucible, and the metal hafnium crucible is located at not
It becomes rusty in steel crucible, by the way that material system A to be placed in metal hafnium crucible, calcium reduction agent is placed in metal hafnium crucible and stainless steel crucible
Between gap in realize separate place.
The alkali halide, alkaline-earth halide are the salt that eutectic melt can be generated with calcium chloride；Preferably,
The alkali halide is potassium chloride.
The anhydrous calcium chloride is obtained by the way that calcium chloride to be dehydrated to 12~36h at 300~600 DEG C.
The hafnium raw material is other special-shaped components or the powder such as bulk, plate, silk material, tubing, bar, band；The gold
Category calcium is high-purity calcium, distillation calcium, industrial calcium, and the calcium alloy is calcium silicon, calloy.
The calcium metal or calcium alloy are preferably clast, powder.
The mass ratio of hafnium raw material and anhydrous calcium chloride is 1:5~1:40 in the material system A, it is to be understood that this
Hafnium raw material should be able to be completely covered after anhydrous calcium chloride fusing in invention material system A.
The calcium reduction agent additional amount be using the quality of calcium in calcium reduction agent as reaction temperature under in anhydrous calcium chloride fused salt
Subject to 0.5~5 times of calcium saturation solubility.
The additional amount of the alkali halide or alkaline-earth halide is the 50%~90% of anhydrous calcium chloride quality.
The reaction temperature is 700~1300 DEG C, and the reaction time is 12~240h；It is understood that in the present invention
Reaction temperature should be higher than that salt fusing point in reaction system, melt salt, and calcium in calcium reduction agent can be made to distil to form high-purity calcium gas.
After the completion of the deoxidation, raw material hafnium is cleaned: first washing removal kish calcium, the salt (chlorination being added in raw material
Calcium, alkali halide or alkaline-earth halide), mixed acid surface clean 1~15 time of 0.5~10M is reused, then distinguish
With deionized water, ethyl alcohol and acetone surface clean 1~15 time；Wherein mixed acid is by two or more in hydrofluoric acid, nitric acid, hydrochloric acid
The mixed acid of composition.
The calcium original position distillation-deoxidation prepare the method for high-purity hafnium specifically includes the following steps:
(1) material filling: material system A, calcium reduction agent separation are placed in reaction vessel, sealed reaction vessel；
(2) it distills deoxidation: sealing reactor is packed into stainless-steel vacuum tank, vacuumize, logical inert gas, heating reaction
Container enters calcium in calcium reduction agent in material system A in fused salt with the dissolution of high-purity calcium gas form, realizes to hafnium raw material deoxidation；
After reaction, cooled to room temperature；
(3) disassembly, cleaning: take out deoxidation after hafnium raw material, washing removal kish calcium, salt, and carry out surface clean,
High-purity hafnium of oxygen content≤0.10wt% is made in drying.
In the method for the present invention, calcium reduction agent calcium is by distillation, and dissolution enters anhydrous calcium chloride in the form of the high-purity calcium of gaseous state
In fused salt, to realize the deoxidation to hafnium raw material.
The invention has the benefit that
(1) compared with traditional calcium distillation-high-purity calcium method of deoxidation, the present invention is by the distilation of calcium and hafnium raw material
Calcium deoxidation merges in the same reaction vessel, effectively prevents high-purity calcium packaging, transport, packaging dismounting, dress in conventional method
To the pollution of high-purity calcium in furnace deoxidation process, while reducing the costs such as energy consumption；The present invention is by calcium reduction agent and is deoxidized hafnium
Raw material is kept apart, and it is reducing agent that cheap industrial calcium, which can be used directly, and calcium melts and generate steam, steam at the reaction temperatures
Pressure can reach 102~1790Pa, and then high-purity calcium steam dissolution enters calcium chloride fused salt and reaches saturation, in the process,
The impurity such as silicon, oxygen, nitrogen in calcium reduction agent are not distilled and are stayed in calcium reduction agent, will not be polluted to hafnium raw band；Calcium saturation
Fused salt the deoxygenation of hafnium occurs again at the reaction temperatures, due to calcium be it is excessive, calcium vapour pressure maintains always instead
Equilibrium vapor pressure at a temperature of answering, the activity of calcium can achieve maximum value in fused salt, be conducive to the removing of oxygen in raw material hafnium；
(2) medium invention introduces anhydrous calcium chloride fused salt as calcium dissolution and deoxidation, firstly, fused calcium chloride pair
Reacting reducing agent calcium has preferable solubility, guarantees that there are activity adequately and uniformly metal calcium reductions on the surface of hafnium raw material
Agent, while fused calcium chloride can reduce calcium oxide activity to reaction product calcium oxide solubility with higher, be conducive to depth
Remove the oxygen in hafnium raw material；Secondly, hafnium raw material is totally submerged by fused salt, one layer of buffer area itself can be used as, isolation is external
Pollution of the residual impurity to hafnium raw material；Third, the reaction of fused salt and hafnium raw material belong to liquid-solid reaction, and the uniformity of reaction is preferable,
Suitable for the deoxidation of other special-shaped components such as all kinds of hafnium plate materials, wire rod, bulk, the direct-reduction deoxidation of hafnium oxide is applied also for,
And the smelting and processing technology of existing hafnium raw material (metal hafnium, hafnium alloy or hafnium oxide) can be connected, had a wide range of application；
(3) although the method for the present invention uses technical grade calcium metal or calcium alloy, but actually occurs deoxidation
It is high-purity calcium by distillation, thus can effectively avoids pollution of the various impurity to hafnium in industrial calcium using the method for the present invention,
Avoiding the calcium oxide on calcium metal surface from entering fused salt causes calcium oxide activity to rise, and reduces while guaranteeing deoxidation effect de-
The cost of oxygen；
(4) the method for the present invention is simple and easy, good to the removal effect of oxygen, nitrogen, and at low cost, a step can prepare high-purity hafnium,
It is long, at high cost to solve the problems, such as that existing deoxy technology oxygen content is difficult to reach hafnium sponge standard, process flow；It is prepared by the present invention
Oxygen content≤0.10wt% in high-purity hafnium, wherein being reached using metal hafnium, hafnium alloy as the equal < 100ppm of oxygen content in the product of raw material
The level purified to iodide process, can satisfy high pure metal hafnium Coating Materials, dielectric material, high temperature alloy, atomic energy industry etc.
The requirement in field.
Detailed description of the invention
Attached drawing 1 is the reaction vessel schematic diagram that calcium original position distillation-deoxidation prepares high-purity hafnium in the specific embodiment of the invention；
Label declaration: 1- anhydrous calcium chloride；2- hafnium raw material；3- calcium reduction agent；4- metal hafnium crucible；5- stainless steel crucible；
6- elevated-temperature seal washer.
Specific embodiment
The present invention provides a kind of methods that calcium original position distillation-deoxidation prepares high-purity hafnium, below with reference to embodiment and attached drawing
The present invention is described further.
Embodiment 1
1 piece, quality 20g, oxygen content 850ppm of metal hafnium block is taken, (CaCl is pressed2): m (Hf)=5:1 weighs anhydrous calcium chloride
100g (is dehydrated for 24 hours at 300 DEG C) using preceding, and weighing high-purity calcium bits 4g, (at 900 DEG C, calcium saturation is molten in anhydrous calcium chloride fused salt
0.5 times of Xie Du), metal hafnium and anhydrous calcium chloride are filled in hafnium crucible, high-purity calcium bits are filled in hafnium crucible and stainless steel
The gap location of crucible, it is then that stainless steel crucible is intact using elevated-temperature seal washer sealing, it is specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.5Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 900 DEG C, and keeps the temperature 40h at 900 DEG C, after heat preservation, is furnace-cooled to
Room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium is washed with clear water and calcium chloride takes out metal hafnium.It uses on metal hafnium surface
Mixing acid elution 15 times of the hydrofluoric acid of 0.5M, nitric acid, then respectively with deionized water, ethyl alcohol, acetone rinsing surface 10 times, then
Drying.Oxygen content is 96ppm in obtained metal hafnium.
Embodiment 2
1 piece, quality 20g, oxygen content 760ppm of metal hafnium block is taken, (CaCl is pressed2): m (Hf)=20:1 weighs anhydrous chlorination
Calcium 400g (is dehydrated 36h at 300 DEG C using preceding), and weighing industrial calcium bits 57g, (at 1050 DEG C, calcium is full in anhydrous calcium chloride fused salt
With 2 times of solubility), metal hafnium and anhydrous calcium chloride are filled in hafnium crucible, industrial calcium bits are filled in hafnium crucible and stainless
The gap location of steel crucible, it is then that stainless steel crucible is intact using elevated-temperature seal washer sealing, it is specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.1Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 1050 DEG C, and keeps the temperature 20h at 1050 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium is washed with clear water and calcium chloride takes out metal hafnium.Metal hafnium surface
With the hydrofluoric acid of 8M, mixing acid elution 2 times of nitric acid, deionized water, ethyl alcohol, acetone rinsing surface 5 times are being used respectively, is then being dried
It is dry.Oxygen content is 86ppm, nitrogen content 24ppm, silicone content 10ppm in obtained metal hafnium.
Embodiment 3
Metal hafnium filament 1, quality 15g, oxygen content 910ppm is taken, (CaCl is pressed2): m (Hf)=40:1 weighs anhydrous chlorination
Calcium 600g (is dehydrated 19h at 400 DEG C using preceding), and weighing industrial calcium bits 213g, (at 1100 DEG C, calcium is full in anhydrous calcium chloride fused salt
With 4 times of solubility), metal hafnium and anhydrous calcium chloride are filled in hafnium crucible, industrial calcium bits are filled in hafnium crucible and stainless
The gap location of steel crucible, it is then that stainless steel crucible is intact using elevated-temperature seal washer sealing, it is specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.2Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 1100 DEG C, and keeps the temperature 14h at 1100 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium is washed with clear water and calcium chloride takes out metal hafnium.Metal hafnium surface
With the hydrofluoric acid of 10M, mixing acid elution 1 time of nitric acid, then respectively with deionized water, ethyl alcohol, acetone rinsing surface 9 times, then
Drying.Oxygen content 90ppm in obtained metal hafnium.
Embodiment 4
Metal hafnium filament 1, quality 20g, oxygen content 880ppm is taken, (CaCl is pressed2): m (Hf)=15:1 weighs anhydrous chlorination
Calcium 300g (is dehydrated 12h at 600 DEG C using preceding), and weighing distillation calcium bits 180g, (at 1300 DEG C, calcium is full in anhydrous calcium chloride fused salt
With 3 times of solubility), metal hafnium and anhydrous calcium chloride are filled in hafnium crucible, distillation calcium bits are filled in hafnium crucible and high temperature
The gap location of alloy crucible, it is then that high temperature alloy crucible is intact using elevated-temperature seal washer sealing, it is specific as shown in Fig. 1.
The crucible being sealed is put into the high-temperature alloy vacuum tank of resistance stove heating, is evacuated to after covering bell
0.6Pa is then washed with argon gas.Under protection of argon gas, 5 DEG C/min is heated to 1300 DEG C, and keeps the temperature 12h at 1300 DEG C, protects
After temperature, it is furnace-cooled to room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium is washed with clear water and calcium chloride takes out metal
Hafnium.Mixing acid elution 4 times of the hydrofluoric acid of metal hafnium surface 7M, hydrochloric acid, then deionized water, ethyl alcohol, acetone rinsing are used respectively
Surface 10 times is then dried.Oxygen content 90ppm in obtained metal hafnium.
Embodiment 5
1 piece of metal hafnium plate, quality 30g, oxygen content 740ppm is taken, (CaCl is pressed2): m (Hf)=12:1 weighs anhydrous chlorination
Calcium 360g (is dehydrated 18h at 500 DEG C using preceding), weigh calcium-silicon (calcium content 42wt%) 157g (at 1000 DEG C, anhydrous chlorine
3 times for changing calcium saturation solubility in calcium fused salt), metal hafnium and anhydrous calcium chloride are filled in hafnium crucible, calcium-silicon loads
It is then that stainless steel crucible is intact using elevated-temperature seal washer sealing in the gap location of hafnium crucible and stainless steel crucible, specifically such as
Shown in attached drawing 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.08Pa after covering bell, then
It is washed with argon gas.Under protection of argon gas, 5 DEG C/min is heated to 1000 DEG C, and keeps the temperature 28h at 1000 DEG C, after heat preservation, furnace
It is cooled to room temperature.Crucible is opened after coming out of the stove, the remaining calcium-silicon of removal is washed with clear water and calcium chloride takes out metal hafnium.Metal hafnium
Mixing acid elution 7 times of the hydrofluoric acid of surface 2M, hydrochloric acid, then respectively with deionized water, ethyl alcohol, acetone rinsing surface 10 times,
Then dry.Oxygen content 84ppm in obtained metal hafnium.
Embodiment 6
1 piece of metal hafnium plate, quality 25g, oxygen content 830ppm is taken, (CaCl is pressed2): m (Hf)=8:1 weighs anhydrous calcium chloride
200g (is dehydrated 15h at 450 DEG C using preceding), weigh calcium-silicon (calcium content 42wt%) 131g (at 880 DEG C, anhydrous chlorination
4 times of calcium saturation solubility in calcium fused salt), metal hafnium and anhydrous calcium chloride are filled in hafnium crucible, calcium-silicon is filled in
The gap location of hafnium crucible and stainless steel crucible, it is then that stainless steel crucible is intact using elevated-temperature seal washer sealing, it is specific as attached
Shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.4Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 880 DEG C, and keeps the temperature 84h at 880 DEG C, after heat preservation, is furnace-cooled to
Room temperature.Crucible is opened after coming out of the stove, the remaining calcium-silicon of removal is washed with clear water and calcium chloride takes out metal hafnium.Metal hafnium surface
It is then dried with the hydrofluoric acid of 5M, mixing acid elution 3 times of nitric acid, then respectively with deionized water, ethyl alcohol, acetone rinsing surface 9 times
It is dry.Oxygen content 73ppm, nitrogen content 18ppm, silicone content 11ppm in obtained metal hafnium.
Embodiment 7
1 piece, quality 30g, oxygen content 920ppm of metal hafnium block is taken, (CaCl is pressed2): m (Hf)=26:1 weighs anhydrous chlorination
Calcium 780g (is dehydrated 31h at 400 DEG C using preceding), weigh kalzium metal (calcium content 75wt%) 137g (at 950 DEG C, anhydrous chlorine
2 times for changing calcium saturation solubility in calcium fused salt), metal hafnium and anhydrous calcium chloride are filled in hafnium crucible, kalzium metal loads
It is then that stainless steel crucible is intact using elevated-temperature seal washer sealing in the gap location of hafnium crucible and stainless steel crucible, specifically such as
Shown in attached drawing 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.1Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 950 DEG C, and keeps the temperature 102h at 950 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, the remaining kalzium metal of removal is washed with clear water and calcium chloride takes out metal hafnium.Metal hafnium table
Mixing acid elution 7 times of the hydrofluoric acid of face 4M, hydrochloric acid, then respectively with deionized water, ethyl alcohol, acetone rinsing surface 8 times, then
Drying.Oxygen content 75ppm in obtained metal hafnium.
Embodiment 8
Metal hafnium filament 1, quality 20g, oxygen content 950ppm is taken, (CaCl is pressed2): m (Hf)=30:1 weighs anhydrous chlorination
Calcium 600g (is dehydrated 37h at 500 DEG C using preceding), and is incorporated the potassium chloride of 50% anhydrous calcium chloride quality, weighs kalzium metal
(calcium content 75wt%) 67g (at 800 DEG C, 2 times of calcium saturation solubility in anhydrous calcium chloride fused salt), by metal hafnium, anhydrous chlorine
Change calcium and potassium chloride is filled in hafnium crucible, kalzium metal is filled in the gap location of hafnium crucible and stainless steel crucible, then will not
The steel crucible that becomes rusty is intact using elevated-temperature seal washer sealing, specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.6Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 800 DEG C, and keeps the temperature 200h at 800 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, the remaining kalzium metal of removal, potassium chloride and calcium chloride is washed with clear water and takes out metal hafnium.
Deionized water, ethyl alcohol, acetone rinsing table are being used in mixing acid elution 13 times of the hydrofluoric acid of metal hafnium surface 1M, nitric acid respectively
Face 10 times is then dried.Oxygen content 89ppm in obtained metal hafnium.
Embodiment 9
Metal hafnium filament 1, quality 32g, oxygen content 1020ppm is taken, (CaCl is pressed2): m (Hf)=40:1 weighs anhydrous chlorination
Calcium 1280g (is dehydrated 30h at 600 DEG C using preceding), and is incorporated the potassium chloride of 60% anhydrous calcium chloride quality, weighs industrial calcium bits
416g (at 1000 DEG C, 5 times of calcium saturation solubility in anhydrous calcium chloride fused salt), by metal hafnium, anhydrous calcium chloride and potassium chloride
It is filled in hafnium crucible, industrial calcium bits are filled in the gap location of hafnium crucible and stainless steel crucible, then utilize stainless steel crucible
Elevated-temperature seal washer sealing is intact, specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.5Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 1000 DEG C, and keeps the temperature 40h at 1000 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium, potassium chloride and calcium chloride is washed with clear water and takes out metal hafnium.Gold
Belong to the hydrofluoric acid of hafnium surface 4M, mixing acid elution 10 times of nitric acid, then uses deionized water, ethyl alcohol, acetone rinsing surface 5 respectively
Time, then dry.Oxygen content 75ppm, nitrogen content 20ppm, silicone content 10ppm in obtained metal hafnium.
Embodiment 10
1 piece, quality 35g, oxygen content 780ppm of metal Nb10Hf alloy is taken, (CaCl is pressed2): m (Nb10Hf)=25:1 claims
It takes anhydrous calcium chloride 875g (being dehydrated 36h at 300 DEG C using preceding), and is incorporated the potassium chloride of 90% anhydrous calcium chloride quality, claim
Industrial calcium bits 70g (at 700 DEG C, 5 times of calcium saturation solubility in anhydrous calcium chloride fused salt) are taken, by Nb10Hf alloy, anhydrous chlorine
Change calcium and potassium chloride is filled in hafnium crucible, industrial calcium bits are filled in the gap location of hafnium crucible and stainless steel crucible, then will not
The steel crucible that becomes rusty is intact using elevated-temperature seal washer sealing, specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.4Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 700 DEG C, and keeps the temperature 240h at 700 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium, calcium chloride, potassium chloride is washed with clear water and takes out Nb10Hf alloy.
Deionized water, ethyl alcohol, acetone rinsing surface 6 are being used in mixing acid elution 2 times of the hydrofluoric acid of alloy surface 7M, hydrochloric acid respectively
Time, then dry.Oxygen content 82ppm in obtained metal hafnium.
Embodiment 11
Oxidation hafnium powder 20g is weighed, (CaCl is pressed2): m (Hf)=30:1 weighs anhydrous calcium chloride 600g (using preceding 600
16h is dehydrated at DEG C), and be incorporated the potassium chloride of 50% anhydrous calcium chloride quality, weigh industrial calcium bits 76g (at 1000 DEG C, anhydrous chlorine
2 times for changing calcium saturation solubility in calcium fused salt), hafnium oxide, anhydrous calcium chloride and potassium chloride are filled in hafnium crucible, industrial calcium
Bits are filled in the gap location of hafnium crucible and stainless steel crucible, then that stainless steel crucible is intact using elevated-temperature seal washer sealing,
It is specific as shown in Fig. 1.
The crucible being sealed is put into the vacuum tank of resistance stove heating, is evacuated to 0.6Pa after covering bell, then uses
Argon gas washing.Under protection of argon gas, 5 DEG C/min is heated to 1000 DEG C, and keeps the temperature 40h at 1000 DEG C, and after heat preservation, furnace is cold
To room temperature.Crucible is opened after coming out of the stove, removal residual metal calcium, calcium chloride, potassium chloride is washed with clear water and obtains hafnium metal powder.Gold
Belong to the hydrofluoric acid of hafnium powder 1M, mixing acid elution 2 times of hydrochloric acid, use deionized water, ethyl alcohol, acetone rinsing surface 3 times respectively,
Then dry.Obtained hafnium metal powder oxygen content 0.10wt%.
Claims (10)
1. a kind of method that calcium original position distillation-deoxidation prepares high-purity hafnium, which is characterized in that by material system
A, calcium reduction agent separation is placed in closed reaction vessel, is heated in an inert atmosphere, calcium is in calcium reduction agent with high-purity calcium
Gas form dissolution enters in material system A in fused salt, realizes to hafnium raw material deoxidation, the high-purity of oxygen content≤0.10wt% is made
Hafnium；
The material system A is the mixture of hafnium raw material and anhydrous calcium chloride, contains or not contain alkali metal halogen in material system A
One or both of compound, alkaline-earth halide, the hafnium raw material are metal hafnium, hafnium alloy or hafnium oxide；The calcium is also
Former agent is calcium metal or calcium alloy；
The separated region placed that separates is mutually isolated simultaneously gas phase connection.
2. high-purity hafnium is made the method according to claim 1, wherein the hafnium raw material is metal hafnium, hafnium alloy
Oxygen content < 100ppm.
3. the method according to claim 1, wherein the closed reaction vessel include metal hafnium crucible, it is stainless
Steel crucible, the metal hafnium crucible are located in stainless steel crucible, by the way that material system A is placed in metal hafnium crucible, calcium reduction
Agent, which is placed in the gap between metal hafnium crucible and stainless steel crucible, realizes that separation is placed.
4. the method according to claim 1, wherein the alkali halide is potassium chloride.
5. the method according to claim 1, wherein the hafnium raw material is bulk, plate, silk material, tubing, stick
Material, band or powder；The calcium metal is high-purity calcium, distillation calcium, industrial calcium, and the calcium alloy is calcium silicon, calloy.
6. the method according to claim 1, wherein hafnium raw material and anhydrous calcium chloride in the material system A
Mass ratio be 1:5~1:40, the calcium reduction agent additional amount using the quality of calcium in calcium reduction agent as reaction temperature under anhydrous chlorination
In calcium fused salt subject to 0.5~5 times of calcium saturation solubility.
7. the method according to claim 1, wherein the alkali halide or alkaline-earth halide plus
Enter 50%~90% that amount is anhydrous calcium chloride quality.
8. the reaction time is the method according to claim 1, wherein the reaction temperature is 700~1300 DEG C
12~240h.
9. the method according to claim 1, wherein cleaning after the completion of the deoxidation to raw material hafnium: first washing is gone
Except kish calcium, salt, reuse mixed acid surface clean 1~15 time of 0.5~10M, then respectively with deionized water, ethyl alcohol and
Acetone surface clean 1~15 time；Wherein mixed acid is by the mixed acid formed two or more in hydrofluoric acid, nitric acid, hydrochloric acid.
10. -9 described in any item methods according to claim 1, which comprises the following steps:
(1) material filling: material system A, calcium reduction agent separation are placed in reaction vessel, sealed reaction vessel；
(2) it distills deoxidation: sealing reactor is packed into stainless-steel vacuum tank, vacuumize, logical inert gas, heat reaction vessel
Enter calcium in calcium reduction agent in material system A in fused salt with the dissolution of high-purity calcium gas form, realizes to hafnium raw material deoxidation；Reaction
After, cooled to room temperature；
(3) disassembly, cleaning: the hafnium raw material after taking out deoxidation, washing removal kish calcium, salt, and surface clean, drying are carried out,
High-purity hafnium of oxygen content≤0.10wt% is made.
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| CN110129588A (en) * | 2019-06-03 | 2019-08-16 | 南通晶朋新材料科技有限公司 | A kind of preparation method of high purity metal hafnium |
| CN112095022A (en) * | 2020-01-21 | 2020-12-18 | 有研资源环境技术研究院(北京)有限公司 | Method for deeply removing oxygen in metal hafnium by using super-oxophilic metal-calcium synergistic method |
| CN114769608A (en) * | 2022-04-29 | 2022-07-22 | 中国科学院近代物理研究所 | Preparation method of metal thorium |
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