CN109321870A - A kind of compound molybdenum crucible and its preparation method and application - Google Patents
A kind of compound molybdenum crucible and its preparation method and application Download PDFInfo
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- CN109321870A CN109321870A CN201811525976.5A CN201811525976A CN109321870A CN 109321870 A CN109321870 A CN 109321870A CN 201811525976 A CN201811525976 A CN 201811525976A CN 109321870 A CN109321870 A CN 109321870A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
- C23C8/64—Carburising
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/04—Crucibles
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/80—After-treatment
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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
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
Abstract
The invention discloses a kind of compound molybdenum crucibles and its preparation method and application, belong to refractory metal article manufacturing field, the compound molybdenum crucible, by matrix molybdenum crucible, and its carbonization molybdenum layer composition on surface, the outer surface of compound molybdenum crucible and/or inner surface are carbonization molybdenum layer.There is the fine and close carbonization molybdenum layer that reaction in-situ generates on the compound molybdenum crucible surface of the present invention, and compound molybdenum crucible had both remained the unsuitable broken feature of high intensity of molybdenum under high temperature, and stablized but also with the high temeperature chemistry property of molybdenum carbide, the strong feature of high-temperature corrosion-resistance sexuality.Suitable for molten-salt electrolysis the preparation method rare earth metal or rare earth alloy, pot life can be greatly improved, saves and protects expensive molybdenum resource, the product quality of rare earth metal or rare earth alloy is improved, can also reduce production cost.Preparation process of the present invention is simple, and molybdenum carbide thickness degree is easy to control, and be carbonized molybdenum layer good compactness, and with substrate combinating strength height, heat resistanceheat resistant vibration performance is strong, stable structure, and preparation cost is low.
Description
Technical field
The invention belongs to refractory metal article manufacturing fields, and in particular to a kind of compound molybdenum crucible and preparation method thereof and
Using.
Background technique
Molybdenum is a kind of refractory metal, and fusing point is up to 2620 DEG C, and there are extremely strong Binding Forces Between Atoms to make it in room temperature
It is all very high with high temperature strength；Molybdenum has the coefficient of expansion small, and conductivity is big, the excellent physical property such as good heat conductivity, simultaneously
At normal temperature, molybdenum chemical stability is high, does not react with hydrochloric acid, hydrofluoric acid and aqueous slkali, be only soluble in nitric acid, chloroazotic acid or the concentrated sulfuric acid it
In, it is also quite stable to most of liquid metals, nonmetallic slag and melten glass.These excellent physical and chemical performances make molybdenum and
Its alloy is widely used in fields such as metallurgy, glass, ceramics, war industry equipment, high-temperature machineries.Molybdenum crucible generally includes pure molybdenum
Crucible and molybdenum alloy crucible.Pure molybdenum crucible (molybdenum content is greater than 99.5%) or molybdenum alloy crucible (be routinely incorporated into a small amount of cerium oxide,
At least one kind of in lanthana, yttrium oxide, incorporation substance gross mass percentage composition is not more than 3%) as one kind of molybdenum materials, wide
It is general to be applied to the processes such as rare earth metal or rare earth alloy melting, glass melting, since rare earth metal or rare earth alloy are very active,
It can almost react at high temperature with all metals, therefore molybdenum crucible is during preparing rare earth metal or rare earth alloy that there are one
The corrosion for determining degree is not grown the rare earth oxide for mixing certain quality is prepared into its service life of molybdenum alloy crucible,
Cause molybdenum crucible consumption big, molybdenum content is exceeded in rare-earth products, and rare earth preparation cost is high.
Molybdenum carbide (Mo2C) crystallization is close-packed hexagonal lattice, and fusing point is 2690 DEG C, be it is a kind of have very high-melting-point and hardness,
The functional material of good thermal stability and mechanical stability, fine anticorrosion properties is widely used in various high temperature resistants, abrasion-resistant
With equal fields resistant to chemical etching；Mo2C has the electronic structure and catalysis characteristics of similar noble metal, can be widely used for hydrogen participation
Reaction such as alkane isomerization, hydrogenation of unsaturated hydrocarbons, hydrodesulfurization and denitrogenation reaction catalyst, hardness height, it is wear-resistant,
Anti scuffing；But Mo2C is a kind of interstitial solid solution, and matter is hard and crisp, it is difficult to independent to use as product.
In consideration of it, improving molybdenum crucible service life it is necessary to be improved to molybdenum crucible, can not only reducing rare earth metal
Or production cost when rare earth alloy preparation, rare-earth products quality is improved, the Mo resource of preciousness can be also saved for country, there is weight
Big meaning.
Summary of the invention
In view of the deficiencies of the prior art, the first purpose of this invention is to provide a kind of compound molybdenum crucible, to solve
Molybdenum crucible in the prior art react with liquid rare earth metal or rare earth alloy cause molybdenum crucible leak so that cracking ask
Topic, improves the service life service life of molybdenum crucible.
Second object of the present invention is to provide a kind of preparation method of compound molybdenum crucible, this method simple process,
Molybdenum carbide thickness degree is controllable, and reaction in-situ is used to prepare tissue in molybdenum crucible matrix surface as fine and close carbonization molybdenum layer, matrix
It is tightly combined with surface carbonation molybdenum, thermal shock resistance is good, long service life.
Third object of the present invention is to provide a kind of application of compound molybdenum crucible, which is suitable for
Rare earth metal or rare earth alloy are prepared, fused salt electrolysis process is particularly suitable for and prepares rare earth metal or rare earth alloy, can be improved dilute
Earth metal or rare earth alloy quality reduce production cost.
In order to achieve the above technical purposes, the present invention the following technical schemes are provided:
The present invention provides a kind of compound molybdenum crucible, is made of the carbonization molybdenum layer on matrix molybdenum crucible and its surface, described multiple
The outer surface of mould assembly molybdenum crucible and/or inner surface are carbonization molybdenum layer.
Preferably, it is described carbonization molybdenum layer with a thickness of 20~500um.
Preferably, the vertical section shape of the compound molybdenum crucible is U-shaped.
Preferably, the bottom thickness of the compound molybdenum crucible is not less than wall thickness.
The present invention also provides the preparation methods of the compound molybdenum crucible, comprising the following steps:
(1) preparation of molybdenum crucible；
Wherein, density >=9.2g/cm of molybdenum crucible3；
(2) assembling of matrix molybdenum crucible component: it is uniformly laid with graphite powder in graphite crucible bottom, stone is laid on graphite powder
The bottom surface of matrix molybdenum crucible is placed on graphite plate or graphite felt by black plate or graphite felt, other faces of matrix molybdenum crucible not with
Graphite powder directly contacts, and there are gaps between matrix molybdenum crucible and graphite crucible, then covers graphite cover, the base after being assembled
Body molybdenum crucible component；
(3) high-temperature carburizing is handled: the matrix molybdenum crucible component after assembling obtained by step (2) being moved into high temperature furnace, hydrogen is led to
Furnace air is discharged in gas, and heat temperature raising monitors furnace temperature, controls temperature between 1100~2000 DEG C, and soaking time 0.5~
20h, 0.5~2m of hydrogen flowing quantity3/ h is cooled to in-furnace temperature less than 100 DEG C；
(4) it is cleaned and dried: being passed through nitrogen in furnace, take out molybdenum crucible from furnace after hydrogen is discharged, cleaned simultaneously
Drying obtains the compound molybdenum crucible that carbonization molybdenum layer is contained on surface.
Preferably, in step (2), the guarantor to match with its surface shape, size is installed additional in the inner surface of matrix molybdenum crucible
Molybdenum crucible is protected, prevents the inner surface of matrix molybdenum crucible from generating carbonization molybdenum layer, only outer surface is prepared and contains answering for carbonization molybdenum layer
Mould assembly molybdenum crucible, cross section structure are molybdenum-molybdenum carbide from inside to outside.
Preferably, in step (2), the guarantor to match with its surface shape, size is installed additional in the outer surface of matrix molybdenum crucible
Molybdenum crucible is protected, the outer bottom of molybdenum crucible is protected to contact with graphite plate or graphite felt, prevents the outer surface of matrix molybdenum crucible from generating carbonization
The compound molybdenum crucible that only inner surface contains carbonization molybdenum layer is prepared in molybdenum layer, and cross section structure is molybdenum carbide-molybdenum from inside to outside.
Preferably, in step (2), the purity of the graphite powder is greater than 99.5%, and graphite felt is the hard felt of graphite or graphite
Soft felt.
Preferably, in step (2), when matrix molybdenum crucible component assembles, more than one piece molybdenum crucible can be placed in same high temperature furnace,
It is not contacted between different molybdenum crucibles.
Preferably, in step (3), the rate of the heat temperature raising is 100~220 DEG C/h, the rate of cooling is 150~
240℃/h。
Preferably, in step (3), holding temperature is 1600~1800 DEG C, and soaking time is 2~8h.
The inventive concept total as one, the present invention also provides a kind of applications of compound molybdenum crucible, will be described compound
Molybdenum crucible prepares rare earth metal or rare earth alloy for fused salt electrolysis process as the container for containing metallic solution.
Further, the compound molybdenum crucible prepares rare earth lanthanum, cerium, praseodymium, neodymium, dysprosium suitable for fused salt electrolysis process；?
Suitable for preparing rare earth alloy neodymium iron, dysprosium iron, praseodymium neodymium.
The principle of the present invention: 2690 DEG C of molybdenum carbide fusing point, there is very high chemical stability and liquid rare earth metal or liquid
State rare earth alloy does not generate reaction, but molybdenum carbide material fragility is big, when fused salt electrolysis process prepares rare earth metal or rare earth alloy
It easily cracks under experience heating-cooling high/low temperature circulation impact, pure carbonization molybdenum product is difficult to obtain independent utility.High temperature,
Under hydrogen shield environment, graphite powder and the volatilization of other carbon-based materials in high temperature furnace, carbon and the molybdenum generation chemistry on molybdenum crucible surface are anti-
It answers, in the molybdenum carbide superficial layer of matrix crucible surface in-situ preparation densification, prepares compound molybdenum crucible.The pyroreaction time gets over
Long, temperature is higher, and carbonization molybdenum layer is thicker, and carbonization molybdenum layer microstructure is uniform, and defect is few, is tightly combined with matrix.Due to carbonization
The presence of molybdenum layer reduces the corrosion of molybdenum, and the molybdenum content in rare earth metal or rare earth alloy can be effectively reduced.Be carbonized molybdenum layer
Thickness and high-temperature temperature and soaking time combination not at stringent proportionate relationship.
Compared with prior art, advantageous effects of the invention are as follows:
1, the fine and close carbonization molybdenum layer for thering is reaction in-situ to generate using compound molybdenum crucible surface prepared by the method for the present invention, it is multiple
Mould assembly molybdenum crucible had both remained the unsuitable broken feature of high intensity of molybdenum under high temperature, steady but also with the high temeperature chemistry property of molybdenum carbide
It is fixed, the strong feature of high-temperature corrosion-resistance sexuality.Suitable for molten-salt electrolysis the preparation method rare earth metal or rare earth alloy, can greatly improve
Pot life is saved and protects expensive molybdenum resource, improves the product quality of rare earth metal or rare earth alloy, can also drop rare earth
The molten-salt electrolysis production cost of metal or rare earth alloy.
2, the method for the present invention preparation process is simple, compound molybdenum crucible its surface carbonation produced using the method for the present invention
Molybdenum layer be it is generated in-situ on Mo substrate, molybdenum carbide thickness degree is easy to control, be carbonized molybdenum layer good compactness, with matrix ining conjunction with by force
Degree is high, and heat resistanceheat resistant vibration performance is strong, stable structure, and preparation cost is low.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of compound molybdenum crucible in the embodiment of the present invention 1.
Fig. 2 is the structural schematic diagram of compound molybdenum crucible in the embodiment of the present invention 2.
Fig. 3 is the structural schematic diagram of compound molybdenum crucible in the embodiment of the present invention 3；
Wherein: 1- matrix molybdenum crucible；2- carbonization molybdenum layer.
Fig. 4 is matrix molybdenum crucible component assembling schematic diagram in the embodiment of the present invention 1；
Wherein: 1- matrix molybdenum crucible；3- graphite crucible；4- graphite plate；5- graphite powder.
Fig. 5 is matrix molybdenum crucible component assembling schematic diagram in the embodiment of the present invention 2；
Wherein: 1- matrix molybdenum alloy crucible；3- graphite crucible；The hard felt of 4- graphite；5- graphite powder；Molybdenum alloy earthenware is protected in 6-
Crucible.
Fig. 6 is matrix molybdenum crucible component assembling schematic diagram in the embodiment of the present invention 3；
Wherein: 1- matrix molybdenum alloy crucible；3- graphite crucible；4- graphite soft felt；5- graphite powder；Pure molybdenum earthenware is protected outside 7-
Crucible.
Fig. 7 is the compound molybdenum crucible section low power metallographic structure figure of the present invention；
Wherein: X is molybdenum, and Y is molybdenum carbide.
Fig. 8 is the compound molybdenum crucible section high power metallographic structure figure of the present invention；
Wherein: X is molybdenum, and Y is molybdenum carbide.
Fig. 9 is the XRD spectrum of the compound molybdenum crucible surface carbonation molybdenum layer of the present invention.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, rather than whole embodiments, based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
The spatially relative terms such as "upper", "lower", "left", "right" can be used herein for ease of explanation, be used for
Relationship of the elements or features relative to another elements or features shown in explanatory diagram.It should be understood that in addition to figure
Shown in except orientation, spatial terminology is intended to include the different direction of device in use or operation.For example, if in figure
Device be squeezed, the element for being stated as being located at other elements or feature "lower" will be located into other elements or feature "upper".
Therefore, exemplary term "lower" may include both upper and lower orientation.Device, which can be positioned in other ways, (to be rotated by 90 ° or position
In other orientation), it can be interpreted accordingly used herein of the opposite explanation in space.It should be strongly noted that describing compound molybdenum
On crucible section molybdenum crucible matrix and carbonization molybdenum layer sequence when from inside to outside, refer to from inner surface of crucible to outer surface direction according to
Secondary observation.
The present invention provides a kind of compound molybdenum crucible, and vertical section shape is the U-shaped at hollow belt bottom, compound molybdenum crucible it is interior
Surface and outer surface are carbonization molybdenum layer, and cross section structure is molybdenum carbide-molybdenum-molybdenum carbide, as shown in Figure 1, molybdenum carbide layer is with a thickness of 20
~500um, molybdenum carbide thickness degree required for being designed and realizing according to actual needs.
The size of compound molybdenum crucible can be designed adjusting, compound molybdenum crucible outer diameter 100 according to required capacity
~300mm, 5~20mm of wall thickness, 5~25mm of base thickness, 100~300mm of height, compound molybdenum crucible is as splendid attire metallic solution
Container, since bottom is constantly in molten bath area, temperature is higher, and base thickness size is not less than wall thickness dimension, is conducive to ensure compound
The service life of molybdenum crucible.
The preparation of the compound molybdenum crucible of the present invention is further described with attached drawing combined with specific embodiments below:
Embodiment 1
The present invention provides a kind of preparation method of compound molybdenum crucible, comprising the following steps:
(1) preparation vertical section shape is the pure molybdenum crucible of U-shaped matrix at hollow belt bottom, having a size of outer diameter 300mm, height
300mm, wall thickness 20mm, base thickness 25mm, density 9.5g/cm3；
(2) assembling of matrix molybdenum crucible component: it is uniformly laid with graphite powder in graphite crucible bottom, stone is laid on graphite powder
The bottom surface of matrix molybdenum crucible is placed on graphite plate by black plate, and other faces of matrix molybdenum crucible do not contact directly with graphite powder, base
There are gaps between body molybdenum crucible and graphite crucible, then cover graphite cover, the matrix molybdenum crucible component after being assembled, specifically
As shown in Figure 4；
(3) high-temperature carburizing is handled: the matrix molybdenum crucible component after assembling obtained by step (2) being moved into high temperature furnace, hydrogen is led to
Furnace air is discharged in gas, and heat temperature raising monitors furnace temperature, and holding temperature is 2000 DEG C, soaking time 0.5h, hydrogen flowing quantity 2m3/
H is cooled to in-furnace temperature to 90 DEG C, and control heating rate is 210 DEG C/h, and rate of temperature fall is 180 DEG C/h；
(4) it is cleaned and dried: being passed through nitrogen in furnace, take out molybdenum crucible from furnace after hydrogen is discharged, cleaned simultaneously
Drying obtains the compound molybdenum crucible that carbonization molybdenum layer is contained on surface, and cross section structure is molybdenum carbide-molybdenum-molybdenum carbide, and Fig. 1 ties for it
Structure schematic diagram, molybdenum carbide thickness degree about 300um, carbonization molybdenum layer are tightly combined with molybdenum crucible matrix, the uniform zero defect of microstructure.
Compound molybdenum crucible prepared by embodiment 1 is used for fused salt electrolysis process as container and prepares rare earth lanthanum, commonly
Pure 150 heat of molybdenum crucible service life, this compound 380 heat of molybdenum crucible service life, service life are about original 2.5
Times, molybdenum content is by using the 450ppm of common molybdenum crucible to be reduced to 90ppm in prepared rare earth lanthanum.
Embodiment 2
The present invention provides a kind of preparation method of compound molybdenum crucible, comprising the following steps:
(1) preparation vertical section shape is the U-shaped matrix molybdenum alloy crucible at hollow belt bottom, and the doped chemical of molybdenum alloy crucible is
Additive amount 0.8% (mass percent) cerium oxide, it is close having a size of outer diameter 100mm, height 100mm, wall thickness 5mm, base thickness 5mm
Degree is 9.4g/cm3；
(2) assembling of matrix molybdenum alloy crucible assembly: graphite powder is uniformly layed in graphite crucible bottom, is set on graphite powder
There is the hard felt of graphite, matrix molybdenum alloy crucible is placed on the hard felt of graphite, is loaded onto inside matrix molybdenum alloy crucible and its inner surface shape
The interior protection molybdenum alloy crucible that shape, size match, matrix molybdenum alloy crucible only have outer bottom to contact with the hard felt of graphite, and matrix molybdenum closes
Golden crucible does not contact directly with graphite powder, and there are gaps between matrix molybdenum alloy crucible and graphite crucible, do not contact, and then covers
Graphite cover, the matrix molybdenum alloy crucible assembly after being assembled are specific as shown in Figure 5；
(3) high-temperature carburizing is handled: the matrix molybdenum alloy crucible assembly after assembling obtained by step (2) is moved into high temperature furnace,
Furnace air is discharged in logical hydrogen, and heat temperature raising monitors furnace temperature, and holding temperature is 1100 DEG C, soaking time 20h, hydrogen flowing quantity
0.5m3/ h is cooled to in-furnace temperature to 80 DEG C, and control heating rate is 110 DEG C/h, and rate of temperature fall is 240 DEG C/h；
(4) it is cleaned and dried: being passed through nitrogen in furnace, take out molybdenum alloy crucible from furnace after hydrogen is discharged, take simultaneously
Molybdenum alloy crucible is protected in out, is cleaned and is dried up, and the compound molybdenum alloy crucible that carbonization molybdenum layer is contained in only outer surface is obtained,
Cross section structure is molybdenum-molybdenum carbide from inside to outside, and Fig. 2 is its structural schematic diagram, molybdenum carbide thickness degree about 500um, carbonization molybdenum layer with
Molybdenum alloy crucible base is tightly combined, the uniform zero defect of microstructure, and Fig. 7-Fig. 8 is that compound molybdenum crucible obtained by the present embodiment is cut
The metallographic structure figure in face, as seen from the figure, molybdenum crucible matrix surface have fine and close carbonization molybdenum layer, and be carbonized molybdenum layer good compactness,
With substrate combinating strength height.Fig. 9 is the XRD spectrum of compound molybdenum crucible surface carbonation molybdenum layer obtained by the present embodiment, can be with by figure
Find out, carbonization molybdenum layer has single phase constituent, better crystallinity degree.
Compound molybdenum alloy crucible prepared by embodiment 2 is used for fused salt electrolysis process as container and prepares rare earth metal cerium,
Common 260 heat of molybdenum alloy pot life, this compound 586 heat of molybdenum alloy pot life, service life are about
Originally more than 2 times, molybdenum content about 400ppm in prepared rare earth metal cerium prepares rare earth metal with common molybdenum alloy crucible is used
Molybdenum content 390ppm in cerium is little compared to variation.
Embodiment 3
The present invention provides a kind of preparation method of compound molybdenum crucible, comprising the following steps:
(1) preparation vertical section shape is the U-shaped matrix molybdenum alloy crucible at hollow belt bottom, and the doped chemical of molybdenum alloy crucible is
Additive amount 1.0% (mass percent) lanthana, having a size of outer diameter 170mm, height 110mm, wall thickness 10mm, base thickness 10mm,
Density is 9.6g/cm3；
(2) assembling of matrix molybdenum alloy crucible assembly: graphite powder is uniformly layed in graphite crucible bottom, is set on graphite powder
There is graphite soft felt, matrix molybdenum alloy crucible is placed on graphite soft felt, is loaded onto outside matrix molybdenum alloy crucible and its outer surface shape
The pure molybdenum crucible of outer protection that shape, size match, the only outer pure molybdenum crucible outer bottom of protection are contacted with graphite soft felt, matrix molybdenum alloy
Crucible does not contact directly with graphite powder, and there are gaps between matrix molybdenum alloy crucible and graphite crucible, do not contact, and then covers stone
Inky cap, the matrix molybdenum alloy crucible assembly after being assembled are specific as shown in Figure 6；
(3) high-temperature carburizing is handled: the matrix molybdenum alloy crucible assembly after assembling obtained by step (2) is moved into high temperature furnace,
Furnace air is discharged in logical hydrogen, and heat temperature raising monitors furnace temperature, and holding temperature is 1400 DEG C, soaking time 15h, hydrogen flowing quantity
1m3/ h is cooled to in-furnace temperature to 90 DEG C, and control heating rate is 190 DEG C/h, and rate of temperature fall is 150 DEG C/h；
(4) it is cleaned and dried: being passed through nitrogen in furnace, take out molybdenum alloy crucible from furnace after hydrogen is discharged, take simultaneously
Pure molybdenum crucible is protected out, cleaned and is dried up, the compound molybdenum alloy crucible that only inner surface contains carbonization molybdenum layer is obtained, and is cut
Face structure is molybdenum carbide-molybdenum from inside to outside, and Fig. 3 is its structural schematic diagram, and molybdenum carbide thickness degree about 400um, be carbonized molybdenum layer and molybdenum
Alloy crucible matrix is tightly combined, the uniform zero defect of microstructure.
Compound molybdenum alloy crucible prepared by embodiment 3 is used for fused salt electrolysis process as container and prepares the conjunction of neodymium iron rare earth
Gold, common 190 heat of molybdenum alloy pot life, this compound 390 heat of molybdenum crucible service life, service life are about original
Come more than 2 times, molybdenum content is by using the 600ppm of common molybdenum alloy crucible to be reduced to 100ppm in prepared neodymium iron rare earth alloy.
Embodiment 4
The present invention provides a kind of preparation method of compound molybdenum crucible, comprising the following steps:
(1) preparation vertical section shape is the U-shaped matrix molybdenum alloy crucible at hollow belt bottom, and the doped chemical of molybdenum alloy crucible is
Additive amount 1.2% (mass percent) yttrium oxide, having a size of outer diameter 265mm, height 200mm, wall thickness 12mm, base thickness 15mm,
Density is 9.3g/cm3；
(2) assembling of matrix molybdenum crucible component: it is uniformly laid with graphite powder in graphite crucible bottom, stone is laid on graphite powder
The bottom surface of matrix molybdenum crucible is placed on graphite plate by black plate, and other faces of matrix molybdenum crucible do not contact directly with graphite powder, base
There are gaps between body molybdenum crucible and graphite crucible, then cover graphite cover, the matrix molybdenum alloy crucible assembly after being assembled；
(3) high-temperature carburizing is handled: the matrix molybdenum alloy crucible assembly after assembling obtained by step (2) is moved into high temperature furnace,
Furnace air is discharged in logical hydrogen, and heat temperature raising monitors furnace temperature, and holding temperature is 1900 DEG C, soaking time 1h, hydrogen flowing quantity
1.5m3/ h is cooled to in-furnace temperature to 90 DEG C, and control heating rate is 180 DEG C/h, and rate of temperature fall is 170 DEG C/h；
(4) it is cleaned and dried: being passed through nitrogen in furnace, take out molybdenum crucible from furnace after hydrogen is discharged, cleaned simultaneously
Drying, obtains the compound molybdenum alloy crucible that carbonization molybdenum layer is contained on surface, and cross section structure is molybdenum carbide-molybdenum-molybdenum carbide, carbonization
Molybdenum layer thickness about 200um, carbonization molybdenum layer are tightly combined with molybdenum crucible matrix, the uniform zero defect of microstructure.
Compound molybdenum alloy crucible prepared by embodiment 4 is used for fused salt electrolysis process as container and prepares rare earth metal praseodymium,
Common 260 heat of molybdenum alloy pot life, this compound 530 heat of molybdenum crucible service life, service life are about original
More than 2 times, molybdenum content is by using the 460ppm of common molybdenum alloy crucible to be reduced to 120ppm in prepared rare earth metal praseodymium.
Embodiment 5
The present invention provides a kind of preparation method of compound molybdenum crucible, comprising the following steps:
(1) preparation vertical section shape is the pure molybdenum crucible of U-shaped matrix at hollow belt bottom, having a size of outer diameter 160mm, height
240mm, wall thickness 12mm, base thickness 18mm, density 9.6g/cm3；
(2) assembling of matrix molybdenum crucible component: it is uniformly laid with graphite powder in graphite crucible bottom, stone is laid on graphite powder
The bottom surface of matrix molybdenum crucible is placed on graphite plate by black plate, and other faces of matrix molybdenum crucible do not contact directly with graphite powder, base
There are gaps between body molybdenum crucible and graphite crucible, then cover graphite cover, the matrix molybdenum crucible component after being assembled；
(3) high-temperature carburizing is handled: the matrix molybdenum crucible component after assembling obtained by step (2) being moved into high temperature furnace, hydrogen is led to
Gas is discharged furnace air, heat temperature raising, monitors furnace temperature, and control holding temperature is at 1800 DEG C, soaking time 2h, hydrogen flowing quantity
2m3Then/h is cooled to 90 DEG C of in-furnace temperature, control 185 DEG C/h of heating rate, 190 DEG C/h of cooling rate；
(4) it is cleaned and dried: being passed through nitrogen in furnace, take out molybdenum crucible from furnace after hydrogen is discharged, cleaned simultaneously
Drying obtains the compound molybdenum crucible that carbonization molybdenum layer is contained on surface, and cross section structure is molybdenum carbide-molybdenum-molybdenum carbide, and be carbonized molybdenum layer
Thickness about 300um, carbonization molybdenum layer are tightly combined with molybdenum crucible matrix, the uniform zero defect of microstructure.
Compound molybdenum crucible prepared by embodiment 5 is used for fused salt electrolysis process as container and prepares rare earth metal neodymium, commonly
240 heat of molybdenum alloy pot life, this compound 600 heat of molybdenum crucible service life, service life is about original
2.5, molybdenum content is by using the 390ppm of common molybdenum alloy crucible to be reduced to 100ppm in prepared rare earth metal neodymium.
Embodiment 6
The present invention provides a kind of preparation method of compound molybdenum crucible, comprising the following steps:
(1) preparation vertical section shape is the pure molybdenum crucible of U-shaped matrix at hollow belt bottom, having a size of outer diameter 160mm, height
110mm, wall thickness 10mm, base thickness 10mm, density 9.7g/cm3；
(2) assembling of matrix molybdenum crucible component: it is uniformly laid with graphite powder in graphite crucible bottom, stone is laid on graphite powder
The bottom surface of matrix molybdenum crucible is placed on graphite plate by black plate, and other faces of matrix molybdenum crucible do not contact directly with graphite powder, base
There are gaps between body molybdenum crucible and graphite crucible, then cover graphite cover, the matrix molybdenum crucible component after being assembled；
(3) high-temperature carburizing is handled: the matrix molybdenum crucible component after assembling obtained by step (2) being moved into high temperature furnace, hydrogen is led to
Gas is discharged furnace air, heat temperature raising, monitors furnace temperature, and control holding temperature is at 1100 DEG C, soaking time 8h, hydrogen flowing quantity
1m3Then/h is cooled to 90 DEG C of in-furnace temperature, control 200 DEG C/h of heating rate, 220 DEG C/h of cooling rate；
(4) it is cleaned and dried: being passed through nitrogen in furnace, take out molybdenum crucible from furnace after hydrogen is discharged, cleaned simultaneously
Drying obtains the compound molybdenum crucible that carbonization molybdenum layer is contained on surface, and cross section structure is molybdenum carbide-molybdenum-molybdenum carbide, and be carbonized molybdenum layer
Thickness about 100um, carbonization molybdenum layer are tightly combined with molybdenum crucible matrix, the uniform zero defect of microstructure.
Compound molybdenum crucible prepared by embodiment 6 is used for fused salt electrolysis process as container and prepares rare earth alloy praseodymium neodymium, it is general
Lead to pure 210 heat of molybdenum crucible service life, this compound 320 heat of molybdenum crucible service life, service life is about original 1.5
Times, molybdenum content is by using the 470ppm of common pure molybdenum crucible to be reduced to 70ppm in prepared rare earth alloy praseodymium neodymium.
Embodiment 7
The present invention provides a kind of preparation method of compound molybdenum crucible, comprising the following steps:
(1) preparation vertical section shape is the pure molybdenum crucible of U-shaped matrix at hollow belt bottom, having a size of outer diameter 140mm, height
110mm, wall thickness 10mm, base thickness 10mm, density 9.6g/cm3；
(2) assembling of matrix molybdenum crucible component: it is uniformly laid with graphite powder in graphite crucible bottom, stone is laid on graphite powder
The bottom surface of matrix molybdenum crucible is placed on graphite plate by black plate, and other faces of matrix molybdenum crucible do not contact directly with graphite powder, base
There are gaps between body molybdenum crucible and graphite crucible, then cover graphite cover, the matrix molybdenum crucible component after being assembled；
(3) high-temperature carburizing is handled: the matrix molybdenum crucible component after assembling obtained by step (2) being moved into high temperature furnace, hydrogen is led to
Gas is discharged furnace air, heat temperature raising, monitors furnace temperature, and control holding temperature is at 1300 DEG C, soaking time 2h, hydrogen flowing quantity
1m3Then/h is cooled to 90 DEG C of in-furnace temperature, control 200 DEG C/h of heating rate, 220 DEG C/h of cooling rate；
(4) it is cleaned and dried: being passed through nitrogen in furnace, take out molybdenum crucible from furnace after hydrogen is discharged, cleaned simultaneously
Drying obtains the compound molybdenum crucible that carbonization molybdenum layer is contained on surface, and cross section structure is molybdenum carbide-molybdenum-molybdenum carbide, and be carbonized molybdenum layer
Thickness about 20um, carbonization molybdenum layer are tightly combined with molybdenum crucible matrix, the uniform zero defect of microstructure.
Compound molybdenum crucible prepared by embodiment 7 is used for fused salt electrolysis process as container and prepares rare earth alloy dysprosium iron, it is general
Lead to pure 310 heat of molybdenum crucible service life, this compound 370 heat of molybdenum crucible service life, service life was about improved than originally
60 heats, molybdenum content is by using the 520ppm of common pure molybdenum crucible to be reduced to 180ppm in prepared rare earth alloy dysprosium iron.
Claims (12)
1. a kind of compound molybdenum crucible, which is characterized in that it is made of the carbonization molybdenum layer on matrix molybdenum crucible and its surface, it is described multiple
The outer surface of mould assembly molybdenum crucible and/or inner surface are carbonization molybdenum layer.
2. compound molybdenum crucible according to claim 1, which is characterized in that the carbonization molybdenum layer with a thickness of 20~
500um。
3. compound molybdenum crucible according to claim 1, which is characterized in that the vertical section shape of the compound molybdenum crucible
For U-shaped.
4. compound molybdenum crucible according to claim 1, which is characterized in that the bottom thickness of the compound molybdenum crucible is not
Less than wall thickness.
5. compound molybdenum crucible according to claim 1, which is characterized in that 100~300mm of compound molybdenum crucible outer diameter,
5~20mm of wall thickness, 5~25mm of base thickness, 100~300mm of height.
6. the preparation method of compound molybdenum crucible described according to claim 1~any one of 5, which is characterized in that including following
Step:
(1) preparation of molybdenum crucible；
Wherein, density >=9.2g/cm of molybdenum crucible3；
(2) assembling of matrix molybdenum crucible component: it is uniformly laid with graphite powder in graphite crucible bottom, graphite plate is laid on graphite powder
Or graphite felt, the bottom surface of matrix molybdenum crucible is placed on graphite plate or graphite felt, other faces of matrix molybdenum crucible not with graphite
Powder directly contacts, and there are gaps between matrix molybdenum crucible and graphite crucible, then covers graphite cover, the matrix molybdenum after being assembled
Crucible assembly；
(3) high-temperature carburizing is handled: the matrix molybdenum crucible component after assembling obtained by step (2) being moved into high temperature furnace, hydrogen row is led to
Clean furnace air, heat temperature raising monitor furnace temperature, control temperature between 1100~2000 DEG C, 0.5~20h of soaking time, hydrogen
0.5~2m of throughput3/ h is cooled to in-furnace temperature less than 100 DEG C；
(4) it is cleaned and dried: being passed through nitrogen in furnace, take out molybdenum crucible from furnace after hydrogen is discharged, cleaned and dried up,
Obtain the compound molybdenum crucible that carbonization molybdenum layer is contained on surface.
7. the preparation method of compound molybdenum crucible according to claim 6, which is characterized in that in step (2), in matrix molybdenum earthenware
The inner surface of crucible installs the protection molybdenum crucible to match with its surface shape, size additional, prevents the inner surface of matrix molybdenum crucible from generating
Be carbonized molybdenum layer, the compound molybdenum crucible that carbonization molybdenum layer is contained in only outer surface is prepared, cross section structure is molybdenum-carbonization from inside to outside
Molybdenum.
8. the preparation method of compound molybdenum crucible according to claim 6, which is characterized in that in step (2), in matrix molybdenum earthenware
The outer surface of crucible installs the protection molybdenum crucible to match with its surface shape, size additional, protect molybdenum crucible outer bottom and graphite plate or
Graphite felt contact prevents the outer surface of matrix molybdenum crucible from generating carbonization molybdenum layer, and only inner surface is prepared and contains carbonization molybdenum layer
Compound molybdenum crucible, cross section structure are molybdenum carbide-molybdenum from inside to outside.
9. the preparation method of compound molybdenum crucible according to claim 6, which is characterized in that in step (3), the heating is risen
The rate of temperature is 100~220 DEG C/h, and the rate of cooling is 150~240 DEG C/h.
10. the preparation method of compound molybdenum crucible according to claim 6, which is characterized in that in step (3), holding temperature
It is 1600~1800 DEG C, soaking time is 2~8h.
11. the application of compound molybdenum crucible described according to claim 1~any one of 5, which is characterized in that will be described compound
Molybdenum crucible prepares rare earth metal or rare earth alloy for fused salt electrolysis process as the container for containing metallic solution.
12. the application of compound molybdenum crucible according to claim 11, which is characterized in that the compound molybdenum crucible is suitable for
Fused salt electrolysis process prepares rare earth lanthanum, cerium, praseodymium, neodymium, dysprosium；It is also applied for preparing rare earth alloy neodymium iron, dysprosium iron, praseodymium neodymium.
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| CN110257862A (en) * | 2019-06-26 | 2019-09-20 | 四川江铜稀土有限责任公司 | A kind of damage revamping method of Rare Earth Electrolysis crucible |
| CN110284088A (en) * | 2019-07-05 | 2019-09-27 | 成都东骏激光股份有限公司 | Molybdenum crucible and its preparation process |
| CN114346245A (en) * | 2020-09-27 | 2022-04-15 | 安泰天龙钨钼科技有限公司 | Long-life rare earth molybdenum crucible and preparation method thereof |
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