CN1060683A - Preparation samarium metal reaction vessel and manufacture method thereof - Google Patents
Preparation samarium metal reaction vessel and manufacture method thereof Download PDFInfo
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- CN1060683A CN1060683A CN 91109915 CN91109915A CN1060683A CN 1060683 A CN1060683 A CN 1060683A CN 91109915 CN91109915 CN 91109915 CN 91109915 A CN91109915 A CN 91109915A CN 1060683 A CN1060683 A CN 1060683A
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- molybdenum powder
- reaction vessel
- samarium
- manufacture method
- molybdenum
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Abstract
The present invention relates to a kind of reduction-oxidation samarium and prepare reaction vessel and the manufacture method thereof that samarium metal is used.This reaction vessel is made up of plumbago crucible and sleeve, condenser, plumbago crucible and telescopic surface-coated one deck molybdenum powder.Its manufacture method is: be dissolved in polyvinyl alcohol in the water and add 27～32% (weight) granularity, 150 order molybdenum powders and be made into molybdenum powder slurry, this molybdenum powder slurry is brushed on the plumbago crucible and telescopic surface of machine-shaping, carry out sintering after to be dried.Adopt this reaction vessel to produce samarium metal, can reduce production costs, be convenient to operate and improve the quality of products.
Description
The present invention relates to a kind of manufacture method for preparing reaction vessel and this container of samarium metal.
At present, the reaction vessel of preparation samarium metal adopts refractory metals such as Mo, W, Ta to make more, generally is to adopt welding of Mo sheet or the compacting of Me powder to form.The reaction principle of preparation samarium metal is: utilize the samarium metal vapour pressure very high, at high temperature remove the reduction-oxidation samarium with very low lanthanoid metal of vapour pressure or norium etc.This reaction is in vacuum (＜10
-1Pa) under carry out, the samarium metal that restores is gaseous state and can separates with furnace charge and rise to and be condensed into ingot metal in the condenser.Usually the reaction vessel of preparation samarium is formed (referring to Fig. 1) by crucible (furnace burdening), sleeve (causing thermograde) and condenser three parts, and crucible and sleeve are formed by the molybdenum powder compacting, and condenser adopts Al
2O
3Manufacture.Yet the reaction vessel that adopts the molybdenum powder compacting costs an arm and a leg, weight is big and operation inconvenience.In addition, in the production in order to obtain the samarium metal ingot that quality is higher, enrich, Al
2O
3The volume of condenser will with how much being complementary of furnace charge amount.This is because in reduction process, because inevitably have some impurity in the Samarium trioxide raw material, the steaming pressure ratio samarium metal of some impurity is also high, before samarium metal also is not reduced out, just be distilled out, they at first condense in condenser surface.When the amount of the capacity of condenser and furnace charge was complementary, each stove can obtain a substantial samarium ingot, and outside surface elder generation agglomerative impurity can remove through cleaning, so the purity of samarium ingot is higher.With the sleeve of molybdenum powder compacting because technologic restriction, be not easy to make complicated shape, generally make straight-tube shape, the volume of condenser is also corresponding like this becomes very big, want to make samarium metal to be full of condenser substantially, just need more than reduction two stoves, the impurity that every stove distills at first after such first stove has just become interlayer to be present in the samarium metal ingot, be difficult for removing, thereby the samarium metal product purity is descended.
The objective of the invention is to obtain a kind of reaction vessel cheap and that process easily that the reduction-oxidation samarium prepares samarium metal that is used for, the production cost of samarium metal is reduced, and the quality of samarium metal ingot is improved.
For achieving the above object, the present invention is achieved in that
The reaction vessel that preparation samarium metal of the present invention is used, be that Samarium trioxide is mixed with the rare earth reductive agent, reducing metal samarium under vacuum high-temperature, this container is made up of crucible, sleeve and condenser, crucible wherein and sleeve are to be made by graphite, its surperficial coated one deck molybdenum powder, the thickness of molybdenum powder coating is 0.2mm～2mm.
The manufacture method of this reaction vessel is: the organic binder bond polyvinyl alcohol is dissolved in the hot water, be made into concentration 3～5%(weight) solution, adding granularity is-150 purpose molybdenum powders, when molybdenum powder content is 27～32%(weight) time, this molybdenum powder slurry is brushed on plumbago crucible that shapes and telescopic surface, after to be dried, put into vacuum sintering furnace again in 10
-2Pa, 1600～1700 ℃ of following sintering 2～3 hours, stove is cold.
In order better to realize the present invention, brush the molybdenum powder slurry method can for: the plumbago crucible and the sleeve that shape are immersed in the molybdenum powder slurry, putting into vacuum chamber again vacuumizes, the intrapore air of graphite is extracted out, inflate again in the vacuum chamber then and return to normal pressure, make the molybdenum powder slurry fully enter into the hole of graphite, carry out sintering after the drying again.
Above-mentioned organic binder bond polyvinyl alcohol is also by a kind of replacement in polyethylene oxide, polyacrylamide and the Polyvinylpyrolidone (PVP).
Below in conjunction with accompanying drawing the present invention is done and to be described in further detail.
Fig. 1 is the reaction vessel of suppressing with molybdenum powder in the prior art.
Fig. 2 is a graphite reaction vessel of the present invention.
Among Fig. 1,1 is crucible, and 2 is the straight-tube shape sleeve, forms by the molybdenum powder compacting, and 3 is Al2O
3Condenser, 4 is by Sm2O
3Furnace charge with the reducing agent mixing.
Among Fig. 2,1,2 are respectively graphite crucible and sleeve, and it is up-small and down-big contraction-like that this sleeve is, and the inner surface of crucible and sleeve is that molybdenum powder coating 5,4 is furnace charge.
Adopt graphite to manufacture the reaction vessel of producing samarium metal, the problem that at first will consider is possible generate Rare Earth Carbides with the graphite reaction, reducing agent La or norium (comprising La, Ce, Nd, Pr) and the Sm that restores may generate Rare Earth Carbides, if the carbide vapour pressure that generates is higher, just may pollute samarium metal. By consulting related documents, learn that in the situation of rich carbon rare earth metal is combined with carbon and is mainly generated RC2The type carbide. The reaction of rare earth and carbon is not so good as and O2、H
2O、CO
2Like that strong Deng reaction. The vapour pressure of rare earth metal carbide can be calculated by equation LnP=A-(B)/(T), and (1773 ° of K are upper limits) is as follows by the data result of calculation that can find under the temperature of preparation samarium metal:
P
LaC
2＝3.35×10
-7Pa，
PCeC
2＝3.13×10
-6Pa，
PNdC
2＝3.85×10
-5Pa，
PSmC
2＝1.13×10
-1Pa，
From above calculation result as can be seen, has only SmC
2Vapour pressure under 1773 ° of K temperature is higher, the vacuum tightness (＜10 of stove during with the production samarium metal
-1Pa) approaching, therefore might pollute samarium metal, therefore need to be coated with layer protective layer at the graphite reaction vessel internal surface.Although test shows: the reaction vessel that is not coated with molybdenum powder is also not serious to the pollution of samarium metal; but because common graphite surface irregularity hole is a lot; when use does not have the graphite reaction vessel of coating to produce samarium metal; reductive agent (lanthanum or norium) and the samarium metal that restores at high temperature all can react generating portion rare earth carbide with carbon; after part rare earth metal pierces in the hole of graphite and to generate carbide with carbon; when the long period deposits in air with graphite reaction vessel; the rare earth carbide is understood the moisture in the suck and is decomposed; volumetric expansion appears; thereby cause the plumbago crucible spalling; therefore, it is necessary being coated with layer protective layer at the internal surface of graphite reaction vessel.
Theoretically, the coated material of protective layer can be Mo, W, Ta, Nb and Al
2O
3Powder, but tungsten powder and Al
2O
3Powder is easy-sintering not, and tantalum powder and niobium powder price are more expensive, and molybdenum powder is low price, easy sintering then, has also bought easily on market, and is therefore suitable.
The organic binder bond that the present invention selects for use is a kind of in polyvinyl alcohol, polyethylene oxide, polyacrylamide and the Polyvinylpyrolidone (PVP), belongs to the aqueous organopolysiloxane tackiness agent.Consider from operational condition and protection aspect, selected polyvinyl alcohol, polyvinyl alcohol belongs to surfactant, adsorptive power is strong, percent hydrolysis reaches 98～99%, and cheap, nontoxicity, being made into the lower concentration tackiness agent, still to show the glued membrane intensity of good bonding force, generation also high, and therefore selecting polyvinyl alcohol for use is caking agent.
The compound method of polyvinyl alcohol water solution is: polyvinyl alcohol is added to the water, under agitation is heated to 80～90 ℃, when content is 3～5%(weight) time, become transparent liquid and get final product.
Then-150 purpose molybdenum powders are joined in the above-mentioned polyvinyl alcohol adhesive aqueous solution, molybdenum powder content is 27～32%(weight in this molybdenum powder slurry).
Apply the molybdenum powder slurry and can adopt spread coating or infiltration method, spread coating is promptly dipped in the molybdenum powder slurry that mixes up with hairbrush in air, molybdenum powder is coated on plumbago crucible and the telescopic surface.Infiltration method is that graphite reaction vessel is immersed in the molybdenum powder slurry, put into again that vital qi is indoor to vacuumize, the intrapore air of graphite is extracted out, inflate again in the vacuum chamber then and recover normal pressure, again graphite reaction vessel is taken out from the molybdenum powder slurry, be coated with a lower surface with hairbrush, like this than easier being filled in the graphite of spread coating molybdenum powder slurry, the better quality of coating.
Brush later plumbago crucible and the sleeve of molybdenum powder, be placed on that seasoning get final product until becoming hard coating in the air, preferably drying is more than 24 hours.
Dried graphite reaction vessel is put into the vacuum oven sintering, and heat-up rate is not less than 9 * 10 in vacuum tightness
-2PaSituation under, rose about 200 ℃ in per ten minutes, in vacuum tightness 10
-2Pa, 1600～1700 ℃ of following sintering 2～3 hours, furnace cooling then.Sintering is in order to prevent the oxidation of graphite, molybdenum powder under higher vacuum, and temperature is relatively poor as the sintering strength that is lower than 1600 ℃ of coatings.In sintering process, polyvinyl alcohol is promptly beginning slow decomposition more than 100 ℃, and color is black by leucismus, calcination under vacuum high-temperature, and the possible degradation production of polyvinyl alcohol has moisture, carbon, carbon monoxide and other hydrocarbon polymer etc.
Compared with prior art, the graphite reaction vessel of the band molybdenum powder coating that the present invention obtains, can be processed into complicated shape as required, do not reducing the samarium metal recovery rate, do not increasing under the situation of carbon content, container weight is reduced to 1/5 of molybdenum powder hold-down container weight, make the effective reaction vessel of vacuum carbon of a cover 50KW, price only needs about 400 yuan, be equivalent to the molybdenum powder compacting the reaction vessel price 1/20.In addition, because crucible, the sleeve of plumbago crucible and the compacting of telescopic ratio of heat capacities molybdenum powder are little, therefore after stopping heating, it is fast that furnace cooling speed is wanted comparatively speaking, compare with sleeve with the crucible that uses the molybdenum powder compacting, the time of coming out of the stove can shift to an earlier date 1～2 hour, can enhance productivity.
Introduce embodiments of the invention below.
With commercially available Graphite Electrodes,, plumbago crucible, graphite sleeve and Al have been determined by the size and the heating element space length to bell suitable for reading of homemade 25KW vacuum carbon tube furnace heating element size
2O
3The size of condenser is also processed.
Be coated with molybdenum powder: polyvinyl alcohol is added to the water by 4% weight ratio, be placed on and constantly be heated with stirring to 80～90 ℃ on the electric furnace pan, dissolve fully until granule of polyvinyl alcohol, solution becomes get transparent till, molybdenum powder with granularity 100～200 orders, purity 99% joins in the polyvinyl alcohol solution under constantly stirring slowly then, treat that the weight ratio of molybdenum powder in solution reaches at 29% o'clock, the molybdenum powder slurry promptly mixes up, with hairbrush molybdenum powder slurry is brushed on the plumbago crucible and telescopic internal surface that cleaned then, for make the molybdenum powder coating have certain thickness (＞0.2mm) can brush repeatedly.
Drying and sintering: the plumbago crucible and the sleeve that will coat molybdenum powder were placed on air drying 24 hours, promptly obtained hard molybdenum coating, then crucible and sleeve were put into vacuum carbon tube furnace, were guaranteeing that vacuum tightness is not less than 9 * 10
-2PaSituation under slowly heat up, approximately heated up 150～200 ℃ in per 10 minutes, when furnace temperature reaches 1650 ℃, be incubated 2 hours, stop then heating crucible and sleeve furnace cooling.
Claims (5)
1, a kind ofly preparing the reaction vessel that samarium metal is used, is that Samarium trioxide is mixed with the rare earth reductive agent, reducing metal samarium under vacuum high-temperature.This container is made up of crucible, sleeve and condenser, it is characterized in that: described crucible and sleeve are to be made by graphite, its surface-coated one deck molybdenum powder.
2, reaction vessel according to claim 1 is characterized in that: the thickness 10.2～2mm of described metal molybdenum coating.
3, according to the manufacture method of the described reaction vessel of claim 1.2, it is characterized in that: the organic binder bond polyvinyl alcohol is dissolved in the hot water, be made into concentration 3～5%(weight) solution, add granularity＜150 purpose molybdenum powders, when molybdenum powder content is 27～32%(weight) time, this molybdenum powder slurry is brushed on plumbago crucible that shapes and telescopic surface, to be dried after, put into vacuum sintering furnace again in 10
-2Pa, 1600～1700 ℃ of following sintering 2～3 hours, stove is cold.
4, manufacture method according to claim 2, it is characterized in that, the best approach of described brushing molybdenum powder slurry is: the plumbago crucible and the sleeve that shape are immersed in the molybdenum powder slurry, putting into vacuum chamber again vacuumizes, the intrapore air of graphite is extracted out, inflate again in the vacuum chamber then and return to normal pressure, the dry sintering that carries out again afterwards.
5, manufacture method according to claim 3 is characterized in that: described organic binder bond polyvinyl alcohol can be by a kind of replacement in polyethylene oxide, polyacrylamide and the polyvinylpyrrolidone.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109915 CN1060683A (en) | 1991-11-07 | 1991-11-07 | Preparation samarium metal reaction vessel and manufacture method thereof |
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|---|---|---|---|
| CN 91109915 CN1060683A (en) | 1991-11-07 | 1991-11-07 | Preparation samarium metal reaction vessel and manufacture method thereof |
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Cited By (12)
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|---|---|---|---|---|
| EP1939566A1 (en) * | 2006-12-27 | 2008-07-02 | General Electric Company | Articles for use with highly reactive alloys |
| US7582133B2 (en) | 2006-12-27 | 2009-09-01 | General Electric Company | Methods for reducing carbon contamination when melting highly reactive alloys |
| CN102719898A (en) * | 2012-02-28 | 2012-10-10 | 浙江上城科技有限公司 | Assembled high-temperature resistant crucible |
| US9803923B2 (en) | 2012-12-04 | 2017-10-31 | General Electric Company | Crucible and extrinsic facecoat compositions and methods for melting titanium and titanium aluminide alloys |
| US9802243B2 (en) | 2012-02-29 | 2017-10-31 | General Electric Company | Methods for casting titanium and titanium aluminide alloys |
| US10391547B2 (en) | 2014-06-04 | 2019-08-27 | General Electric Company | Casting mold of grading with silicon carbide |
| CN111410562A (en) * | 2019-09-10 | 2020-07-14 | 包头稀土研究院 | Alkaline earth oxide crucible with rare earth oxyfluoride coating and preparation method thereof |
| CN114657420A (en) * | 2022-04-08 | 2022-06-24 | 包头稀土研究院 | Light rare earth-zinc alloy, preparation method and application thereof, and application of smelting container |
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| CN114717433A (en) * | 2022-04-08 | 2022-07-08 | 包头稀土研究院 | Samarium-zinc alloy, production method thereof and application of niobium-containing container |
| CN114717432A (en) * | 2022-04-08 | 2022-07-08 | 包头稀土研究院 | Zinc holmium alloy, method for the production thereof and use of a container |
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-
1991
- 1991-11-07 CN CN 91109915 patent/CN1060683A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1939566A1 (en) * | 2006-12-27 | 2008-07-02 | General Electric Company | Articles for use with highly reactive alloys |
| JP2009115441A (en) * | 2006-12-27 | 2009-05-28 | General Electric Co <Ge> | Article for use with highly reactive alloy |
| US7582133B2 (en) | 2006-12-27 | 2009-09-01 | General Electric Company | Methods for reducing carbon contamination when melting highly reactive alloys |
| US7790101B2 (en) | 2006-12-27 | 2010-09-07 | General Electric Company | Articles for use with highly reactive alloys |
| CN101210290B (en) * | 2006-12-27 | 2012-10-10 | 通用电气公司 | Articles for use with highly reactive alloys |
| CN101230424B (en) * | 2006-12-27 | 2013-09-18 | 通用电气公司 | Methods for reducing carbon contamination when melting highly reactive alloys |
| CN102719898A (en) * | 2012-02-28 | 2012-10-10 | 浙江上城科技有限公司 | Assembled high-temperature resistant crucible |
| CN102719898B (en) * | 2012-02-28 | 2015-10-07 | 浙江上城科技有限公司 | A kind of assembly type high-temperature crucible |
| US9802243B2 (en) | 2012-02-29 | 2017-10-31 | General Electric Company | Methods for casting titanium and titanium aluminide alloys |
| US9803923B2 (en) | 2012-12-04 | 2017-10-31 | General Electric Company | Crucible and extrinsic facecoat compositions and methods for melting titanium and titanium aluminide alloys |
| US10391547B2 (en) | 2014-06-04 | 2019-08-27 | General Electric Company | Casting mold of grading with silicon carbide |
| CN111410562A (en) * | 2019-09-10 | 2020-07-14 | 包头稀土研究院 | Alkaline earth oxide crucible with rare earth oxyfluoride coating and preparation method thereof |
| CN114657420A (en) * | 2022-04-08 | 2022-06-24 | 包头稀土研究院 | Light rare earth-zinc alloy, preparation method and application thereof, and application of smelting container |
| CN114657421A (en) * | 2022-04-08 | 2022-06-24 | 包头稀土研究院 | Ce-Zn alloy, method for producing same and use of smelting vessel |
| CN114717433A (en) * | 2022-04-08 | 2022-07-08 | 包头稀土研究院 | Samarium-zinc alloy, production method thereof and application of niobium-containing container |
| CN114717432A (en) * | 2022-04-08 | 2022-07-08 | 包头稀土研究院 | Zinc holmium alloy, method for the production thereof and use of a container |
| CN114752814A (en) * | 2022-04-08 | 2022-07-15 | 包头稀土研究院 | Heavy rare earth zinc alloy, manufacturing method and application thereof, and application of tungsten-containing container |
| CN114717433B (en) * | 2022-04-08 | 2023-10-20 | 包头稀土研究院 | Samarium-zinc alloy, production method thereof and use of niobium-containing container |
| CN114657421B (en) * | 2022-04-08 | 2023-10-20 | 包头稀土研究院 | Ce-Zn alloy, production method thereof and application of smelting vessel |
| CN114752814B (en) * | 2022-04-08 | 2023-10-20 | 包头稀土研究院 | Heavy rare earth zinc alloy, method for producing same, use thereof, and use of tungsten-containing container |
| CN114717432B (en) * | 2022-04-08 | 2023-10-20 | 包头稀土研究院 | Zinc-holmium alloy, method for producing same and use of container |
| CN114657420B (en) * | 2022-04-08 | 2023-10-20 | 包头稀土研究院 | Light rare earth-zinc alloy, preparation method and application thereof and application of smelting container |
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