CN101493284A - Crucible for fusing titan and method of preparation thereof - Google Patents
Crucible for fusing titan and method of preparation thereof Download PDFInfo
- Publication number
- CN101493284A CN101493284A CNA2009100465084A CN200910046508A CN101493284A CN 101493284 A CN101493284 A CN 101493284A CN A2009100465084 A CNA2009100465084 A CN A2009100465084A CN 200910046508 A CN200910046508 A CN 200910046508A CN 101493284 A CN101493284 A CN 101493284A
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- crucible
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- titanium
- stable compound
- fusing
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Abstract
The invention relates to a crucible for fusing titanium and a production method thereof, mainly used for fusing titanium alloy as well as for fusion cast of other special alloys. Highly stable compounds (yttrium oxide, calcium zirconate or cerium sulphide, etc.) are used as the outer layer of the crucible for fusing titanium; refractory metals (tungsten, molybdenum or tantalum) and the like are combined with the compounds to form transition gradient coating; hot spray processes (laser cladding, plasma spraying, etc.) are used for spraying the transition layers and the transition gradient coating onto the inner surface of a graphite container layer by layer to form a firm and compact composite coating with good thermal shock resistance. By adopting the crucible of the invention to carry out vacuum induction fusion of titanium and titanium alloy, the fused alloy has uniform component, the fusion process consumes less energy and the crucible produces less contamination to the molten titanium.
Description
Technical field
The present invention relates to a kind of crucible and manufacture method thereof that is used for melting titanium or titanium alloy liquation, belong to the titanium alloy smelting technical field.
Background technology
Because the fusing point height of titanium, chemical property is active, when melting, almost can react with refractory material such as zirconia, magnesia, silica etc. with all crucibles, therefore, can not adopt induction furnace melting usually.At present, vacuum consumable electrode electric arc skull melting and the cooling of Forced water cooling copper crucible are often adopted in the melting of titanium or titanium alloy.On copper mould wall, solidify earlier a formation thin layer " scull " during the vacuum arc skull melting, play protection titanium liquid, make it not polluted and heat-blocking action by crucible material.Make titanium liquid temp field inhomogeneous because the water jacketed copper crucible cooling velocity is very fast and form scull, add that titanium alloy is very short in the liquid retention time, make that the casting composition after the cast is inhomogeneous, very big to performance impact.Energy consumption height has simultaneously increased the melting cost of molten titanium.Calcium oxide or boron nitride crucible once were used for the melting titanium or titanium alloy for this reason.But because lime crucible is difficult to sinter molding, and hydrolysis easily under air.As use the lime crucible melting, the oxygen content in the alloy can increase, and influences alloy property; The boron nitride crucible cost of manufacture is very high, and intensity is low, has B, the N element pollution to alloy liquid, and therefore, calcium oxide or boron nitride crucible just can't satisfy the requirement of high-quality alloy.
Graphite has very high refractory refining degree and intensity, and thermal shock resistance is good, is a kind of good heat-resistance material, is commonly used for the melting kettle that melts non-ferrous metals such as copper.But graphite and titanium can react, and pollute, and have a strong impact on the performance of titanium or titanium alloy, therefore can not directly make the crucible of molten titanium.
Summary of the invention
In order to overcome in the prior art complex process in the high melt titanium alloy process, energy consumption is huge, and is seriously polluted, and the problem of uneven components the invention provides a kind of crucible for fusing titan.
Another object of the present invention provides a kind of manufacture method of crucible for fusing titan.
Task of the present invention is achieved in that
A kind of crucible for fusing titan, it is characterized in that: this crucible is that the inner surface of graphite crucible has a composite coating, this composite coating is internal layer, transition gradient coating and outer three-decker, internal layer is the SiC thin layer, transition zone is by a kind of composition the in a kind of and refractory metals tungsten, molybdenum or the tantalum in high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide, and skin is a kind of in high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide.
A kind of manufacture method of crucible for fusing titan is characterized in that the technical process of this method is as follows: the inner surface of the graphite crucible that processes is carried out ultrasonic purification handle, carried out high-temperature heat treatment 0.5～1 hour under 900～1100 ℃ again; Graphite crucible is embedded in and carries out surperficial high temperature siliconising processing in the Si powder then, forms fine and close SiC internal layer; With hot spray process (laser melting coating, ionomer spray etc.) a kind of mixture in a kind of and high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide in refractory metals tungsten, molybdenum or the tantalum is sprayed on formation transition gradient coating on the internal layer; And with a kind of in high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide be sprayed on form on the transition gradient coating outer; Last crucible carries out heat treatment in 0.5～1 hour at 1100～1300 ℃ under argon shield, form firmly fine and close and have the composite coating of good thermal shock resistance.
Transition gradient coating described in the above-mentioned manufacture method be by a kind of powder in a kind of powder in high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide and refractory metals tungsten, molybdenum or the tantalum with different quality than mixing and with three layers of the Asias of hot spray process (laser melting coating, ionomer spray etc.) preparation, from inside to outside, in high-temperature stable compound and refractory metal mass ratio, first subgrade is 1: 3, second subgrade is 1: 1, and the 3rd subgrade is 3: 1.
The specific embodiment
The preparation method of molten titanium crucible composite coating comprises following link:
(1) graphite base preliminary treatment
(2) preparation of graphite surface siliconising layer
(3) preparation of the gradient coating that is combined to form of high stability compound and refractory metal
(4) the coating integration is handled
The graphite base preliminary treatment, the inner surface of the graphite crucible that is about to process carries out ultrasonic purification to be handled, under 1000 ℃, carried out high-temperature heat treatment 1 hour again, to reduce the volatility carbon source and attached to the graphite dust on surface, simultaneously, form micropore, make between SiC internal layer and the graphite and form interlock on the graphite base surface, improve the interface bond strength of SiC internal layer and graphite, and improve graphite and the physical compatibility that is coated with interlayer.
The present invention carries out surperficial high temperature siliconising with the method for Si powder embedding heating process (thermo-chemical treatment) and handles, preparation SiC internal layer.This technology prepares SiC layer preparation temperature low (1050 ℃), and even compact, gaseous carbon is had the good barrier effect, thermal coefficient of expansion (4.0 * 10
-6/ cm) between in graphite (1.0 * 10
-6/ cm) with refractory metals tungsten (5.5 * 10
-6/ cm) between.Alleviate the thermal expansion mismatch between the metals such as graphite and tungsten, aluminium or tantalum, therefore had good physical compatibility.
Yittrium oxide, calcium zirconate or cerium sulphide be find up to now least easily and the oxide that reacts of titanium liquid, thermal coefficient of expansion is low, the fusing point height.Melting point metal height such as tungsten, molybdenum or tantalum, but between thermal coefficient of expansion between yittrium oxide, calcium zirconate or cerium sulphide and graphite.With hot spray process (laser melting coating, ionomer spray etc.) metal powders such as yittrium oxide, calcium zirconate or cerium sulphide and tungsten, molybdenum or tantalum are sprayed on the graphite crucible inner surface, are combined into composite coating, both utilized Y
2O
3, CaZrO
3Or the CeS particle is to the high stability of titanium liquid, utilizes refractory metal tungsten, molybdenum or tantalum etc. as the bonding phase again, overcomes Y
2O
3, CaZrO
3Or CeS is more frangible, has given full play to the advantage that composite is learnt from other's strong points to offset one's weaknesses.
With refractory metals tungsten and high-temperature stable compound oxidation yttrium is example.With hot spray process (laser melting coating, ionomer spray etc.) mixture of metal tungsten powder and yittrium oxide powder is sprayed on and forms the transition gradient coating on the internal layer; And with the yittrium oxide powder be sprayed on the transition gradient coating form outer.
The transition gradient coating is to mix (1: 3,1: 1,3: 1) with refractory metals tungsten by different proportion by high-temperature stable compound oxidation yttrium, successively spray with hot spray process, form inferior three layers transition gradient coating, from inside to outside, in high-temperature stable compound and refractory metal mass ratio, first subgrade is 1: 3, and second subgrade is 1: 1, and the 3rd subgrade is 3: 1.The content of its high-temperature stable compound successively successively decreases from the skin to the internal layer.
It is to carry out heat treatment in 1 hour at 1200 ℃ under argon shield that the coating integration is handled.After the composite coating preparation, also there is tangible interface between each layer.Need by the heat treatment under protective atmosphere tangible interface between eliminating layer and the layer.And make the coating sintering, form integral body with substrate.The content that forms the high-temperature stable compound is by 100% 0% the concentration gradient continuous transition to the internal layer place at skin place.
Molten titanium compound coating crucible of the present invention has the following advantages:
(1) carries out the vacuum induction melting of titanium or titanium alloy with crucible of the present invention, the molten alloy homogeneous chemical composition;
(2) finish the function that hinders carbon by inside and outside complex gradient coating, can realize the no carburetting of titanium alloy smelting;
(3) crucible coating layer has good thermal shock resistance and sintering strength, and fusion process is not fragile, can be real Now reuse;
(4) decrease melting energy consumption is with low cost.
Claims (3)
1, a kind of crucible for fusing titan, it is characterized in that: this crucible is that the inner surface of graphite crucible has a composite coating, this composite coating is internal layer, transition gradient coating and outer three-decker, internal layer is the SiC thin layer, transition zone is by a kind of composition the in a kind of and refractory metals tungsten, molybdenum or the tantalum in high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide, and skin is a kind of in high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide.
2, a kind of manufacture method that is used for the described crucible for fusing titan of claim 1, the technical process that it is characterized in that this method is as follows: the inner surface of the graphite crucible that processes is carried out ultrasonic purification handle, carried out high-temperature heat treatment 0.5～1 hour under 900～1100 ℃ again; Graphite crucible is embedded in and carries out surperficial high temperature siliconising processing in the Si powder then, forms fine and close SiC internal layer; With hot spray process (laser melting coating, ionomer spray etc.) a kind of mixture in a kind of and high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide in refractory metals tungsten, molybdenum or the tantalum is sprayed on formation transition gradient coating on the internal layer; And with a kind of in high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide be sprayed on form on the transition gradient coating outer; Last crucible carries out heat treatment in 0.5～1 hour at 1100～1300 ℃ under argon shield, form firmly fine and close and have the composite coating of good thermal shock resistance.
3, manufacture method as claimed in claim 2, it is characterized in that described transition gradient coating be by a kind of powder in a kind of powder in high-temperature stable compound oxidation yttrium, calcium zirconate or the cerium sulphide and refractory metals tungsten, molybdenum or the tantalum with different quality than mixing and with three layers of the Asias of hot spray process (laser melting coating, ionomer spray etc.) preparation, from inside to outside, in high-temperature stable compound and refractory metal mass ratio, first subgrade is 1: 3, second subgrade is 1: 1, and the 3rd subgrade is 3: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100465084A CN101493284A (en) | 2009-02-24 | 2009-02-24 | Crucible for fusing titan and method of preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100465084A CN101493284A (en) | 2009-02-24 | 2009-02-24 | Crucible for fusing titan and method of preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101493284A true CN101493284A (en) | 2009-07-29 |
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|---|---|---|---|
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|---|---|---|---|---|
| CN102503489A (en) * | 2011-11-09 | 2012-06-20 | 上海大学 | BaZrO3 refractory material for smelting titanium alloy and preparation method of crucibles |
| CN103014374A (en) * | 2012-11-16 | 2013-04-03 | 云南钛业股份有限公司 | Process for establishing kish on smelting cold bed of EB (Electronic Beam) furnace |
| KR101382968B1 (en) | 2012-05-08 | 2014-04-09 | 에이트 세라믹스 주식회사 | apparatus for fabricating sapphire ingot and manufacturing method thereof |
| CN103787694A (en) * | 2013-12-23 | 2014-05-14 | 大连理工大学 | Method for preparing SiC coating on surface of graphite crucible by using in-situ reaction method |
| CN103827048A (en) * | 2011-08-05 | 2014-05-28 | 科卢斯博知识产权有限公司 | Crucible materials |
| CN104470658A (en) * | 2012-05-29 | 2015-03-25 | H·C·施塔克公司 | Metallic crucibles and methods of forming the same |
| CN104662387A (en) * | 2012-07-27 | 2015-05-27 | 通用电气公司 | Crucible and facecoat compositions and methods for melting titanium and titanium aluminide alloys |
| CN104668503A (en) * | 2013-11-30 | 2015-06-03 | 中国科学院金属研究所 | Amorphous alloy member cast forming device and process |
| CN104668504A (en) * | 2013-11-30 | 2015-06-03 | 中国科学院金属研究所 | Casting forming equipment and process for amorphous alloy component |
| CN107245698A (en) * | 2017-06-30 | 2017-10-13 | 福州大学 | A kind of integrated evaporating basket of the internal heat type with aluminum oxide porous textured buffer layers |
| CN109053202A (en) * | 2018-10-09 | 2018-12-21 | 武汉科技大学 | A kind of calcium zirconate crucible and preparation method thereof |
| CN109321865A (en) * | 2018-12-06 | 2019-02-12 | 江苏丰东热技术有限公司 | One kind forming MoSi in titanium alloy surface2The method of antioxidant coating |
| CN109457202A (en) * | 2018-11-02 | 2019-03-12 | 南京宝色股份公司 | A kind of tantalum zirconium clad steel plate reaction kettle heat treatment method |
| CN110643929A (en) * | 2019-11-05 | 2020-01-03 | 江西省科学院应用物理研究所 | Anti-sticking coating on surface of hard alloy sintered boat and preparation method thereof |
| CN112111702A (en) * | 2020-10-13 | 2020-12-22 | 中国南方电网有限责任公司超高压输电公司柳州局 | High-density corrosion-resistant gradient metal ceramic composite coating and spraying method thereof |
| CN114105682A (en) * | 2021-11-26 | 2022-03-01 | 中钢热能金灿新能源科技(湖州)有限公司 | Improved method and device for prolonging service life of graphite crucible |
| CN114394855A (en) * | 2021-12-31 | 2022-04-26 | 中核四0四有限公司 | Preparation method of composite coating for antigravity casting ultrahigh-temperature melt induction heating |
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| CN116675536A (en) * | 2023-05-11 | 2023-09-01 | 武汉科技大学 | Yttria ceramic crucible for smelting titanium alloy and preparation method thereof |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827048A (en) * | 2011-08-05 | 2014-05-28 | 科卢斯博知识产权有限公司 | Crucible materials |
| CN103827048B (en) * | 2011-08-05 | 2017-05-10 | 科卢斯博知识产权有限公司 | Crucible materials |
| CN102503489A (en) * | 2011-11-09 | 2012-06-20 | 上海大学 | BaZrO3 refractory material for smelting titanium alloy and preparation method of crucibles |
| KR101382968B1 (en) | 2012-05-08 | 2014-04-09 | 에이트 세라믹스 주식회사 | apparatus for fabricating sapphire ingot and manufacturing method thereof |
| CN104470658A (en) * | 2012-05-29 | 2015-03-25 | H·C·施塔克公司 | Metallic crucibles and methods of forming the same |
| CN104662387B (en) * | 2012-07-27 | 2017-01-18 | 通用电气公司 | Crucible and facecoat compositions and methods for melting titanium and titanium aluminide alloys |
| CN104662387A (en) * | 2012-07-27 | 2015-05-27 | 通用电气公司 | Crucible and facecoat compositions and methods for melting titanium and titanium aluminide alloys |
| CN103014374A (en) * | 2012-11-16 | 2013-04-03 | 云南钛业股份有限公司 | Process for establishing kish on smelting cold bed of EB (Electronic Beam) furnace |
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| CN104668503B (en) * | 2013-11-30 | 2017-05-31 | 中国科学院金属研究所 | A kind of non-crystaline amorphous metal component casting equipment and technique |
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| CN104668504A (en) * | 2013-11-30 | 2015-06-03 | 中国科学院金属研究所 | Casting forming equipment and process for amorphous alloy component |
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| CN110643929A (en) * | 2019-11-05 | 2020-01-03 | 江西省科学院应用物理研究所 | Anti-sticking coating on surface of hard alloy sintered boat and preparation method thereof |
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| CN114394855A (en) * | 2021-12-31 | 2022-04-26 | 中核四0四有限公司 | Preparation method of composite coating for antigravity casting ultrahigh-temperature melt induction heating |
| CN114951649A (en) * | 2022-06-21 | 2022-08-30 | 重庆三航新材料技术研究院有限公司 | Mold for rapid discharge plasma smelting or vacuum heat treatment and use method thereof |
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