CN101823141B - Grain-refined high-temperature alloy casting technology - Google Patents
Grain-refined high-temperature alloy casting technology Download PDFInfo
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- CN101823141B CN101823141B CN2009100105572A CN200910010557A CN101823141B CN 101823141 B CN101823141 B CN 101823141B CN 2009100105572 A CN2009100105572 A CN 2009100105572A CN 200910010557 A CN200910010557 A CN 200910010557A CN 101823141 B CN101823141 B CN 101823141B
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Abstract
The invention relates to a grain-refined high-temperature alloy casting technology, which is characterized in that the high-temperature alloy casting technology specifically satisfies the following requirements that: first a powder metallurgical method is adopted and the basic main element, i.e. nickel of high-temperature ally is used as binder to bind high melting-point metal oxide particles to prepare intermediate alloy; the intermediate alloy and mother ally are smelted jointly and pouring is conducted by adopting normal pouring technological parameters; and the high melting-point fine metal oxide particles are used as nucleating centers to form a great number of grains to finally obtain a fine grain high-temperature alloy structure. Since the powder metallurgical method is adopted and nickel is used as the binder to bind nano micron-scale yttrium oxide particles together to prepare refiner, the refiner and the mother alloy are smelted together and are agitated and the pouring is conducted according to the normal production technology, the invention has the advantages that the refinement technology is greatly simplified and the refiner is ensured not to lose effectiveness for long time under high temperature.
Description
Technical field
The present invention relates to casting technology field, a kind of high temperature alloy casting technique of grain refinement is provided especially.
Background technology
High temperature alloy has been widely used in fields such as Aeronautics and Astronautics, and different purposes and applied environment are also inequality to composition, tissue, the performance demands of high temperature alloy.Some parts of aero-engine such as the serviceability temperature of structural members such as low-pressure turbine blade and starter motor blisk are relatively low.As a rule, even tiny equiax crystal can improve the combination property of material.Some new casting methods can be produced very thin crystal grain in recent years; Commonly used in industry have three kinds of crystal fining methods; Be in thermal control method, mechanical vibration method and the chemical method; Adopt the thermal control method, promptly the preheat temperature through control casting pouring temperature and formwork can obtain thinner crystal grain, but in foundry goods, has a large amount of microporosities; Vibratory drilling method is through introducing mechanical oscillation, makes the dendrite fragmentation that solidifies in the alloy liquid and forms more nucleus, and then make crystal grain obtain refinement, but need to transform or drop into a large amount of fund reforming equipments, and price comparison is expensive; Simple to operate, good in refining effect that chemical method has, for example: use CoO+Al
2O
3Be coated on the precise casting mould shell inner surface, make the refinement of cast(ing) surface layer tissue.The B that adds trace also has certain thinning effect, and adding intermetallic compound such as Co-Nb-Ni etc. in addition also has certain effect; But concerning high temperature alloy, these elements can only change in very little scope, otherwise tissue can become unstable; Mutually harmful or low melting point phase occur, the thinning effect that a spot of fining agent does not have, too much fining agent also possibly reduce the performance of alloy; In addition; Because the fusing point of high temperature alloy is very high, fining agent at high temperature lost efficacy easily, caused thinning effect and not obvious.Good fining agent should have high fusing point; With melt similar crystal structure is arranged; With melt close density is arranged; Good dispersiveness is arranged, alloy property is not had adverse effect.Therefore, be necessary to adopt new fining agent to satisfy the specific (special) requirements of high temperature alloy industry and make foundry goods have higher performance.
Summary of the invention
The object of the invention provides the demand that a kind of new fining agent satisfies the high temperature alloy refinement, makes high temperature alloy have comprehensive performance.
Basic principle of the present invention: adopt powder metallurgy process; Utilize the basic pivot nickel of high temperature alloy to bond the high-melting point metal oxide particle as binding agent; Process intermediate alloy, with the melting of foundry alloy material, adopt normal casting process parameters to pour into a mould intermediate alloy; Utilize high-melting-point, the tiny metal oxide particle of size to form great number of grains, obtain compact grained high temperature alloy tissue at last as the nucleating center.
The high temperature alloy casting technique of a kind of grain refinement of the present invention is characterized in that: said high temperature alloy casting technique requires below specifically satisfying:
At first adopt powder metallurgy process, utilize the basic pivot nickel of high temperature alloy to bond the high-melting point metal oxide particle, process intermediate alloy as binding agent;
Then with intermediate alloy with the melting of foundry alloy material, pour into a mould (adopt prior art in common casting process parameters get final product);
Utilize high-melting-point, tiny metal oxide particle to form great number of grains, obtain compact grained high temperature alloy tissue at last as the nucleating center.
In the high temperature alloy casting technique of said grain refinement; Preparation casting is following with the concrete technical process of intermediate alloy: at first with the other nickel powder of nano-micro level, refractory metal oxide powder, evenly mix; Then with mold pressing or etc. molding modes such as static pressure carry out moulding; Under 1200 ℃～1400 ℃ reducing atmospheres, carry out isothermal sintering, 1～3 hour temperature retention time time, make nickel-metal oxide intermediate alloy fining agent.
In the high temperature alloy casting technique of grain refinement according to the invention; With the fining agent intermediate alloy be with the specific requirement of melting of high temperature alloy foundry alloy and cast: at first with the metal oxide intermediate alloy with the melting in vaccum sensitive stove of high temperature alloy foundry alloy; After treating that alloy all melts; Add the high-power electromagnetic agitation of carrying out, the back that stirs reduces power and lowers the temperature, and treats to pour into a mould when the alloy liquid temp is reduced to pouring temperature.
In the high temperature alloy casting technique of grain refinement according to the invention, the refractory metal oxide powder that is used as the intermediate alloy raw material specifically adopts the yttria powder.
At least also one of require below satisfying in the high temperature alloy casting technique of said grain refinement:
High-melting-point yttria powder size as the intermediate alloy raw material is 0.1～3 micron;
When making intermediate alloy, adopt the mechanical ball milling mode that micron level nickel powder, yttria powder are evenly mixed, blending agent adopts acetone or/and hexane, and the ball milling time is 1～60 hour, then powder is dried;
Can adopt then mold pressing or etc. molding modes such as static pressure the nickel powder that mixes, yttria powder mixed powder are carried out moulding.
In the high temperature alloy casting technique of said grain refinement, require below the intermediate alloy after the moulding being carried out satisfy in the process of isothermal sintering:
Described sintering adopts continous way atmosphere protection tube furnace, perhaps adopts batch (-type) atmosphere protection tube furnace;
Sintering and reducing property protective atmosphere adopts high-purity hydrogen; Perhaps adopt the mist of high-purity hydrogen and high-purity nitrogen, this moment, the volume ratio of hydrogen and nitrogen was between 1: 1～1: 5; Flow can be controlled in 5～50ml/min.cm
2
In the high temperature alloy casting technique of said grain refinement; Require below intermediate alloy after mechanical-moulded being carried out also satisfy in the process of isothermal sintering: the sintering temperature of the intermediate alloy after the moulding being carried out sintering is 1200～1400 ℃, and temperature retention time is 1～3 hour.
In the high temperature alloy casting technique of said grain refinement; With the fining agent intermediate alloy with the melting in vaccum sensitive stove of foundry alloy material; After treating that thoroughization of furnace charge is clear, improve power and carry out stir process, mixing time 2～10 minutes; Treat to pour into a mould after temperature drops to the normal pouring temperature of alloy, obtain the alloy-steel casting of refinement at last.
Advantage of the present invention: adopt nickel other yttria particle of nano-micro level to be bondd through the powder metallurgy mode and make fining agent as binding agent; Fining agent is also stirred with the foundry alloy melting; Pour into a mould by ordinary production technology; Simplified process for refining greatly, this fining agent can guarantee at high temperature not lose efficacy for a long time simultaneously.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed explanation:
Fig. 1 is Ni-10%Yi
2O
3The fining agent microscopic structure;
Fig. 2 is the K441 alloy microscopic structure of process for refining preparation;
Fig. 3 is the K441 alloy microscopic structure of common process preparation;
Fig. 4 is Ni-1%Yi
2O
3The fining agent microscopic structure;
Fig. 5 is the K441 alloy microscopic structure of process for refining preparation.
The specific embodiment
The high temperature alloy casting technique of 1 one kinds of grain refinements of embodiment
At first micron level nickel powder (0.5-3 micron), yttria powder (1-3 micron) are prepared burden; Its mass ratio is 90: 10; Adopt the mechanical ball milling mode that micron level nickel powder, yttria powder are evenly mixed, blending agent adopts hexane, and the ball milling time is 20 hours; After evenly mixing, adopt the compression molding mode that the nickel powder that mixes, yttria powder mixed powder are carried out moulding; The biscuit of moulding is put into continous way atmosphere protection tube furnace, and restitutive protection's property atmosphere adopts high-purity hydrogen, and flow-control is at 20ml/min.cm
2The isothermal sintering temperature is 1400 ℃, and temperature retention time is 1 hour; Alloy makes fining agent at last with the stove cool to room temperature then, and alloy structure is seen Fig. 1; Fining agent (mass ratio 0.1%) with high temperature alloy K441 foundry alloy (mass ratio 99.9%) melting in induction furnace, is treated that alloy all after the fusing, adds the high-power electromagnetic agitation of carrying out; Mixing time 2 minutes; The back that stirs reduces power and lowers the temperature, and treats to pour into a mould when the alloy liquid temp is reduced to 1420 ℃, obtains the alloy-steel casting of refinement at last; The foundry goods microscopic structure is seen Fig. 2, and the alloy-steel casting microscopic structure that traditional handicraft is produced is seen Fig. 3.
The high temperature alloy casting technique of 2 one kinds of grain refinements of embodiment
At first micron level nickel powder (0.5-3 micron), yttria powder (1-3 micron) are prepared burden; Its mass ratio is 99: 1; Adopt the mechanical ball milling mode that micron level nickel powder, yttria powder are evenly mixed, blending agent adopts acetone, and the ball milling time is 30 hours; After evenly mixing, adopt the compression molding mode that the nickel powder that mixes, yttria powder mixed powder are carried out moulding; The biscuit of moulding is put into continous way atmosphere protection tube furnace, and restitutive protection's property atmosphere adopts high-purity hydrogen, and flow-control is at 15ml/min.cm
2The isothermal sintering temperature is 1300 ℃, and temperature retention time is 3 hours; Alloy makes fining agent at last with the stove cool to room temperature then, and alloy structure is seen Fig. 4; With fining agent (mass ratio 0.4%) with high temperature alloy K4169 foundry alloy (mass ratio 99.9%) melting in induction furnace; After treating that alloy all melts, add the high-power electromagnetic agitation of carrying out, mixing time 2 minutes; The back that stirs reduces power and lowers the temperature; Treat to pour into a mould when the alloy liquid temp is reduced to 1400 ℃, obtain the alloy-steel casting of refinement at last, the foundry goods microscopic structure is seen Fig. 5.
The high temperature alloy casting technique of 3 one kinds of grain refinements of embodiment
At first micron level nickel powder (0.5-3 micron), yttria powder (1-3 micron) are prepared burden; Its mass ratio is 95: 5; Adopt the mechanical ball milling mode that micron level nickel powder, yttria powder are evenly mixed, blending agent adopts hexane, and the ball milling time is 10 hours; After evenly mixing, adopt the cold isostatic compaction mode that the nickel powder that mixes, yttria powder mixed powder are carried out moulding; The biscuit of moulding is put into continous way atmosphere protection tube furnace, and restitutive protection's property atmosphere adopts high-purity hydrogen, and flow-control is at 40ml/min.cm
2The isothermal sintering temperature is 1200 ℃, and temperature retention time is 3 hours; Alloy makes fining agent at last with the stove cool to room temperature then; With fining agent (mass ratio 0.05%) with high temperature alloy K418 foundry alloy (mass ratio 99.95%) melting in induction furnace; After treating that alloy all melts; Add the high-power electromagnetic agitation of carrying out, mixing time 2 minutes, the back that stirs reduces power and lowers the temperature; Treat to pour into a mould when the alloy liquid temp is reduced to 1420 ℃, obtain the alloy-steel casting of refinement at last.
The high temperature alloy casting technique of 4 one kinds of grain refinements of embodiment
At first micron level nickel powder (0.5-3 micron), yttria powder (0.5-3 micron) are prepared burden; Its mass ratio is 90: 10; Adopt the mechanical ball milling mode that micron level nickel powder, yttria powder are evenly mixed, blending agent adopts acetone, and the ball milling time is 20 hours; After evenly mixing, molding modes such as employing isostatic cool pressing carry out moulding with the nickel powder that mixes, yttria powder mixed powder; The biscuit of moulding is put into continous way atmosphere protection tube furnace, and restitutive protection's property atmosphere adopts high-purity hydrogen, and flow-control is at 20ml/min.cm
2The isothermal sintering temperature is 1400 ℃, and temperature retention time is 2 hours; Alloy makes fining agent at last with the stove cool to room temperature then, and alloy structure is seen Fig. 1; With fining agent (mass ratio 0.2%) with high temperature alloy K417 foundry alloy (mass ratio 99.8%) melting in induction furnace; After treating that alloy all melts; Add the high-power electromagnetic agitation of carrying out, mixing time 3 minutes, the back that stirs reduces power and lowers the temperature; Treat to pour into a mould when the alloy liquid temp is reduced to 1430 ℃, obtain the alloy-steel casting of refinement at last.
Claims (8)
1. the high temperature alloy casting technique of a grain refinement is characterized in that: said high temperature alloy casting technique requires below specifically satisfying:
At first adopt powder metallurgy process, utilize the basic pivot nickel of high temperature alloy to bond the high-melting point metal oxide particle, process intermediate alloy as binding agent;
Then with intermediate alloy with the melting of foundry alloy material, pour into a mould;
Utilize high-melting-point, tiny metal oxide particle to form great number of grains, obtain compact grained high temperature alloy tissue at last as the nucleating center;
Said high-melting point metal oxide particle is 0.1～3 millimeter a yttria powder.
2. according to the high temperature alloy casting technique of the said grain refinement of claim 1, it is characterized in that:
In the high temperature alloy casting technique of said grain refinement; The preparation casting is following with the concrete technical process of intermediate alloy: at first the other nickel powder of nano-micro level, refractory metal oxide powder are evenly mixed; Carry out moulding then; Under 1200 ℃～1400 ℃ reducing atmospheres, carry out isothermal sintering, temperature retention time 1～3 hour makes nickel-metal oxide intermediate alloy fining agent.
3. according to the high temperature alloy casting technique of the said grain refinement of claim 1, it is characterized in that:
In the high temperature alloy casting technique of said grain refinement; With the fining agent intermediate alloy be with the specific requirement of melting of high temperature alloy foundry alloy and cast: at first with the metal oxide intermediate alloy with the melting in vaccum sensitive stove of high temperature alloy foundry alloy; After treating that alloy all melts; Carry out electromagnetic agitation, lower the temperature after stirring, treat to pour into a mould when the alloy liquid temp is reduced to pouring temperature.
4. according to the high temperature alloy casting technique of claim 1 or 2 or 3 said grain refinements, it is characterized in that: in the high temperature alloy casting technique of said grain refinement, the refractory metal oxide powder that is used as the intermediate alloy raw material specifically adopts the yttria powder.
5. according to the high temperature alloy casting technique of the said grain refinement of claim 4, it is characterized in that: one of require below at least also satisfying in the high temperature alloy casting technique of said grain refinement:
When making intermediate alloy, adopt the mechanical ball milling mode that the other nickel powder of nano-micro level, yttria powder are evenly mixed, blending agent adopts acetone or/and hexane, and the ball milling time is 1～60 hour, then powder is dried;
Adopt then mold pressing or etc. the mechanical-moulded mode of static pressure the nickel powder that mixes, yttria powder mixed powder are carried out moulding.
6. according to the high temperature alloy casting technique of the said grain refinement of claim 4, it is characterized in that: in the high temperature alloy casting technique of said grain refinement, require below biscuit after the moulding being carried out satisfy in the process of isothermal sintering:
Described sintering adopts continous way atmosphere protection tube furnace, perhaps adopts batch (-type) atmosphere protection tube furnace;
Sintering and reducing property protective atmosphere adopts high-purity hydrogen; Perhaps adopt the mist of high-purity hydrogen and high-purity nitrogen, this moment, the volume ratio of hydrogen and nitrogen was between 1: 1～1: 5; Flow can be controlled in 5～50ml/min.cm
2
7. according to the high temperature alloy casting technique of the said grain refinement of claim 6, it is characterized in that: in the high temperature alloy casting technique of said grain refinement, require below the intermediate alloy after mechanical-moulded being carried out satisfy in the process of isothermal sintering:
The sintering temperature of the intermediate alloy after the moulding being carried out sintering is 1200 ℃～1400 ℃, and temperature retention time is 1～3 hour.
8. according to the high temperature alloy casting technique of the said grain refinement of claim 6; It is characterized in that: in the high temperature alloy casting technique of said grain refinement, with the fining agent intermediate alloy with the melting in vaccum sensitive stove of foundry alloy material, treat that thoroughization of furnace charge is clear after; Carry out stir process; Mixing time 2～10 minutes is treated to pour into a mould after temperature drops to the normal pouring temperature of alloy, obtains the alloy-steel casting of refinement at last.
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| CN110872652A (en) * | 2018-08-29 | 2020-03-10 | 中国科学院金属研究所 | Preparation method and application of grain refiner in high-temperature alloy |
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| CN102251129A (en) * | 2011-07-15 | 2011-11-23 | 燕山大学 | Refiner for magnesium-aluminum-based alloy and preparation method thereof |
| CN104894464A (en) * | 2015-05-14 | 2015-09-09 | 浙江工贸职业技术学院 | Preparation method of iron-yttria intermediate alloy for casting |
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| CN110976773A (en) * | 2019-12-31 | 2020-04-10 | 南通海泰科特精密材料有限公司 | Method for improving performance of nickel-based alloy casting |
| CN111545710A (en) * | 2020-05-13 | 2020-08-18 | 南京工程学院 | Technological method and system for precisely casting refined grains and tissues of nickel-based superalloy |
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| CN1348016A (en) * | 2001-10-19 | 2002-05-08 | 钢铁研究总院 | High-performance high-temperature nickel-base alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1348016A (en) * | 2001-10-19 | 2002-05-08 | 钢铁研究总院 | High-performance high-temperature nickel-base alloy |
| CN1544677A (en) * | 2003-11-20 | 2004-11-10 | 上海交通大学 | Ultra-fine grain refining agent prefabricated block and process for preparing same |
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| JP特开2005-281804A 2005.10.13 |
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| CN110872652A (en) * | 2018-08-29 | 2020-03-10 | 中国科学院金属研究所 | Preparation method and application of grain refiner in high-temperature alloy |
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