CN103894537A - Composite oxide shell for directional solidification technology as well as application thereof - Google Patents
Composite oxide shell for directional solidification technology as well as application thereof Download PDFInfo
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- CN103894537A CN103894537A CN201410123268.4A CN201410123268A CN103894537A CN 103894537 A CN103894537 A CN 103894537A CN 201410123268 A CN201410123268 A CN 201410123268A CN 103894537 A CN103894537 A CN 103894537A
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Abstract
The invention discloses a composite oxide shell for a directional solidification technology. A surface material of the shell is mainly a SrO-ZrO2-type composite oxide fireproof material. According to the mass percentage of components, the SrO-ZrO2-type composite oxide fireproof material contains main components of 40-45wt% of SrO, 55-60wt% of ZrO2 and 0-3wt% of other impurities. According to the invention, the SrO-ZrO2-type composite oxide for the shell provided by the invention, acting as the main component of the surface material of the shell, can obviously reduce the interface reaction degree of a high-activity alloy and the shell material in the directional solidification process so as to obtain a more ideal directional solidification tissue, especially a columnar crystal or a monocrystal tissue prepared by solidification, and is suitable for application in high-activity alloy directional solidification technology or the monocrystal preparation process.
Description
Technical field
The present invention relates to a kind of refractory material and application, particularly relate to the application of a kind of refractory material in alloy melt directional solidification processes, be applied to directional solidification cast technique field.
Background technology
Directional solidification processes process is updated and is perfect, more and more ripe, is therefore successfully applied to foundry goods such as manufacturing aero-engine and industry gas turbine turbo blade.Directional solidification has determined that by the course of work of ceramic shell the condition of work of ceramic shell material is very harsh.Shell need to work long hours under the high temperature of 1500～1600 DEG C, and in directional solidification process, shell contacts with high temperature alloy liquation and keeps complete at least 1h or longer of time.Therefore will obtain high-quality shell, type shell material should meet following requirement: 1. type shell material and high temperature alloy liquid wetting are good, under long-time high temperature high vacuum condition, does not produce obvious chemical reaction between molten metal and shell; 2. shell has enough heat resisting temperatures, elevated temperature strength and high-temperature creep resistance, can resist mechanical shock and the thermal shock of motlten metal; 3. shell has good and stable thermophysical property, and thermal coefficient of expansion is low, heat conductivility meets the demands; Collapsibility is good, after cast, easily removes from foundry goods.
For titanium alloy, the chemism high due to alloy melt can react with common shell refractory material, the field trash that reaction generates is except meeting impacts the surface quality of cast alloy, also can destroy the growth of column crystal or monocrystalline, to such an extent as to cast can not get the oriented freezing organization that we want later.Taking the TiAl alloy in titanium alloy as example, TiAl intermetallic compound has high specific strength, high elastic modulus, good creep resistant, anti-oxidant, high temperature resistant and fire resistance, density is low less than 50% of nickel-base alloy, is considered to the lightweight high-temperature structural material meriting attention most within the scope of 85～1000 DEG C.But this alloy mechanical property at high temperature has obvious directionality, be 0 ° with the angle of lamellar orientation in loading time, the plasticity of alloy and intensity can reach good coupling.For example, according to molar fraction, the ingot casting with directional solidification lamellar structure of Ti-46Al-1.5Mo-0.2C can obtain at 210 MPa, and at 750 DEG C, through 200 h, the deformation of creep is only 0.15%, steady state creep strain rate approaches 10
-10s
-1excellent properties, if conventional cast TiAl alloy vane can be developed into orientation or single crystal blade, can greatly improve the performance level of compressor.But due to the high chemism of melts of titanium alloy, can there is chemical reaction in various degree with common refractory material, so that can not get desirable oriented freezing organization in the alloy directionally solidified process of TiAl.Therefore yet there are no the relevant report about the alloy directionally solidified foundry goods application of TiAl.
At SrO-ZrO
2in binary system, SrZrO
3be the infusible compound with cubic perovskite structure of a fusing point up to 2600 DEG C, macroscopic property is stable, can be used as high-temperature solid electrolyte, high-temperature structural ceramics and refractory material.At present, both at home and abroad to SrZrO
3research as refractory material is sprawled and is come, and in some melting, has been used as the raw material of reaction vessel as refractory material, for example, reports by SrZrO
3be prepared into crucible and be successfully applied to the TiNi that chemism is slightly low, the melting of TiFe alloy, be applied in directional solidification processes but yet there are no it.
Summary of the invention
In order to solve prior art problem, the object of the invention is to overcome the deficiency that prior art exists, a kind of directional solidification composite oxides shell is provided, use SrO-ZrO
2composite oxide is as the key component of the surface material of shell, adopt shell of the present invention can significantly reduce alloy with high activity in directional solidification process with the interfacial reaction degree of type shell material, obtain more preferably oriented freezing organization, especially solidify and prepare column crystal or single crystal organization, be adapted at applying in alloy with high activity directional solidification processes or single crystal preparation process.
Create object for reaching foregoing invention, the present invention adopts following technical proposals:
A kind of directional solidification processes composite oxides shell, the surface material of shell is mainly SrO-ZrO
2type composite oxide refractory material, according to constituent mass percentage, described SrO-ZrO
2the SrO that composite oxide refractory material main component is 40-45wt%, the ZrO of 55-60wt%
2other impurity with content 0-3wt %.
As the preferred technical scheme of the present invention, shell surface layer solidifies connecting shaping by shell surface layer slurry and shell surface layer sanding material, the blending ingredients of described shell surface layer slurry mainly comprises prepares powder, binding agent and auxiliary additive for slurry, wherein auxiliary additive comprises surfactant and defoamer, the aggregate of described shell surface layer stucco is powder body material, and the preparation slurry in described shell surface layer slurry is all SrO-ZrO with the aggregate powder of powder and shell surface layer sanding material
2composite oxide refractory material, the preparation slurry in shell surface layer slurry is 10-40um by the average grain diameter of powder, the average grain diameter of the aggregate powder that the stucco of shell surface layer is used is 160-200um.
As the further preferred technical scheme of the present invention, according to constituent mass percentage, described shell surface layer slurry formula is: preparation slurry powder is 65-95%, binding agent is 5-35%, and the consumption of auxiliary additive adds by the usage of sizing agent of actual preparation, and wherein surfactant is 0-0.5wt%, defoamer is 0-0.5wt%, that is: slurry gross mass is 100g, and surfactant should add 0-0.5g, and defoamer should add 0-0.5g.
The binding agent of above-mentioned preparation surface layer slurry preferably adopts yttrium colloidal sol or zirconium colloidal sol.
Above-mentioned preparation surface layer slurry surfactant used preferably adopts stearic acid or JFC, and above-mentioned preparation surface layer slurry defoamer used preferably adopts dimethyl silicone polymer or n-butanol.
Above-mentioned directional solidification processes is applied to the directional solidification processes of melts of titanium alloy with composite oxides shell.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. directional solidification processes of the present invention uses in directional solidification processes with composite oxides shell, compared with common precision casting shell, can stand rugged environment more, and investment shell intensity is high, and high-temperature stability is good;
2. for having under high temperature compared with for high chemically active titanium alloy, directional solidification processes of the present invention possesses very high chemical stability with composite oxides shell, can effectively prevent that type shell material reacts with alloy melt in directional solidification process, the forming process of protection oriented freezing organization;
3. directional solidification processes use composite oxides shell of the present invention and graphite, CaO, ZrO
2, Al
2o
3compare etc. common shell, can reduce alloy with high activity in directional solidification process with the interfacial reaction degree of type shell material, obtain more preferably oriented freezing organization, especially prepare column crystal or single crystal organization, be adapted at the application in alloy with high activity directional solidification style or monocrystalline style preparation process.
Brief description of the drawings
Fig. 1 the present embodiment shell of the present invention carries out type shell material and the metal freezing contact interface sector scanning Electronic Speculum picture of directional solidification experiment.
Detailed description of the invention
Details are as follows for the preferred embodiments of the present invention:
In the present embodiment, taking the directional solidification of the TiAl alloy in titanium alloy as example, under the prerequisite of the present embodiment, implement, provided detailed embodiment and concrete steps process, but protection scope of the present invention is not limited to the present embodiment.Surface layer binding agent yttrium colloidal sol, backing layer refractory material EC95 electrofused mullite, the backing layer adhesive silicon sol in this example, mentioned are all Modeling Materials conventional in hot investment casting, and the protection domain of application is not subject to these materials limitations.The present embodiment is realized the application of composite oxides shell in the alloy directionally solidified technique of TiAl by following steps.
one) preparation of composite oxides shell for directional solidification processes
1. the preparation of shell surface layer slurry: 10L yttrium colloidal sol is poured in size barrel, and start button stirs size barrel; In size barrel, add 5g surfactant stearic acid; To cross 325 mesh sieves with powder through pretreated above-mentioned preparation slurry, sub-sieve obtains powder 35kg; Powder is slowly added in size barrel and stirred; After adding, powder in size barrel, adds 5g defoamer n-butanol again.After stirring 24h, control viscosity between 27-52s, flow cup used is for using the portable copper flow cup of LND-3.
2. the preparation of shell backing layer layer slurry: 10L Ludox is poured in size barrel, and start button stirs size barrel; 27kg technical grade 325 order EC95 electrofused mullites are poured in size barrel and stirred.After stirring 24h, control viscosity between 17-27s, flow cup used is for using the portable copper flow cup of LND-3.
3. the preparation of shell surface layer: middle temperature wax is pressed into shell required form, puts into cleaning fluid after compacting and clean with wipe oil, rinse with clear water subsequently and dry; Wax pattern, before invading investment precoat, first records slurry viscosity with viscosimeter, and viscosity can be invaded between 27-52s; Wax pattern is put into slurry, rotates 3-5s, then takes out wax pattern is controlled to slurry, after treating that unnecessary slurry pours off, carries out surperficial stucco with 100-80 object refractory material powder, and stucco forms shell surface layer evenly, comprehensively.
4. shell surface layer is dry: the surface shell that painting is hung up properly is dried as for 21 ° of C of thermostatic chamber, and controlled humidity scope is 65-75%, and be 24h drying time.
5. the preparation of shell backing layer: the preparation of shell backing layer is identical with the step of common hot investment casting, slurry viscosity is controlled at 17-27s, humidity range is that 40-50%, drying time are 12 hours.
6. the dewaxing of shell: adopt high steam dewaxing, 180 ° of C of dewaxing temperature, dewaxing pressure 7.2MPa, dewaxing time 10min.
7. the roasting of shell: the sintering temperature of shell is 200 ° of C insulation 1h, and 1550 ° of C are incubated 4 hours, then cool to room temperature with the furnace.
two) metal directional solidification experiment
In vacuum oriented stove, carry out directional solidification experiment, the composite oxide crucible that the crucible that vacuum oriented stove adopts is same material.Load weighted TiAl alloy bar or ingot are placed in crucible, made shell is fixed on water-cooled copper is tried to get to the heart of a matter seat, close fire door.Furnace is evacuated to 5 × 10
-3pa, the more anti-high-purity argon gas that fills is to 0.05MPa, prepurging 3-5 time so repeatedly, last directional solidification experiment is carried out under the protection of 0.05MPa high-purity argon gas.Shell is carried out to preheating, the TiAl alloy in crucible is carried out to induction melting simultaneously, treat that the alloy in crucible melts completely, and the preheat temperature of shell is while reaching 1600 ° of C, pours into a mould; Be poured rear alloy melt and in shell, be incubated 10min, carry out directional solidification experiment with v=3mm/min subsequently.Adopt the present embodiment shell to carry out the type shell material of directional solidification experiment and the interface zone constituent analysis of metal freezing material referring to table 1.
Table 1. adopts the present embodiment shell to carry out the interface zone constituent analysis of type shell material and the metal freezing material of directional solidification experiment
The SrO-ZrO of the present embodiment
2the powder of type composite oxide refractory material comprises that preparation slurry use and surface layer stucco are with two kinds, the powder of composite oxide refractory material all passes through the special pre-treatment of physics or chemical method, the binding agent that will use in the present embodiment shell surface layer slurry does not react with titanium alloy, zircaloy melt, has good stability.Referring to Fig. 1, adopting the present embodiment powder is shell moulds in directional solidification prepared by surface material, faint with the interfacial reaction of TiAl alloy after directional solidification, can obtain having the TiAl alloy of oriented freezing organization.With common graphite, CaO, ZrO
2or Al
2o
3compare Deng shell, the present embodiment composite shell can reduce high activity TiAl alloy in directional solidification process with the interfacial reaction degree of type shell material, obtain the oriented freezing organization of more preferably column crystal or monocrystalline.Be adapted at the application in the alloy directionally solidified style of TiAl or monocrystalline style preparation process.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; can also make multiple variation according to the object of innovation and creation of the present invention; the change made under all Spirit Essences according to technical solution of the present invention and principle, modification, substitute, combination, simplify; all should be equivalent substitute mode; as long as goal of the invention according to the invention; only otherwise deviate from know-why and the inventive concept of directional solidification processes of the present invention composite oxides shell and application thereof, all belong to protection scope of the present invention.
Claims (6)
1. a directional solidification processes composite oxides shell, is characterized in that: the surface material of shell is mainly SrO-ZrO
2type composite oxide refractory material, according to constituent mass percentage, described SrO-ZrO
2the SrO that composite oxide refractory material main component is 40-45wt%, the ZrO of 55-60wt%
2other impurity with content 0-3 wt %.
2. directional solidification processes composite oxides shell according to claim 1, it is characterized in that: shell surface layer solidifies connecting shaping by shell surface layer slurry and shell surface layer sanding material, the blending ingredients of described shell surface layer slurry mainly comprises prepares powder, binding agent and auxiliary additive for slurry, wherein auxiliary additive comprises surfactant and defoamer, the aggregate of described shell surface layer stucco is powder body material, and the preparation slurry in described shell surface layer slurry is all SrO-ZrO with the aggregate powder of powder and shell surface layer sanding material
2composite oxide refractory material, the preparation slurry in shell surface layer slurry is 10-40um by the average grain diameter of powder, the average grain diameter of the aggregate powder that the stucco of shell surface layer is used is 160-200um.
3. directional solidification processes composite oxides shell according to claim 2, it is characterized in that, according to constituent mass percentage, described shell surface layer slurry formula is: preparation slurry powder is 65-95%, and binding agent is 5-35%, the consumption of auxiliary additive adds by the usage of sizing agent of actual preparation, wherein surfactant is 0-0.5wt%, and defoamer is 0-0.5wt%, that is: slurry gross mass is 100g, surfactant should add 0-0.5g, and defoamer should add 0-0.5g.
4. according to the composite oxides shell of directional solidification processes described in claim 2 or 3, it is characterized in that: the binding agent of preparation surface layer slurry is yttrium colloidal sol or zirconium colloidal sol.
5. according to the composite oxides shell of directional solidification processes described in claim 2 or 3, it is characterized in that: preparation surface layer slurry surfactant used is stearic acid or JFC, preparation surface layer slurry defoamer used is dimethyl silicone polymer or n-butanol.
6. an application for composite oxides shell for directional solidification processes described in claim 1, is characterized in that: the directional solidification processes that is applied to melts of titanium alloy.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282857A (en) * | 2017-05-12 | 2017-10-24 | 上海大学 | MgO‑SrZrO3Composite shell, using and preparation method thereof |
| CN107311668A (en) * | 2017-05-12 | 2017-11-03 | 上海大学 | MgO‑BaZrO3Composite shell, using and preparation method thereof |
| CN107344856A (en) * | 2017-05-12 | 2017-11-14 | 上海大学 | MgAl2O4‑BaZrO3Composite shell, using and preparation method thereof |
| CN111545711A (en) * | 2020-05-19 | 2020-08-18 | 中国科学院金属研究所 | Preparation method of thermal shock resistant ceramic shell for high-temperature alloy LMC (melt-solidified metallic) directional solidification |
| CN111590056A (en) * | 2020-05-22 | 2020-08-28 | 东方电气集团东方汽轮机有限公司 | Casting structure and casting method for directional solidification of high-temperature alloy |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282857A (en) * | 2017-05-12 | 2017-10-24 | 上海大学 | MgO‑SrZrO3Composite shell, using and preparation method thereof |
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| CN107344856A (en) * | 2017-05-12 | 2017-11-14 | 上海大学 | MgAl2O4‑BaZrO3Composite shell, using and preparation method thereof |
| CN107282857B (en) * | 2017-05-12 | 2019-08-06 | 上海大学 | MgO-SrZrO3Composite shell, using and preparation method thereof |
| CN107344856B (en) * | 2017-05-12 | 2021-01-12 | 上海大学 | MgAl2O4-BaZrO3Composite shell, application and preparation method thereof |
| CN111545711A (en) * | 2020-05-19 | 2020-08-18 | 中国科学院金属研究所 | Preparation method of thermal shock resistant ceramic shell for high-temperature alloy LMC (melt-solidified metallic) directional solidification |
| CN111545711B (en) * | 2020-05-19 | 2022-04-05 | 中国科学院金属研究所 | Preparation method of thermal shock resistant ceramic shell for high-temperature alloy LMC (melt-solidified metallic) directional solidification |
| CN111590056A (en) * | 2020-05-22 | 2020-08-28 | 东方电气集团东方汽轮机有限公司 | Casting structure and casting method for directional solidification of high-temperature alloy |
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Application publication date: 20140702 |