CN107216156A - MgAl2O4‑SrZrO3Composite shell, using and preparation method thereof - Google Patents

MgAl2O4‑SrZrO3Composite shell, using and preparation method thereof Download PDF

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CN107216156A
CN107216156A CN201710333129.8A CN201710333129A CN107216156A CN 107216156 A CN107216156 A CN 107216156A CN 201710333129 A CN201710333129 A CN 201710333129A CN 107216156 A CN107216156 A CN 107216156A
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shell
mgal
srzro
surface layer
slurry
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李重河
鲁雄刚
高鹏越
李凯
周路海
王世华
张东
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • B22C9/04—Use of lost patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
    • B28B1/38—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon by dipping
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C04B35/443—Magnesium aluminate spinel
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/482—Refractories from grain sized mixtures
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron

Abstract

The invention discloses a kind of MgAl2O4‑SrZrO3Composite shell, using and preparation method thereof, based on MgAl2O4Alloy with high activity SrZrO3Composite shell, and be applied in hot investment casting and directional solidification.The Modeling Material of the composite shell includes SrZrO3, aluminum-spinel, yttrium colloidal sol, Ludox, surfactant stearic acid, defoamer n-butanol.Composite form is prepared using precision casting process, including wax-pattern making, coating preparation, the process such as aggregate is coated with, formwork is dewaxed, formwork is calcined.The composite form size performance of the present invention is stable, is coated with and good flowing properties, it is easy to preserve, the features such as formwork has preferable stability, intensity, thermal shock resistance, the alloy with high activity any surface finish obtained after hot investment casting and directional solidification, pollution layer is relatively thin.

Description

MgAl2O4-SrZrO3Composite shell, using and preparation method thereof
Technical field
The present invention relates to a kind of refractory material, using and preparation method thereof, more particularly to a kind of shell, using and its system Preparation Method, applied to alloy with high activity hot investment casting and directional solidification technique field.
Background technology
For high activity alloy, because the high chemism of alloy melt can be sent out with common shell refractory material Raw reaction, reacts the field trash of generation in addition to it can not only be impacted to the surface quality for pouring into a mould alloy, and solidifying in orientation Gu during can also destroy the growth of column crystal or monocrystalline so that cast after cannot get the directional solidification group that we want Knit.By taking the TiAl alloy in titanium alloy as an example, TiAl intermetallic compound has high specific strength, high elastic modulus, and excellent is anti- Creep, anti-oxidant, high temperature resistant and fire resistance, density are low less than the 50% of nickel-base alloy, it is considered to be 850 DEG C~1000 DEG C models The lightweight high-temperature structural material most merited attention in enclosing.But the mechanical property of this alloy at high temperature has obvious direction Property, when the angle in loading with lamellar orientation is 0 °, the plasticity and intensity of alloy can reach good matching.Such as Ti- 46Al-1.5Mo-0.2C (molar fraction %) ingot casting with directional solidification lamellar structure can be obtained in 210MPa, 750 DEG C Under, through 200h, the deformation of creep is only 0.15%, excellent properties, if can be fixed by conventional cast TiAl alloy developer blade To or single crystal blade, will can greatly improve the performance level of compressor.But it is due to the high chemism of melts of titanium alloy, can be with Different degrees of chemical reaction occurs for common refractory material, so that cannot be preferable in TiAl alloy directional solidification process Oriented freezing organization.Al in hot investment casting2O3And mullite is a kind of most frequently used refractory material, is typically used to formwork Surface layer and backing layer making, but because the requirement in alloy with high activity hot investment casting and directional solidification process to formwork is more severe Carve, traditional Al2O3Surface material and mullite backsheet can not be met.
More high activity hot investment casting shell is used at present, is broadly divided into：Graphite shell, tungsten surface layer ceramic mould Shell, New Oxide Ceramic Shell Mould etc..Wherein, the casting that graphite shell is poured into a mould out, the α fragility for having one layer of carburizing on the surface Layer, thickness is about 0.2~0.3mm, and it is possible to trigger under stress the generation and extension of crackle.Such as graphite shell Heat endurance have certain limit, when graphite is contacted with titanium liquid, under conditions of Activation energy is reached, it is possible to occur anxious Acute heat release chain reaction, therefore the complicated titanium alloy casting of the unsuitable casting large of graphite shell.When prepared by tungsten surface layer ceramic shell, Tungsten powder is used as the filler in coating, and the performance of tungsten powder has great influence to the quality of shell, and tungsten powder should have higher pure Degree, impurity content no more than defined standard, oxygen, carbon content it is exceeded, the quality of casting will be influenceed.Tungsten surface layer investment shell Solvent dewaxing must be used, thus has very big injury to health, while also polluting environment.The face of New Oxide Ceramic Shell Mould It is main in layer and adjacent bed coating to have used zirconium oxide, yittrium oxide, calcium oxide etc. to react less oxide with titanium liquid, wherein with oxygen Change yttrium preferable as the investment precoat casting character of filler, but yittrium oxide price is expensive, and easily oxygenation.Other oxide ceramics Shell can not be avoided in cast(ing) surface formation α pickups layer, and the thickness of α pickups layer is from 0.02~0.2mm.
SrZrO3It is a kind of highly stable refractory material of chemical property, with stable chemical property, it is in water, weak Do not chemically reacted in acid, highly basic, so containing SrZrO3Coating stabilization be difficult gelling.SrZrO3Fusing point be up to 2600 DEG C of the infusible compound with cubic perovskite structure, macroscopic property is stable, can be used as high-temperature solid electrolyte, height Warm structural ceramics and refractory material, with good thermal shock resistance, and it is cheap.At present, both at home and abroad to SrZrO3As resistance to Drawout comes for the research of fiery material, has been used as the raw material of reaction vessel in some meltings as refractory material, for example, having Report SrZrO3It is prepared into crucible and is successfully applied to Ti6Al4V and slightly lower TiNi, TiFe alloy of chemism Melting, but have no relevant report applied to alloy with high activity melting.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind MgAl2O4-SrZrO3Composite shell, using and preparation method thereof, material more stable SrZrO higher using fusing point3With MgAl2O4Respectively as the surface layer and backsheet of formwork, applied in alloy with high activity hot investment casting and directional solidification processes, The composite form size performance of the present invention is stable, is coated with and good flowing properties, it is easy to preserve, formwork have preferable stability, The features such as intensity, thermal shock resistance, the alloy with high activity any surface finish obtained after hot investment casting and directional solidification, pollution layer compared with It is thin, with important industrial value.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of MgAl2O4-SrZrO3Composite shell, using SrZrO3As the surface material of shell, and use MgAl2O4Do For the backsheet of shell, mainly by SrZrO3Surface layer and MgAl2O4Backing layer combines to form composite shell.
As currently preferred technical scheme, in SrZrO3In surface layer, SrZrO3Particle diameter be 44-74 μm, or SrZrO3With particle diameter it is respectively that 44-74 μm and granularity less than 44 μm form combination grain material by level.
As currently preferred technical scheme, in MgAl2O4In backing layer, MgAl2O4Particle diameter be 44-124 μm.
As the further preferred technical scheme of such scheme, in SrZrO3Surface layer and MgAl2O4It is additionally provided between backing layer SrZrO3Stucco layer, SrZrO3The particle diameter for the SrZrO3 aggregates that stucco layer is used is 150-420 μm；In MgAl2O4The appearance of backing layer Face is herein in connection with one layer of MgAl2O4Stucco layer, MgAl2O4The MgAl that stucco layer is used2O4The particle diameter of aggregate is 124-710 μm.
A kind of MgAl of the present invention2O4-SrZrO3The application of composite shell, applied to the hot investment casting of alloy with high activity and fixed To solidifying process.MgAl of the present invention2O4-SrZrO3Composite shell is preferably as smelting titanium alloy or the sidewall of crucible of zircaloy.
A kind of MgAl of the present invention2O4-SrZrO3The preparation method of composite shell, comprises the following steps：
A. the preparation of shell surface layer slurry：
Measured with weight percentages of components, the coating raw material formula of the surface material of shell is mainly：SrZrO3For 95-65%, yttrium colloidal sol is 5-35%；Coating raw material is configured to SrZrO3Slurries, are used as the SrZrO of raw material3Particle diameter be 44- 74 μm, or SrZrO3With particle diameter it is respectively that 44-74 μm and granularity less than 44 μm form combination grain raw material by level, SrZrO3The specific preparation process of slurries is：Yttrium colloidal sol is poured into size barrel first, and the material in size barrel is stirred Mix pretreatment；Then SrZrO3 powder powders are gradually added in size barrel and continue to be stirred；Controlled after stirring at least 24h Viscosity obtains shell surface layer slurry between 17-37s；As currently preferred technical scheme, in shell surface layer slurry also Addition shell surface layer slurry total amount 0.1-0.5wt% surfactant and disappearing for shell surface layer slurry total amount 0.1-0.5wt% Infusion, when carrying out the preparation of shell surface layer slurry, first pours into yttrium colloidal sol in size barrel, and the material in size barrel is entered Row stirring pretreatment, then add into size barrel surfactant；Then SrZrO3 powders powder is gradually added size barrel relaying It is continuous to be stirred, after SrZrO3 powders powder is added and finished, then add into size barrel defoamer；After being stirred, then Slurry viscosity control is carried out, shell surface layer slurry is obtained；Surfactant is preferred to use stearic acid, and defoamer is preferred to use positive fourth Alcohol；
B. the preparation of shell backing layer slurry：
Measured with weight percentages of components, the backing layer coating raw material formula of shell is mainly：MgAl2O4For 95- 65%, Ludox is 5-35%；Coating raw material is configured to MgAl2O4Slurries, MgAl2O4Slurries use MgAl2O4Particle size diameter For 44-124 μm of MgAl2O4Powder body material is made, MgAl2O4The specific preparation process of slurries is：Ludox is poured into slurry first In charging basket, and pretreatment is stirred to the material in size barrel；Then by MgAl2O4Powder powder is progressively poured into size barrel Proceed stirring；Control viscosity obtains shell backing layer slurry between 17-27s after stirring at least 24h；It is used as the present invention It is preferred that technical scheme, shell backing layer slurry total amount 0.1-0.5wt% surfactant is also added in shell backing layer slurry With shell backing layer slurry total amount 0.1-0.5wt% defoamer, carry out shell backing layer slurry preparation when, first by Ludox Pour into size barrel, and pretreatment is stirred to the material in size barrel, then add into size barrel surfactant；Then By MgAl2O4Powder powder, which is gradually added in size barrel, to be continued to be stirred, in MgAl2O4After the addition of powder powder is finished, then to Defoamer is added in size barrel；After being stirred, then slurry viscosity control is carried out, obtain shell backing layer slurry；Surface-active Agent is preferred to use stearic acid, and defoamer is preferred to use n-butanol；
C. the preparation of shell surface layer：
Shape needed for middle temperature wax is pressed into shell first, is put into cleaning fluid after compacting and cleans to go to degrease, then Rinsed and dried with clear water；In wax pattern before immersion shell surface layer slurry, shell surface layer slurry viscosity is first measured with viscosimeter, When shell surface layer slurry viscosity can immerse wax pattern between 17-37s；Then wax pattern is put into the shell prepared in step a In surface layer slurry, and wax pattern is kept into rotation 3-5s, further take out and drain pulp is carried out to wax pattern, treat that unnecessary shell surface layer slurry pours off Afterwards, with the SrZrO that particle diameter is 150-420 μm3Aggregate powder carries out the uniform stucco in surface, that is, forms shell surface layer precast body；
D. the drying of shell surface layer：
The shell surface layer precast body that hangs up properly will be applied in step c it is placed in temperature and be not less than in 21 DEG C of thermostatic chamber, is done Dry, it is 65-75% to control the humidity range in thermostatic chamber, and drying time is no less than 24h, makes to be incorporated into the shell surface layer in wax pattern Dry solidification；
E. the preparation of shell backing layer：
In the wax pattern for combining shell surface layer before immersion shell backing layer slurry, shell backing layer slurry is first measured with viscosimeter Viscosity, when shell backing layer slurry viscosity can immerse the wax pattern with reference to shell surface layer between 17-27s；Wax pattern is put into In the shell backing layer slurry prepared in step b, and the wax pattern for combining shell surface layer is kept rotating 3-5s, then wax pattern is taken out Come, drain pulp is carried out to shell surface layer surface, is 124-710 μm with particle diameter after treating that unnecessary shell backing layer slurry pours off MgAl2O4Aggregate powder carries out the uniform stucco in surface, that is, forms composite shell precast body；
F. the drying of shell backing layer：
The composite shell precast body that hangs up properly will be applied in step e it is placed in temperature and be not less than in 21 DEG C of thermostatic chamber, is done Dry, it is 40-50% to control the humidity range in thermostatic chamber, and drying time is no less than 12h, makes to be incorporated into SrZrO3Stucco layer is outside Shell outer layer dry solidification, that is, obtain MgAl2O4-SrZrO3The assembly of composite shell and wax pattern；
G. the dewaxing of shell：
Using high steam process for dewaxing, control dewaxing temperature is not less than 180 DEG C, and control dewaxing pressure is not less than 7.2MPa, the control dewaxing time is not less than 10min, completes the MgAl to being prepared in step f2O4-SrZrO3Composite shell and wax pattern Assembly dewaxing treatment process, obtain MgAl2O4-SrZrO3Composite shell biscuit；
H. the roasting of composite shell：
The MgAl that will be prepared in step g2O4-SrZrO3Composite shell biscuit carries out calcination process, first control roasting temperature Not higher than 200 DEG C of degree, and at least insulation 1h carries out low-temperature bake；Then sintering temperature is controlled to be not less than 1600 DEG C, and at least It is incubated 8h and carries out high-temperature roasting；Then carry out cooling to room temperature with the furnace, finally give MgAl2O4-SrZrO3Composite shell finished product.
The present invention compared with prior art, substantive distinguishing features and remarkable advantage is obviously protruded with following：
1. composite form size performance of the present invention is stable, it is coated with and good flowing properties, it is easy to preserve, formwork has preferable The features such as stability, intensity, thermal shock resistance, the alloy with high activity any surface finish obtained after hot investment casting and directional solidification, Pollution layer is relatively thin, is adapted to the application in alloy with high activity hot investment casting and directional solidification process；
2. MgAl of the present invention2O4-SrZrO3Composite shell can reduce including titanium alloy, zircaloy alloy with high activity in essence Interfacial reaction degree in close casting and directional solidification process with type shell material, obtains the less casting of pollution layer and more preferable Column crystal or monocrystalline oriented freezing organization, with important industrial value.
Brief description of the drawings
Fig. 1 is the MgAl of the embodiment of the present invention one2O4-SrZrO3The Interface Microstructure shape appearance figure of composite shell and high activity metal.
Embodiment
Details are as follows for the preferred embodiments of the present invention：
Embodiment one：
In the present embodiment, a kind of MgAl2O4-SrZrO3Composite shell, using SrZrO3As the surface material of shell, And use MgAl2O4As the backsheet of shell, mainly by SrZrO3Surface layer and MgAl2O4Backing layer combines to form composite shell.
A kind of the present embodiment MgAl2O4-SrZrO3The preparation method of composite shell, comprises the following steps：
A. the preparation of shell surface layer slurry：
Measured with weight percentages of components, the coating raw material formula of the surface material of shell is：SrZrO3, yttrium it is molten Glue, surfactant and defoamer；Above-mentioned coating raw material is configured to SrZrO3Slurries, the preparation slurry by pretreatment is used SrZrO3Powder crosses 325 mesh sieves, obtains the SrZrO that particle diameter is 44 μm3Powder body material, sub-sieve obtains powder 35kg, SrZrO3Slurry The specific preparation process of liquid is：10L yttrium colloidal sols are poured into size barrel first, and start agitator button, in size barrel Material is stirred pretreatment, then the addition 5g surfactant stearic acid into size barrel；Then by 35kg SrZrO3 powder powder Material, which is gradually added in size barrel, to be continued to be stirred, and is added after SrZrO3 powders powder is added and finished, then into size barrel 5g defoamer n-butanols；Control viscosity obtains shell surface layer slurry between 17-37s after stirring 24h, measures shell surface layer Flow cup used in the viscosity of slurry is the portable copper flow cups of LND-3；
B. the preparation of shell backing layer slurry：
Measured with weight percentages of components, the backing layer coating raw material formula of shell is mainly：MgAl2O4, Ludox, Surfactant and defoamer；Coating raw material is configured to MgAl2O4Slurries, by the preparation slurry by pretreatment MgAl2O4Powder uses the mesh aluminum-spinel of 27kg technical grades 325, MgAl2O4The specific preparation process of slurries is：First by 10L Ludox is poured into size barrel, and starts agitator button, and pretreatment is stirred to the material in size barrel；Then will 27kgMgAl2O4Powder powder, which is progressively poured into size barrel, to be continued to be stirred；Stirring 24h after control viscosity 17-27s it Between, shell backing layer slurry is obtained, it is the portable copper viscosity of LND-3 to measure the flow cup used in the viscosity of shell backing layer slurry Cup；
C. the preparation of shell surface layer：
Shape needed for middle temperature wax is pressed into shell first, is put into cleaning fluid after compacting and cleans to go to degrease, then Rinsed and dried with clear water；In wax pattern before immersion shell surface layer slurry, shell surface layer slurry viscosity is first measured with viscosimeter, When shell surface layer slurry viscosity can immerse wax pattern between 17-37s；Then wax pattern is put into the shell prepared in step a In surface layer slurry, and wax pattern is kept into rotation 3s, further take out and drain pulp is carried out to wax pattern, treat that unnecessary shell surface layer slurry pours off it Afterwards, with the SrZrO that particle diameter is 150 μm3Aggregate powder carries out the uniform stucco in surface, that is, forms shell surface layer precast body, stucco is equal It is even, then form shell surface layer comprehensively；
D. the drying of shell surface layer：
The shell surface layer precast body that hangs up properly will be applied in step c to be placed in the thermostatic chamber of 21 DEG C of temperature, is dried, and is controlled Humidity range in thermostatic chamber is 65-75%, and drying time is 24h, makes to be incorporated into the shell surface layer dry solidification in wax pattern；
E. the preparation of shell backing layer：
In the wax pattern for combining shell surface layer before immersion shell backing layer slurry, shell backing layer slurry is first measured with viscosimeter Viscosity, when shell backing layer slurry viscosity can immerse the wax pattern with reference to shell surface layer between 17-27s；Wax pattern is put into In the shell backing layer slurry prepared in step b, and the wax pattern for combining shell surface layer is kept rotating 3s, then wax pattern is taken out, Drain pulp is carried out to shell surface layer surface, after treating that unnecessary shell backing layer slurry pours off, with the MgAl that particle diameter is 124 μm2O4Aggregate powder Body carries out the uniform stucco in surface, that is, forms composite shell precast body, and stucco is uniform, then form shell backing layer comprehensively；
F. the drying of shell backing layer：
The composite shell precast body that hangs up properly will be applied in step e to be placed in the thermostatic chamber that temperature is 21 DEG C, is dried, is controlled Humidity range in thermostatic chamber processed is 40-50%, and drying time is 12h, makes to be incorporated into SrZrO3Outside shell outside stucco layer Layer dry solidification, that is, obtain MgAl2O4-SrZrO3The assembly of composite shell and wax pattern；
G. the dewaxing of shell：
Using high steam process for dewaxing, it is 180 DEG C to control dewaxing temperature, and it is 7.2MPa to control dewaxing pressure, and control is de- The wax time is 10min, completes the MgAl to being prepared in step f2O4-SrZrO3The assembly dewaxing treatment of composite shell and wax pattern Process, obtains MgAl2O4-SrZrO3Composite shell biscuit；
H. the roasting of composite shell：
The MgAl that will be prepared in step g2O4-SrZrO3Composite shell biscuit carries out calcination process, first control roasting temperature Spend for 200 DEG C, and be incubated 1h and carry out low-temperature bake；Then it is 1600 DEG C to control sintering temperature, and is incubated 8h progress high-temperature roastings； Then carry out cooling to room temperature with the furnace, finally give MgAl2O4-SrZrO3Composite shell finished product.
Directional solidification is tested：
Solidification experiments are oriented in vacuum oriented stove, the crucible that vacuum oriented stove is used is manufactured in the present embodiment MgAl2O4-SrZrO3The compound crucible of composite shell phase same material.Load weighted titanium sponge, aluminium niobium alloy and fine aluminium are placed In crucible, made shell is fixed on water cooled copper plate base, fire door is closed.Furnace is evacuated to 5 × 10-3Pa, then instead High-purity argon gas is filled to 0.05MPa, so prepurging 3-5 times repeatedly, and last directional solidification experiment is in the protection of 0.05MPa high-purity argon gas Lower progress.To MgAl manufactured in the present embodiment2O4-SrZrO3Composite shell is preheated, while being carried out to the alloy in crucible Induction melting, treats that the alloy in crucible is completely melt, and the preheating temperature of shell is when reaching 1500 DEG C, is poured into a mould；Pour Alloy melt is then oriented solidification experiments in shell inside holding 30min with v=1mm/min after finishing.
MgAl manufactured in the present embodiment2O4-SrZrO3The experiment beneficial effect of composite shell：
Using SrZrO3For surface layer, MgAl2O4With TiAl after the shell moulds in directional solidification prepared for backsheet, directional solidification The interfacial reaction of alloy is faint, the TiAl alloy with directed tissue can be obtained, referring to Fig. 1.
The present embodiment is prepared for a kind of alloy with high activity hot investment casting and directional solidification composite shell, the composite shell Modeling Material include SrZrO3, aluminum-spinel, yttrium colloidal sol, Ludox, surfactant stearic acid, defoamer n-butanol. Composite form is prepared using precision casting process, including wax-pattern making, coating preparation, aggregate is coated with, formwork is dewaxed, formwork is calcined Etc. process.The present embodiment is based on MgAl2O4Alloy with high activity SrZrO3Composite shell, and in hot investment casting and directional solidification It is applied.High activity hot investment casting and directional solidification shell should have very high refractoriness, and high-temperature stability, high temperature is strong Degree, thermal shock resistance.MgAl manufactured in the present embodiment2O4-SrZrO3It is fixed in TiAl alloy that composite shell is entirely capable of meeting composite form Application requirement into solidifying process, the titanium alloy that is particularly suitable for use in, the hot investment casting of zircaloy alloy with high activity and directional solidification work Skill.State shell surface layer coating and stucco aggregate SrZrO3Pre-processed by specific physical or chemical method, by SrZrO3Surface layer and MgAl2O4SrZrO is additionally provided between backing layer3Stucco layer, makes SrZrO3Surface layer and MgAl2O4Backing layer is combined closely Together, MgAl is prevented2O4-SrZrO3Composite shell such as cracks at the defect.MgAl manufactured in the present embodiment2O4-SrZrO3It is multiple Mould assembly shell and graphite, CaO, ZrO2、Al2O3Etc. plain edition shell phase ratio, alloy with high activity can be reduced solidifying in hot investment casting and orientation Gu during interfacial reaction degree with type shell material, obtain the less casting of pollution layer and more preferably column crystal or monocrystalline Oriented freezing organization.It is adapted to the application in alloy with high activity hot investment casting and directional solidification process.The present embodiment introduces fusing point It is higher, the more stable SrZrO of material3And MgAl2O4Respectively as the surface layer and backsheet of formwork, it can realize that composite form exists Application in TiAl alloy directional solidification processes, the composite form has slurry performance stable, and coating property is good, it is easy to preserve, The features such as formwork high temperature resistant, good thermal shock, high chemical stability, the cast(ing) surface pollution layer of preparation is thin, dimensional accuracy height etc. Feature.
The present embodiment is carried out by example of the directional solidification of the TiAl alloy in titanium alloy on the premise of the technical program Implement, give detailed embodiment and specific steps process, but protection scope of the present invention is not limited in following examples. The surface layer binding agent yttrium colloidal sol mentioned in this example, backing layer adhesive silicon sol are the Modeling Materials commonly used in hot investment casting, The protection domain of application is not limited by these materials.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, a kind of the present embodiment MgAl2O4-SrZrO3The preparation method of composite shell, including following step Suddenly：
A. the preparation of shell surface layer slurry：This step is identical with embodiment one；
B. the preparation of shell backing layer slurry：
Measured with weight percentages of components, the backing layer coating raw material formula of shell is mainly：MgAl2O4, Ludox, Surfactant and defoamer；Coating raw material is configured to MgAl2O4Slurries, by the preparation slurry by pretreatment MgAl2O4Powder uses the mesh aluminum-spinel of 27kg technical grades 325, MgAl2O4The specific preparation process of slurries is：First by 10L Ludox is poured into size barrel, and starts agitator button, is stirred pretreatment to the material in size barrel, then to size barrel Middle addition 5g surfactant stearic acid；Then by 27kg MgAl2O4Powder powder, which is progressively poured into size barrel, to be proceeded to stir Mix, and after SrZrO3 powders powder is added and finished, then the addition 5g defoamer n-butanols into size barrel；Controlled after stirring 24h Viscosity processed obtains shell backing layer slurry between 17-27s, and it is LND-3 to measure the flow cup used in the viscosity of shell backing layer slurry Portable copper flow cup；
C. the preparation of shell surface layer：
Shape needed for middle temperature wax is pressed into shell first, is put into cleaning fluid after compacting and cleans to go to degrease, then Rinsed and dried with clear water；In wax pattern before immersion shell surface layer slurry, shell surface layer slurry viscosity is first measured with viscosimeter, When shell surface layer slurry viscosity can immerse wax pattern between 17-37s；Then wax pattern is put into the shell prepared in step a In surface layer slurry, and wax pattern is kept into rotation 5s, further take out and drain pulp is carried out to wax pattern, treat that unnecessary shell surface layer slurry pours off it Afterwards, with the SrZrO that particle diameter is 420 μm3Aggregate powder carries out the uniform stucco in surface, that is, forms shell surface layer precast body, stucco is equal It is even, then form shell surface layer comprehensively；
D. the drying of shell surface layer：This step is identical with embodiment one；
E. the preparation of shell backing layer：
In the wax pattern for combining shell surface layer before immersion shell backing layer slurry, shell backing layer slurry is first measured with viscosimeter Viscosity, when shell backing layer slurry viscosity can immerse the wax pattern with reference to shell surface layer between 17-27s；Wax pattern is put into In the shell backing layer slurry prepared in step b, and the wax pattern for combining shell surface layer is kept rotating 5s, then wax pattern is taken out, Drain pulp is carried out to shell surface layer surface, after treating that unnecessary shell backing layer slurry pours off, with the MgAl that particle diameter is 710 μm2O4Aggregate powder Body carries out the uniform stucco in surface, that is, forms composite shell precast body, and stucco is uniform, then form shell backing layer comprehensively；
F. the drying of shell backing layer：This step is identical with embodiment one；
G. the dewaxing of shell：This step is identical with embodiment one；
H. the roasting of composite shell：This step is identical with embodiment one.
The present embodiment is also prepared for a kind of alloy with high activity hot investment casting and directional solidification composite shell, the moulding of shell Material includes SrZrO3, magnesium aluminate spinel, yttrium colloidal sol, Ludox, surfactant stearic acid, defoamer n-butanol.Shell Surface material is SrZrO3, backsheet is magnesium aluminate spinel.MgAl manufactured in the present embodiment2O4-SrZrO3Composite shell is complete Application requirement of the composite form in TiAl alloy directional solidification processes can be met, the titanium alloy that is particularly suitable for use in, zircaloy height are living Property alloy precision casting and directional solidification processes.The composite form has slurry performance stable, and coating property is good, it is easy to preserve, The features such as formwork high temperature resistant, good thermal shock, high chemical stability, the cast(ing) surface pollution layer of preparation is thin, dimensional accuracy height etc. Feature.
The embodiment of the present invention is illustrated above in conjunction with accompanying drawing, but the invention is not restricted to above-described embodiment, can be with Made according to the purpose of the innovation and creation of the present invention under a variety of changes, all Spirit Essence and principle according to technical solution of the present invention Change, modification, replacement, the combination or simplified made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention, Without departing from MgAl of the present invention2O4-SrZrO3Composite shell, using and preparation method thereof technical principle and inventive concept, all Belong to protection scope of the present invention.

Claims (10)

1. a kind of MgAl2O4-SrZrO3Composite shell, it is characterised in that：Using SrZrO3As the surface material of shell, and use MgAl2O4As the backsheet of shell, mainly by SrZrO3Surface layer and MgAl2O4Backing layer combines to form composite shell.
2. MgAl according to claim 12O4-SrZrO3Composite shell, it is characterised in that：In SrZrO3It is described in surface layer SrZrO3Particle diameter be 44-74 μm, or SrZrO3With particle diameter it is respectively that 44-74 μm and granularity less than 44 μm form mixed by level Close particle size materials.
3. MgAl according to claim 12O4-SrZrO3Composite shell, it is characterised in that：In MgAl2O4It is described in backing layer MgAl2O4Particle diameter be 44-124 μm.
4. the MgAl according to Claims 2 or 32O4-SrZrO3Composite shell, it is characterised in that：In SrZrO3Surface layer and MgAl2O4SrZrO is additionally provided between backing layer3Stucco layer, SrZrO3The particle diameter for the SrZrO3 aggregates that stucco layer is used is 150-420 μ m；In MgAl2O4The outer surface of backing layer is herein in connection with one layer of MgAl2O4Stucco layer, MgAl2O4The MgAl that stucco layer is used2O4Aggregate Particle diameter is 124-710 μm.
5. MgAl described in a kind of claim 12O4-SrZrO3The application of composite shell, it is characterised in that：Closed applied to high activity The hot investment casting of gold and directional solidification processes.
6. MgAl according to claim 52O4-SrZrO3The application of composite shell, it is characterised in that：It is used as smelting titanium alloy Or the sidewall of crucible of zircaloy.
7. MgAl described in a kind of claim 12O4-SrZrO3The preparation method of composite shell, it is characterised in that including following step Suddenly：
A. the preparation of shell surface layer slurry：
Measured with weight percentages of components, the coating raw material formula of the surface material of the shell is mainly：SrZrO3For 95-65%, yttrium colloidal sol is 5-35%；Coating raw material is configured to SrZrO3Slurries, are used as the SrZrO of raw material3Particle diameter be 44-74 μm, or SrZrO3With particle diameter it is respectively that 44-74 μm and granularity less than 44 μm form combination grain raw material material by level Material, SrZrO3The specific preparation process of slurries is：Yttrium colloidal sol is poured into size barrel first, and the material in size barrel is carried out Stirring pretreatment；Then SrZrO3 powder powders are gradually added in size barrel and continue to be stirred；Controlled after stirring at least 24h Viscosity processed obtains shell surface layer slurry between 17-37s；
B. the preparation of shell backing layer slurry：
Measured with weight percentages of components, the backing layer coating raw material formula of the shell is mainly：MgAl2O4For 95- 65%, Ludox is 5-35%；Coating raw material is configured to MgAl2O4Slurries, the MgAl2O4Slurries use MgAl2O4Particle diameter A diameter of 44-124 μm of MgAl2O4Powder body material is made, MgAl2O4The specific preparation process of slurries is：Ludox is fallen first Enter in size barrel, and pretreatment is stirred to the material in size barrel；Then by MgAl2O4Powder powder progressively pours into slurry Continue to be stirred in bucket；Control viscosity obtains shell backing layer slurry between 17-27s after stirring at least 24h；
C. the preparation of shell surface layer：
Shape needed for middle temperature wax is pressed into shell first, is put into cleaning fluid after compacting and cleans to go to degrease, then with clear Water is rinsed and dried；In wax pattern before immersion shell surface layer slurry, shell surface layer slurry viscosity is first measured with viscosimeter, works as type Shell surface layer slurry viscosity can immerse wax pattern between 17-37s；Then wax pattern is put into the shell prepared in the step a In surface layer slurry, and wax pattern is kept into rotation 3-5s, further take out and drain pulp is carried out to wax pattern, treat that unnecessary shell surface layer slurry pours off Afterwards, with the SrZrO that particle diameter is 150-420 μm3Aggregate powder carries out the uniform stucco in surface, that is, forms shell surface layer precast body；
D. the drying of shell surface layer：
The shell surface layer precast body that hangs up properly will be applied in the step c it is placed in temperature and be not less than in 21 DEG C of thermostatic chamber, is done Dry, it is 65-75% to control the humidity range in thermostatic chamber, and drying time is no less than 24h, makes to be incorporated into the shell surface layer in wax pattern Dry solidification；
E. the preparation of shell backing layer：
In the wax pattern for combining shell surface layer before immersion shell backing layer slurry, shell backing layer slurry is first measured with viscosimeter and is glued Degree, when shell backing layer slurry viscosity can immerse the wax pattern with reference to shell surface layer between 17-27s；Wax pattern is put into institute State in the shell backing layer slurry prepared in step b, and the wax pattern for combining shell surface layer is kept rotating 3-5s, then wax pattern is taken out Come, drain pulp is carried out to shell surface layer surface, is 124-710 μm with particle diameter after treating that unnecessary shell backing layer slurry pours off MgAl2O4Aggregate powder carries out the uniform stucco in surface, that is, forms composite shell precast body；
F. the drying of shell backing layer：
The composite shell precast body that hangs up properly will be applied in the step e it is placed in temperature and be not less than in 21 DEG C of thermostatic chamber, is done Dry, it is 40-50% to control the humidity range in thermostatic chamber, and drying time is no less than 12h, makes to be incorporated into SrZrO3Stucco layer is outside Shell outer layer dry solidification, that is, obtain MgAl2O4-SrZrO3The assembly of composite shell and wax pattern；
G. the dewaxing of shell：
Using high steam process for dewaxing, control dewaxing temperature is not less than 180 DEG C, and control dewaxing pressure is not less than 7.2MPa, controls The dewaxing time processed is not less than 10min, completes the MgAl to being prepared in the step f2O4-SrZrO3The group of composite shell and wax pattern Fit dewaxing treatment process, obtains MgAl2O4-SrZrO3Composite shell biscuit；
H. the roasting of composite shell：
The MgAl that will be prepared in the step g2O4-SrZrO3Composite shell biscuit carries out calcination process, first control roasting temperature Not higher than 200 DEG C of degree, and at least insulation 1h carries out low-temperature bake；Then sintering temperature is controlled to be not less than 1600 DEG C, and at least It is incubated 8h and carries out high-temperature roasting；Then carry out cooling to room temperature with the furnace, finally give MgAl2O4-SrZrO3Composite shell finished product.
8. MgAl according to claim 72O4-SrZrO3The preparation method of composite shell, it is characterised in that：In the step a In, shell surface layer slurry total amount 0.1-0.5wt% surfactant and shell face is also added in the shell surface layer slurry Layer slurry total amount 0.1-0.5wt% defoamer, when carrying out the preparation of shell surface layer slurry, pours into slurry by yttrium colloidal sol first In bucket, and pretreatment is stirred to the material in size barrel, then adds into size barrel surfactant；Then SrZrO3 powder Body powder, which is gradually added in size barrel, to be continued to be stirred, and is added after SrZrO3 powders powder is added and finished, then into size barrel Enter defoamer；After being stirred, then slurry viscosity control is carried out, obtain shell surface layer slurry.
9. MgAl according to claim 72O4-SrZrO3The preparation method of composite shell, it is characterised in that：In the step b In, shell backing layer slurry total amount 0.1-0.5wt% surfactant and the shell back of the body is also added in the shell backing layer slurry Layer slurry total amount 0.1-0.5wt% defoamer, when carrying out the preparation of shell backing layer slurry, pours into slurry by Ludox first In bucket, and pretreatment is stirred to the material in size barrel, then adds into size barrel surfactant；Then by MgAl2O4 Powder powder, which is gradually added in size barrel, to be continued to be stirred, in MgAl2O4After the addition of powder powder is finished, then into size barrel Add defoamer；After being stirred, then slurry viscosity control is carried out, obtain shell backing layer slurry.
10. MgAl according to claim 8 or claim 92O4-SrZrO3The preparation method of composite shell, it is characterised in that：The table Face activating agent uses stearic acid, and the defoamer uses n-butanol.
CN201710333129.8A 2017-05-12 2017-05-12 MgAl2O4‑SrZrO3Composite shell, using and preparation method thereof Pending CN107216156A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108889924A (en) * 2018-07-27 2018-11-27 江阴鑫宝利金属制品有限公司 Ferromagnetic alloy vacuum casting short route casting method
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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CN101386067A (en) * 2008-10-28 2009-03-18 南京钢铁联合有限公司 Ladle liner and laying technique thereof
CN102962401A (en) * 2012-11-30 2013-03-13 上海大学 SrZrO3 shell for titanium and titanium alloy precise casting and preparation method thereof
CN102990006A (en) * 2012-11-30 2013-03-27 上海大学 Shell for titanium and titanium alloy precision casting and preparation method thereof

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Publication number Priority date Publication date Assignee Title
EP0268166A2 (en) * 1986-11-18 1988-05-25 Bayer Ag Molten metal and fused salt resistant materials, their production and application
CN101386067A (en) * 2008-10-28 2009-03-18 南京钢铁联合有限公司 Ladle liner and laying technique thereof
CN102962401A (en) * 2012-11-30 2013-03-13 上海大学 SrZrO3 shell for titanium and titanium alloy precise casting and preparation method thereof
CN102990006A (en) * 2012-11-30 2013-03-27 上海大学 Shell for titanium and titanium alloy precision casting and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN108889924A (en) * 2018-07-27 2018-11-27 江阴鑫宝利金属制品有限公司 Ferromagnetic alloy vacuum casting short route casting method
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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