CN107344856A - MgAl2O4‑BaZrO3Composite shell, using and preparation method thereof - Google Patents

MgAl2O4‑BaZrO3Composite shell, using and preparation method thereof Download PDF

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CN107344856A
CN107344856A CN201710333041.6A CN201710333041A CN107344856A CN 107344856 A CN107344856 A CN 107344856A CN 201710333041 A CN201710333041 A CN 201710333041A CN 107344856 A CN107344856 A CN 107344856A
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shell
mgal
bazro
surface layer
slurry
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CN107344856B (en
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周路海
李重河
孟德珍
李凯
王静
鲁雄刚
王世华
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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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    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract

The invention discloses a kind of MgAl2O4‑BaZrO3Composite shell, using and preparation method thereof, the Modeling Material of shell includes BaZrO3, aluminum-spinel, yttrium colloidal sol, Ludox, surfactant stearic acid, defoamer n-butanol.The surface material of shell is BaZrO3, backsheet is aluminum-spinel.Shell provided by the present invention and graphite, CaO, ZrO2、Al2O3Etc. plain edition shell phase ratio, the interfacial reaction degree of titanium alloy, zircaloy alloy with high activity with type shell material in hot investment casting and directional solidification process can be reduced, obtains the less casting of pollution layer and more preferably column crystal or monocrystalline oriented freezing organization.It is adapted to apply in hot investment casting and directional solidification, there is very high refractoriness, high-temperature stability, elevated temperature strength and thermal shock resistance is excellent, have important industrial value.

Description

MgAl2O4-BaZrO3Composite 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, application and its system Preparation Method, applied to alloy with high activity hot investment casting and directional solidification technique field.
Background technology
In general, alloy with high activity hot investment casting and unidirectional solidification material should meet to require as follows：
1. having high chemical stability, contacted with molten titanium and physical-chemical reaction does not occur；2. there should be high refractoriness And thermal shock resistance, after pouring liquid titanium, casting mold does not occur weak；3. intensity is high, casting mold is indeformable in operation With it is broken；4. low thermal coefficient of expansion and thermal conductivity, there is good performance；5. there are rational granularity and size distribution And granule-morphology, moisture content and gas are few；It is 6. nontoxic, "dead"；Al in hot investment casting2O3And mullite is most frequently to use A kind of refractory material arrived, is typically used to the making of the surface layer and backing layer of formwork, but due to alloy with high activity hot investment casting and Requirement in directional solidification process to formwork is harsher, traditional Al2O3Surface material and mullite backsheet can not Meet.
BaZrO3It is the infusible compound that a fusing point is up to 2600 DEG C, macroscopic property is stable, can be used as high-temp solid Electrolyte, high-temperature structural ceramics and refractory material, there is good thermal shock resistance, cubic perovskite structure, density 5.562g/ cm3It is cheap.At present, both at home and abroad to BaZrO3Drawout comes for research as refractory material, as refractory material at certain It is used as the raw material of reaction vessel in a little meltings, for example, studies have reported that, it is at present in the monocrystal yttrium barium of melting high quality Most stable of crucible material in copper oxide superconducting material, this new refractory material during yttrium barium copper oxygen superconductive material for having Advantages below：Do not contain the impurity element from crucible in monocrystal after melting, while because of change caused by crucible erosion No longer influence the alloy composition of melting, the product that can so overcome crucible material to be reacted with alloy melt and generate.And have Report BaZrO3The melting of Ti6Al4V and slightly lower TiNi, TiFe alloy of chemism is successfully applied to, but should Relevant report is had no for 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-BaZrO3Composite shell, using and preparation method thereof, material more stable BaZrO 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, Interface of the alloy with high activity for including titanium alloy, zircaloy in hot investment casting and directional solidification process with type shell material can be reduced The extent of reaction, the less casting of pollution layer and more preferably column crystal or monocrystalline oriented freezing organization are obtained, is had important Industrial value.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of MgAl2O4-BaZrO3Composite shell, using BaZrO3As the surface material of shell, and use MgAl2O4Do For the backsheet of shell, mainly by BaZrO3Surface layer and MgAl2O4Backing layer combines to form composite shell.
As currently preferred technical scheme, in BaZrO3In surface layer, BaZrO3Particle diameter be 44-74 μm, or BaZrO3It is respectively that 44-74 μm and granularity less than 44 μm form combination grain material by grading particle diameter.
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 BaZrO3Surface layer and MgAl2O4It is additionally provided between backing layer BaZrO3Stucco layer, BaZrO3The particle diameter for the BaZrO3 aggregates that stucco layer uses 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 uses2O4The particle diameter of aggregate is 124-710 μm.
A kind of MgAl of the present invention2O4-BaZrO3The 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-BaZrO3Composite shell is preferably as smelting titanium alloy or the sidewall of crucible of zircaloy.
A kind of MgAl of the present invention2O4-BaZrO3The 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：BaZrO3For 95-65%, yttrium colloidal sol are 5-35%；Coating raw material is configured to BaZrO3Slurries, the BaZrO as raw material3Particle diameter be 44- 74 μm, or BaZrO3It is respectively that 44-74 μm and granularity less than 44 μm form combination grain raw material by grading particle diameter, BaZrO3The 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 BaZrO3 powder powders are gradually added in size barrel and continue to be stirred；Controlled after at least 24h is stirred Viscosity obtains shell surface layer slurry between 17-37s；As currently preferred technical scheme, gone back in shell surface layer slurry 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, yttrium colloidal sol is poured into size barrel first, and the material in size barrel is entered Row stirring pretreatment, then surfactant is added into size barrel；Then BaZrO3 powders powder is gradually added size barrel relaying It is continuous to be stirred, after BaZrO3 powders powder adds, then defoamer is added into size barrel；After being stirred, then Slurry viscosity control is carried out, obtains shell surface layer slurry；Surfactant preferably uses stearic acid, and defoamer preferably uses 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 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 Continue to stir；Viscosity is controlled to obtain shell backing layer slurry between 17-27s after at least 24h is stirred；As the present invention Preferable 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 surfactant is added into size barrel；Then By MgAl2O4Powder powder, which is gradually added in size barrel, to be continued to be stirred, in MgAl2O4After powder powder adds, 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 preferably uses stearic acid, and defoamer preferably uses n-butanol；
C. the preparation of shell surface layer：
Medium temperature wax is pressed into shape needed for shell first, is put into cleaning fluid and is cleaned to degrease after compacting, then Rinsed and dried with clear water；In wax pattern before shell surface layer slurry is immersed, shell surface layer slurry viscosity first is measured with viscosimeter, When shell surface layer slurry viscosity can immerse wax pattern between 17-37s；Then wax pattern is put into step a the shell prepared 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, the BaZrO for being 150-420 μm with particle diameter3Aggregate 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 to be placed in thermostatic chamber of the temperature not less than 21 DEG C, 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 shell backing layer slurry is immersed, first shell backing layer slurry is 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 to be placed in thermostatic chamber of the temperature not less than 21 DEG C, 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 BaZrO3Outside stucco layer Shell outer layer dry solidification, that is, obtain MgAl2O4-BaZrO3The 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, control dewaxing time are not less than 10min, complete the MgAl to being prepared in step f2O4-BaZrO3Composite shell and wax pattern Assembly dewaxing treatment process, obtain MgAl2O4-BaZrO3Composite shell biscuit；
H. the roasting of composite shell：
The MgAl that will be prepared in step g2O4-BaZrO3Composite shell biscuit carries out calcination process, first control roasting temperature Degree is not higher than 200 DEG C, and is at least incubated 1h and carries out low-temperature bake；Then it is not less than 1600 DEG C, and at least to control sintering temperature It is incubated 8h and carries out high-temperature roasting；Then carry out cooling to room temperature with the furnace, finally give MgAl2O4-BaZrO3Composite shell finished product.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. shell provided by the present invention and graphite, CaO, ZrO2、Al2O3Etc. plain edition shell phase ratio, can reduce includes titanium conjunction Interfacial reaction degree of the alloy with high activity in hot investment casting and directional solidification process with type shell material including gold, zircaloy, The less casting of pollution layer and more preferably column crystal or monocrystalline oriented freezing organization are obtained, is adapted to accurate in alloy with high activity Application in casting and directional solidification process, applied to high activity hot investment casting and directional solidification shell, have very high resistance to Fiery degree, high-temperature stability, elevated temperature strength, thermal shock resistance；
2. the present invention uses BaZrO3For surface layer, MgAl2O4The shell moulds in directional solidification prepared for backsheet, directional solidification It is faint with the interfacial reaction of alloy with high activity afterwards, the alloy with high activity with directed tissue can be obtained, using MgAl of the present invention2O4- BaZrO3Composite shell, the alloy with high activity for including titanium alloy, zircaloy can be reduced in hot investment casting and directional solidification process With the interfacial reaction degree of type shell material, the less casting of pollution layer and more preferably column crystal or monocrystalline directional solidification are obtained Tissue, has important industrial value.
Brief description of the drawings
Fig. 1 is the MgAl of the embodiment of the present invention one2O4-BaZrO3The interfacial reaction tissue shape of composite shell and high activity metal Looks figure.
Fig. 2 is the MgAl of the embodiment of the present invention one2O4-BaZrO3Composite shell is used for metal structure shape prepared by directional solidification Looks figure.
Embodiment
Details are as follows for the preferred embodiments of the present invention：
Embodiment one：
In the present embodiment, a kind of MgAl2O4-BaZrO3Composite shell, using BaZrO3As the surface material of shell, And use MgAl2O4As the backsheet of shell, mainly by BaZrO3Surface layer and MgAl2O4Backing layer combines to form composite shell. The present embodiment MgAl2O4-BaZrO3It is as shown in Figure 2 that composite shell is used for metal structure pattern prepared by directional solidification.
A kind of the present embodiment MgAl2O4-BaZrO3The 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：BaZrO3, yttrium it is molten Glue, surfactant and defoamer；Above-mentioned coating raw material is configured to BaZrO3Slurries, the preparation slurry by pretreatment is used BaZrO3Powder crosses 325 mesh sieves, obtains the BaZrO that particle diameter is 44 μm3Powder body material, sub-sieve obtain powder 35kg, BaZrO3Slurry 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 5g surfactant stearic acid is added into size barrel；Then by 35kg BaZrO3 powder powder Material, which is gradually added in size barrel, to be continued to be stirred, and after BaZrO3 powders powder adds, then added into size barrel 5g defoamer n-butanols；Viscosity is controlled to obtain shell surface layer slurry between 17-37s, measure shell surface layer after 24h is stirred 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 by 27kg MgAl2O4Powder powder, which is progressively poured into size barrel, to be continued to be stirred；Viscosity is controlled to be obtained between 17-27s after 24h is stirred To shell backing layer slurry, the flow cup measured used in the viscosity of shell backing layer slurry is the portable copper flow cups of LND-3；
C. the preparation of shell surface layer：
Medium temperature wax is pressed into shape needed for shell first, is put into cleaning fluid and is cleaned to degrease after compacting, then Rinsed and dried with clear water；In wax pattern before shell surface layer slurry is immersed, shell surface layer slurry viscosity first is measured with viscosimeter, When shell surface layer slurry viscosity can immerse wax pattern between 17-37s；Then wax pattern is put into step a the shell prepared 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 BaZrO 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%, drying time 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 shell backing layer slurry is immersed, first shell backing layer slurry is 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 forms 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%, drying time 12h, makes to be incorporated into BaZrO3Outside shell outside stucco layer Layer dry solidification, that is, obtain MgAl2O4-BaZrO3The 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-BaZrO3The assembly dewaxing treatment of composite shell and wax pattern Process, obtain MgAl2O4-BaZrO3Composite shell biscuit；
H. the roasting of composite shell：
The MgAl that will be prepared in step g2O4-BaZrO3Composite 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 and carries out high-temperature roasting； Then carry out cooling to room temperature with the furnace, finally give MgAl2O4-BaZrO3Composite shell finished product.
Directional solidification is tested：
Solidification experiments are oriented in vacuum oriented stove, crucible is manufactured in the present embodiment used by vacuum oriented stove MgAl2O4-BaZrO3The 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, closes fire door.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 protected in 0.05MPa high-purity argon gas Lower progress.To MgAl manufactured in the present embodiment2O4-BaZrO3Composite shell is preheated, while the alloy in crucible is carried out Induction melting, treat that the alloy in crucible is completely melt, and when the preheating temperature of shell reaches 1500 DEG C, 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-BaZrO3The experiment beneficial effect of composite shell：
Using BaZrO3For surface layer, MgAl2O4The shell moulds in directional solidification prepared for backsheet, after directional solidification with TiAl 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 Modeling Materials of shell Material includes BaZrO3, magnesium aluminate spinel, yttrium colloidal sol, Ludox, surfactant stearic acid, defoamer n-butanol.The face of shell Layer material is BaZrO3, backsheet is magnesium aluminate spinel.MgAl manufactured in the present embodiment2O4-BaZrO3Composite shell is entirely capable of Meet application requirement of the composite form in TiAl alloy directional solidification processes, the titanium alloy that is particularly suitable for use in, zircaloy high activity Alloy precision is cast and directional solidification processes.State shell surface layer coating and stucco aggregate BaZrO3Pass through specific physical or change Method pre-processes, by BaZrO3Surface layer and MgAl2O4BaZrO is additionally provided between backing layer3Stucco layer, makes BaZrO3Surface layer And MgAl2O4Backing layer is closely linked, and prevents MgAl2O4-BaZrO3The defects of composite shell cracks.The present embodiment system Standby MgAl2O4-BaZrO3Composite shell and graphite, CaO, ZrO2、Al2O3Etc. plain edition shell phase ratio, high activity conjunction can be reduced Interfacial reaction degree of the gold in hot investment casting and directional solidification process 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 answering in alloy with high activity hot investment casting and directional solidification process With.
The present embodiment is carried out on the premise of the technical program using the directional solidification of the TiAl alloy in titanium alloy as example 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-BaZrO3The 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 continued to stir Mix, and after BaZrO3 powders powder adds, then 5g defoamer n-butanols are added into size barrel；Controlled after 24h is stirred Viscosity processed obtains shell backing layer slurry between 17-27s, and the flow cup measured used in the viscosity of shell backing layer slurry is LND-3 Portable copper flow cup；
C. the preparation of shell surface layer：
Medium temperature wax is pressed into shape needed for shell first, is put into cleaning fluid and is cleaned to degrease after compacting, then Rinsed and dried with clear water；In wax pattern before shell surface layer slurry is immersed, shell surface layer slurry viscosity first is measured with viscosimeter, When shell surface layer slurry viscosity can immerse wax pattern between 17-37s；Then wax pattern is put into step a the shell prepared 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 BaZrO 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 shell backing layer slurry is immersed, first shell backing layer slurry is 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 forms 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 BaZrO3, magnesium aluminate spinel, yttrium colloidal sol, Ludox, surfactant stearic acid, defoamer n-butanol.Shell Surface material is BaZrO3, backsheet is magnesium aluminate spinel.MgAl manufactured in the present embodiment2O4-BaZrO3Composite 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 are high living Property alloy precision casting and directional solidification processes.
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 A variety of changes are made according to the purpose of the innovation and creation of the present invention, under all Spirit Essence and principle according to technical solution of the present invention Change, modification, replacement, combination or the simplification 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-BaZrO3Composite 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 1. MgAl2O4-BaZrO3Composite shell, it is characterised in that：Using BaZrO3As the surface material of shell, and use MgAl2O4As the backsheet of shell, mainly by BaZrO3Surface layer and MgAl2O4Backing layer combines to form composite shell.
  2. 2. MgAl according to claim 12O4-BaZrO3Composite shell, it is characterised in that：In BaZrO3It is described in surface layer BaZrO3Particle diameter be 44-74 μm, or BaZrO3Be respectively 44-74 μm by grading particle diameter and granularity less than 44 μm formed it is mixed Close particle size materials.
  3. 3. MgAl according to claim 12O4-BaZrO3Composite shell, it is characterised in that：In MgAl2O4It is described in backing layer MgAl2O4Particle diameter be 44-124 μm.
  4. 4. the MgAl according to Claims 2 or 32O4-BaZrO3Composite shell, it is characterised in that：In BaZrO3Surface layer and MgAl2O4BaZrO is additionally provided between backing layer3Stucco layer, BaZrO3The particle diameter for the BaZrO3 aggregates that stucco layer uses 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 uses2O4Aggregate Particle diameter is 124-710 μm.
  5. A kind of 5. MgAl described in claim 12O4-BaZrO3The 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. 6. MgAl according to claim 52O4-BaZrO3The application of composite shell, it is characterised in that：As smelting titanium alloy Or the sidewall of crucible of zircaloy.
  7. A kind of 7. MgAl described in claim 12O4-BaZrO3The 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：BaZrO3For 95-65%, yttrium colloidal sol are 5-35%；Coating raw material is configured to BaZrO3Slurries, the BaZrO as raw material3Particle diameter be 44-74 μm, or BaZrO3It is respectively that 44-74 μm and granularity less than 44 μm form combination grain raw material material by grading particle diameter Material, BaZrO3The 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 BaZrO3 powder powders are gradually added in size barrel and continue to be stirred；Controlled after at least 24h is stirred 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 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；Viscosity is controlled to obtain shell backing layer slurry between 17-27s after at least 24h is stirred；
    C. the preparation of shell surface layer：
    Medium temperature wax is pressed into shape needed for shell first, cleaning in cleaning fluid is put into after compacting and, to degrease, is then used clear Water is rinsed and dried；In wax pattern before shell surface layer slurry is immersed, shell surface layer slurry viscosity first is 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 step a shell prepared 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, the BaZrO for being 150-420 μm with particle diameter3Aggregate 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 to be placed in thermostatic chamber of the temperature not less than 21 DEG C, 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 shell backing layer slurry is immersed, first measure shell backing layer slurry with viscosimeter and glue 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 to be placed in thermostatic chamber of the temperature not less than 21 DEG C, 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 BaZrO3Outside stucco layer Shell outer layer dry solidification, that is, obtain MgAl2O4-BaZrO3The 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 system dewaxing time is not less than 10min, completes the MgAl to being prepared in the step f2O4-BaZrO3The group of composite shell and wax pattern Fit dewaxing treatment process, obtains MgAl2O4-BaZrO3Composite shell biscuit；
    H. the roasting of composite shell：
    The MgAl that will be prepared in the step g2O4-BaZrO3Composite shell biscuit carries out calcination process, first control roasting temperature Degree is not higher than 200 DEG C, and is at least incubated 1h and carries out low-temperature bake；Then it is not less than 1600 DEG C, and at least to control sintering temperature It is incubated 8h and carries out high-temperature roasting；Then carry out cooling to room temperature with the furnace, finally give MgAl2O4-BaZrO3Composite shell finished product.
  8. 8. MgAl according to claim 72O4-BaZrO3The 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 are 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, yttrium colloidal sol is poured into slurry first In bucket, and pretreatment is stirred to the material in size barrel, then surfactant is added into size barrel；Then BaZrO3 powder Body powder, which is gradually added in size barrel, to be continued to be stirred, and after BaZrO3 powders powder adds, then is added into size barrel Enter defoamer；After being stirred, then slurry viscosity control is carried out, obtain shell surface layer slurry.
  9. 9. MgAl according to claim 72O4-BaZrO3The preparation method of composite shell, it is characterised in that：In the step b In, surfactant and shell that shell backing layer slurry total amount 0.1-0.5wt% is also added in the shell backing layer slurry are carried on the back Layer slurry total amount 0.1-0.5wt% defoamer, when carrying out the preparation of shell backing layer slurry, Ludox is poured into slurry first In bucket, and pretreatment is stirred to the material in size barrel, then surfactant is added into size barrel；Then by MgAl2O4 Powder powder, which is gradually added in size barrel, to be continued to be stirred, in MgAl2O4After powder powder adds, then into size barrel Add defoamer；After being stirred, then slurry viscosity control is carried out, obtain shell backing layer slurry.
  10. 10. MgAl according to claim 8 or claim 92O4-BaZrO3The preparation method of composite shell, it is characterised in that：The table Face activating agent uses stearic acid, and the defoamer uses n-butanol.
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* Cited by examiner, † Cited by third party
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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
CN103898610A (en) * 2014-03-31 2014-07-02 上海大学 Shell mold for directional solidification of highly active alloys and application of shell mold
CN103894537A (en) * 2014-03-31 2014-07-02 上海大学 Composite oxide shell for directional solidification technology as well as application thereof
CN104001856A (en) * 2014-05-30 2014-08-27 张勇弢 Preparation method of oxide ceramic composite shell for precision casting of titanium alloy

Patent Citations (7)

* Cited by examiner, † Cited by third party
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
CN103898610A (en) * 2014-03-31 2014-07-02 上海大学 Shell mold for directional solidification of highly active alloys and application of shell mold
CN103894537A (en) * 2014-03-31 2014-07-02 上海大学 Composite oxide shell for directional solidification technology as well as application thereof
CN104001856A (en) * 2014-05-30 2014-08-27 张勇弢 Preparation method of oxide ceramic composite shell for precision casting of titanium alloy

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