CN107021771A - A kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique - Google Patents
A kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique Download PDFInfo
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- CN107021771A CN107021771A CN201710284229.6A CN201710284229A CN107021771A CN 107021771 A CN107021771 A CN 107021771A CN 201710284229 A CN201710284229 A CN 201710284229A CN 107021771 A CN107021771 A CN 107021771A
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Abstract
The invention discloses a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique, this method adds appropriate sintering aid and enhancing chopped fiber is well mixed and the calcium oxide-based ceramic powders of 3D printing are made by being carried out to the calcium oxide ceramics powder after grain composition after organic-treating；Then 3D printing is carried out using the calcium oxide-based ceramic powders after light-curing adhesive and organic-treating, realizes the shaping of calcium oxide-based ceramic-mould biscuit；Degreasing, reaction infiltration and High-Temperature Strengthening are carried out to calcium oxide-based ceramic-mould again to sinter, and finally give the calcium oxide-based ceramic-mould of high intensity, and surface waterproofing processing is carried out to the ceramic-mould of preparation.This method improves the hydration resistance of calcium oxide-based ceramic-mould；Calcium oxide-based ceramic-mould produced by the present invention has excellent high-temperature comprehensive property, can meet the casting requirement of higher temperature alloy and high temeperature chemistry property active metal, and core is readily removed.
Description
Technical field
The invention belongs to Rapid Precision Casting technical field, and in particular to a kind of calcium oxide-based pottery based on 3D printing technique
Porcelain mold molding methods.
Background technology
At present, be at home and abroad widely used for near-net-shape hot investment casting the main silica base of ceramic-mould and
Two kinds of alumina base.It is 1520 DEG C~1560 DEG C to aoxidize silicon based ceramic temperature in use, in 1500 DEG C~1550 DEG C of pouring condition
Under, yield rate is higher, but when temperature in use be more than 1550 DEG C when, high-temperature behavior extreme difference, thus oxidation silicon based ceramic be not suitable for
The high temperature alloy pouring condition of higher temperature；Alumina-based ceramic has good, the good heat of high refractoriness, chemical stability steady
Qualitative, creep-resistant property is good, without crystal transfer the advantages of, its temperature in use is more than 1550 DEG C, reaches as high as 1850 DEG C.Although oxygen
Change Al-base ceramic casting mold has some excellent performances compared to oxidation silicon substrate ceramic-mould, but alumina-based ceramic casting mold is de-
Core is extremely difficult, it will usually bring 40% percent defective, this is also to hinder its wide variety of main cause always for a long time.
Calcium oxide fusing point is 2572 DEG C, and boiling point is 2850 DEG C, and other basic anhydride of saturated vapor pressure ratio are low under high temperature.
Therefore, calcium oxide can bear very high temperature in use；Chemical heat endurance is good, at high temperature not with the metal reaction such as titanium, can be with
Improve the surface quality of blade；Calcium oxide ceramics thermal coefficient of expansion is close with high temperature alloy, and molten metal can be same with metal when solidifying
Step is shunk, and is avoided that because heat expansion is split caused by stress, and its creep-resistant property is good, is closed with that can meet superhigh temperature of new generation
The casting use requirement of gold leaf piece；Calcium oxide-based ceramic core is readily removed, it is to avoid corrosion of the depoling to blade, reduces de-
Core difficulty and cost；Calcium oxide raw material is easily obtained and cheap.Therefore, calcium oxide is a kind of manufacture hollow blade ceramics casting
The ideal material of type.But either design of material or manufacturing process are all more complicated for the preparation of calcium oxide-based ceramic-mould,
And the easy moisture absorption aquation of calcium oxide, also increase the manufacture difficulty of calcium oxide-based ceramic-mould.Therefore, produce with good comprehensive
Performance, the accuracy of manufacture and the calcium oxide-based ceramic-mould with good hydration resistance is closed to be significant.
The content of the invention
It is an object of the invention to overcome above-mentioned deficiency, there is provided a kind of calcium oxide-based ceramic-mould based on 3D printing technique
Manufacture method, the 3D printing technique based on powder bed and non-water-base adhesive can once-forming manufacture core, shell integrated oxidization
Calcium ceramic-mould, with good combination property, the accuracy of manufacture and hydration resistance.
In order to achieve the above object, the present invention comprises the following steps：
Step one, by 40 μm, 20 μm and 5 μm of calcium oxide ceramics powder according to 50：35：15 mass ratio carries out granular-grade
With being handled with surface organic；
Step 2, the calcium oxide ceramics powder after organic-treating, mineralizer powder and enhancing chopped fiber are uniformly mixed,
Obtain the calcium oxide-based ceramic powder of 3D printing；
Step 3, sets up the three-dimensional CAD model of calcium oxide-based ceramic-mould and sets up the data of layering and scanning pattern；
The making data of calcium oxide-based ceramic-mould are imported 3D printer, and the pottery prepared using step 2 by step 4
Porcelain powder carries out 3D printing shaping, obtains the plain embryo of calcium oxide-based ceramic-mould；
Step 5, vacuum degreasing processing is carried out to the plain embryo of calcium oxide-based ceramic-mould；
Step 6, vacuum reaction infiltration intensive treatment is carried out to the calcium oxide-based ceramic-mould of degreasing；
Step 7, the calcium oxide-based casting mold base substrate after strengthening to infiltration carries out High-Temperature Strengthening sintering in an atmosphere, and height is made
The calcium oxide-based ceramic-mould of intensity.
Step 8, surface waterproofing processing is carried out to calcium oxide-based ceramic-mould.
In the step one, the granularity of calcium oxide ceramics powder is 2 μm~40 μm.
In the step one, surface organic processing is to select Kh50 silane couplers to be raw material, in calcium oxide ceramics powder
Last one layer of organic film of Surface Creation, specific method is as follows：
The first step, silane coupler is uniformly mixed with absolute ethyl alcohol, the solution that organises is configured to, silicon in the solution that organises
The mass fraction of alkane coupling agent is 5%, and the mass fraction of absolute ethyl alcohol is 95%；
Second step, by 3:1 mass ratio will complete the lime powder of grain composition and the solution that organises is full and uniform
Mixing, is made mixed slurry；
3rd step, 3~5h is stood by mixed slurry at room temperature, then is placed in vacuum drying chamber, and powder is completely dried
The calcium oxide ceramics powder of surface organic processing is obtained afterwards.
In the step 2, mineralizer is nanometer ZrO2, nano-MgO and nanometer Y2O3In a kind of or three kinds of mixing
Thing, its addition is the 2%~5% of calcium oxide powder weight；
In the step 2, enhancing chopped fiber is ZrO2Fiber, its length is 0.5mm~2mm, and its addition is calcium oxide
The 2%~5% of powder quality；
In the step 4,3D printing technique is the resin base bonding agent 3D printing technique based on powder bed, and its bonding agent is
Containing 80% photosensitive resin in photosensitive resin base bonding agent, photosensitive resin base bonding agent, 10% ethanol, 5% it is light-initiated
Agent, 5% colouring agent.
In the step 5, vacuum degreasing is that calcium oxide ceramics casting mold is placed in vacuum degreasing stove, is heated to 1200 DEG C,
3h is incubated, degreasing is carried out pre-sintered.
In the step 6, vacuum reaction infiltration is by the calcium oxide ceramics casting mold after degreasing and calcium metal particle or gold
Category magnesium granules are placed in infiltration in vacuum device, are heated to infiltrated metal melting temperature, insulation infiltration 2h.
In the step 7, High-Temperature Strengthening sintering is that the calcium oxide ceramics casting mold after infiltration is placed in air sintering furnace to add
Heat is incubated 3h to 1500~1600 DEG C, carries out intensified-sintered.
In the step 8, carrying out method for waterproofing to calcium oxide-based ceramic-mould surface is：It will be prepared in step 7
Calcium oxide-based ceramic-mould be placed in 200 DEG C~300 DEG C of carbon dioxide atmosphere case, it is fine and close in mo(U)ld face in-situ preparation
Calcium carbonate layer.
Compared with prior art, the invention has the advantages that：
1st, the 3DP techniques based on powder bed bonding forming can quickly manufacture the type of baroque casting mold, especially casting mold
Core, shell are once-forming, and the defects such as group is molded as in traditional investment casting process core shift, perforation can be avoided to advantageously ensure that
The dimensional accuracy of casting；
2nd, the greatest difficulty that the manufacture of calcium oxide-based ceramic-mould faces is exactly the aquation problem of calcium oxide, is adopted in the present invention
3D printing technique employs resin base bonding agent, and manufacturing process is carried out in vacuum drying environment so that calcium oxide is not
Produce and contact with water, the aquation of calcium oxide can be prevented effectively from；Secondly, the present invention is by adding appropriate mineralizer such as oxidation
Zirconium, yittrium oxide etc., can both promote the sintering of calcium oxide-based ceramic-mould, and the hydration resistance after casting mold sintering can be improved again；
3rd, can effectively to solve alumina-based ceramic casting mold depoling difficult, useless for the calcium oxide-based ceramic-mould prepared of the present invention
The high technical barrier of product rate, is greatly improved fabrication yield, and temperature in use is high, and high-temperature behavior is good, can meet at higher temperature
The hot investment casting of degree.
Brief description of the drawings
Fig. 1 is flow chart of the invention.
Embodiment
The present invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1：
1) 40 μm, 20 μm and 5 μm of calcium oxide ceramics powder is chosen according to 50:35:15 mass ratio carries out grain composition
And be well mixed；
2) above-mentioned well mixed powder is subjected to surface organic processing, concrete operations are：
(1) silane coupler is uniformly mixed with absolute ethyl alcohol, is configured to the solution that organises, silane is even in the solution that organises
The mass fraction for joining agent is 5%, and the mass fraction of absolute ethyl alcohol is 95%；
(2) 3 are pressed:1 mass ratio by the lime powder after grain composition with the solution that organises is full and uniform mixes, be made
Mixed slurry；
(3) mixed slurry is stood into 3~5h at room temperature, then be placed in vacuum drying chamber, powder is obtained after being completely dried
To the calcium oxide ceramics powder of surface organic processing；
3) the nanometer ZrO of 5% mass fraction is added into the calcium oxide ceramics powder after organic-treating2Mineralizer powder
With 0.5mm~2mm of 5% mass fraction ZrO2Chopped fiber, and by its uniform mixing, obtain the calcium oxide-based pottery of 3D printing
Porcelain powder；
3) set up the three-dimensional CAD model of calcium oxide-based ceramic-mould and set up the data of layering and scanning pattern；
4) the making data of calcium oxide-based ceramic-mould are imported into 3D printer, carries out 3D printing shaping, obtain calcium oxide
Base ceramic-mould element embryo；
5) 1200 DEG C are heated in vacuum degreasing stove to the plain embryo of calcium oxide-based ceramics, are incubated 3h, carry out degreasing pre-sintered；
6) the calcium oxide ceramics casting mold after degreasing and metal magnesium granules are pressed 1:2 quality is placed in infiltration in vacuum device,
It is heated to 650 DEG C, insulation infiltration 2h；；
7) the calcium oxide-based casting mold base substrate after strengthening to infiltration is placed in air sintering furnace, is heated to 1550 DEG C, is incubated 3h,
High-Temperature Strengthening sintering is carried out, the calcium oxide-based ceramic-mould of high intensity is made；
8) the calcium oxide-based ceramic-mould that said process is prepared is placed in 200 DEG C DEG C of carbon dioxide atmosphere case,
In the calcium carbonate layer that mo(U)ld face in-situ preparation is fine and close.
Embodiment 2：
Step one, by 40 μm, 20 μm and 5 μm of calcium oxide ceramics powder according to 50：35：15 mass ratio carries out granular-grade
With being handled with surface organic, surface organic processing is to select Kh50 silane couplers to be raw material；
Step 2, silane coupler is uniformly mixed with absolute ethyl alcohol, the solution that organises is configured to, silicon in the solution that organises
The mass fraction of alkane coupling agent is 5%, and the mass fraction of absolute ethyl alcohol is 95%；
Step 3, by 3:1 mass ratio will complete the lime powder of grain composition and the solution that organises is full and uniform
Mixing, is made mixed slurry；
Step 4,3h is stood by mixed slurry at room temperature, then is placed in vacuum drying chamber, and powder is obtained after being completely dried
To the calcium oxide ceramics powder of surface organic processing；
Step 5, the calcium oxide ceramics powder after organic-treating, mineralizer powder and enhancing chopped fiber are uniformly mixed,
The calcium oxide-based ceramic powder of 3D printing is obtained, mineralizer is nano-MgO, its addition is the 2% of calcium oxide powder weight,
Enhancing chopped fiber is ZrO2Fiber, its length is 0.5mm, and its addition is the 2% of calcium oxide powder weight；
Step 6, sets up the three-dimensional CAD model of calcium oxide-based ceramic-mould and sets up the data of layering and scanning pattern；
The making data of calcium oxide-based ceramic-mould are imported 3D printer, and the pottery prepared using step 2 by step 7
Porcelain powder carries out 3D printing shaping, obtains the plain embryo of calcium oxide-based ceramic-mould, and 3D printing technique is that the resin base based on powder bed glues
Connect agent 3D printing technique, its bonding agent is to contain 80% photosensitive tree in photosensitive resin base bonding agent, photosensitive resin base bonding agent
Fat, 10% ethanol, 5% light trigger, 5% colouring agent；
Step 8, calcium oxide ceramics casting mold is placed in vacuum degreasing stove, is heated to 1200 DEG C, is incubated 3h, carries out degreasing
It is pre-sintered；
Step 9, the calcium oxide ceramics casting mold after degreasing and calcium metal particle are placed in infiltration in vacuum device, are heated to
850 DEG C, infiltration 2h is incubated, completes to carry out vacuum reaction infiltration intensive treatment to the calcium oxide-based ceramic-mould of degreasing；
Step 10, High-Temperature Strengthening sintering is that the calcium oxide ceramics casting mold after infiltration is placed in air sintering furnace to be heated to
1500 DEG C, 3h is incubated, intensified-sintered, the calcium oxide-based ceramic-mould of obtained high intensity is carried out；
Step 11, the calcium oxide-based ceramic-mould that above-mentioned steps are prepared is placed in 300 DEG C of carbon dioxide atmosphere
In case, in the calcium carbonate layer that mo(U)ld face in-situ preparation is fine and close.
Embodiment 3：
Step one, by 40 μm, 20 μm and 5 μm of calcium oxide ceramics powder according to 50：35：15 mass ratio carries out granular-grade
With being handled with surface organic, surface organic processing is to select Kh50 silane couplers to be raw material；
Step 2, silane coupler is uniformly mixed with absolute ethyl alcohol, the solution that organises is configured to, silicon in the solution that organises
The mass fraction of alkane coupling agent is 5%, and the mass fraction of absolute ethyl alcohol is 95%；
Step 3, by 3:1 mass ratio will complete the lime powder of grain composition and the solution that organises is full and uniform
Mixing, is made mixed slurry；
Step 4,5h is stood by mixed slurry at room temperature, then is placed in vacuum drying chamber, and powder is obtained after being completely dried
To the calcium oxide ceramics powder of surface organic processing；
Step 5, the calcium oxide ceramics powder after organic-treating, mineralizer powder and enhancing chopped fiber are uniformly mixed,
The calcium oxide-based ceramic powder of 3D printing is obtained, mineralizer is nanometer Y2O3, its addition is the 5% of calcium oxide powder weight,
Enhancing chopped fiber is ZrO2Fiber, its length is 2mm, and its addition is the 5% of calcium oxide powder weight；
Step 6, sets up the three-dimensional CAD model of calcium oxide-based ceramic-mould and sets up the data of layering and scanning pattern；
The making data of calcium oxide-based ceramic-mould are imported 3D printer, and the pottery prepared using step 2 by step 7
Porcelain powder carries out 3D printing shaping, obtains the plain embryo of calcium oxide-based ceramic-mould, and 3D printing technique is that the resin base based on powder bed glues
Connect agent 3D printing technique, its bonding agent is to contain 80% photosensitive tree in photosensitive resin base bonding agent, photosensitive resin base bonding agent
Fat, 10% ethanol, 5% light trigger, 5% colouring agent；
Step 8, calcium oxide ceramics casting mold is placed in vacuum degreasing stove, is heated to 1200 DEG C, is incubated 3h, carries out degreasing
It is pre-sintered；
Step 9, the calcium oxide ceramics casting mold after degreasing and calcium metal particle are placed in infiltration in vacuum device, are heated to
850 DEG C, infiltration 2h is incubated, completes to carry out vacuum reaction infiltration intensive treatment to the calcium oxide-based ceramic-mould of degreasing；
Step 10, High-Temperature Strengthening sintering is that the calcium oxide ceramics casting mold after infiltration is placed in air sintering furnace to be heated to
1600 DEG C, 3h is incubated, intensified-sintered, the calcium oxide-based ceramic-mould of obtained high intensity is carried out；
Step 11, the calcium oxide-based ceramic-mould that above-mentioned steps are prepared is placed in 150 DEG C of carbon dioxide atmosphere
In case, in the calcium carbonate layer that mo(U)ld face in-situ preparation is fine and close.
Embodiment 4：
Step one, by 40 μm, 20 μm and 5 μm of calcium oxide ceramics powder according to 50：35：15 mass ratio carries out granular-grade
With being handled with surface organic, surface organic processing is to select Kh50 silane couplers to be raw material；
Step 2, silane coupler is uniformly mixed with absolute ethyl alcohol, the solution that organises is configured to, silicon in the solution that organises
The mass fraction of alkane coupling agent is 5%, and the mass fraction of absolute ethyl alcohol is 95%；
Step 3, by 3:1 mass ratio will complete the lime powder of grain composition and the solution that organises is full and uniform
Mixing, is made mixed slurry；
Step 4,4h is stood by mixed slurry at room temperature, then is placed in vacuum drying chamber, and powder is obtained after being completely dried
To the calcium oxide ceramics powder of surface organic processing；
Step 5, the calcium oxide ceramics powder after organic-treating, mineralizer powder and enhancing chopped fiber are uniformly mixed,
The calcium oxide-based ceramic powder of 3D printing is obtained, mineralizer is nanometer ZrO2, nano-MgO and nanometer Y2O3Three kinds of mixture,
Its mixed proportion is that mass ratio is equal to 1:1:1, its addition is the 3% of calcium oxide powder weight, and enhancing chopped fiber is ZrO2It is fine
Dimension, its length is 1.2mm, and its addition is the 4% of calcium oxide powder weight；
Step 6, sets up the three-dimensional CAD model of calcium oxide-based ceramic-mould and sets up the data of layering and scanning pattern；
The making data of calcium oxide-based ceramic-mould are imported 3D printer, and the pottery prepared using step 2 by step 7
Porcelain powder carries out 3D printing shaping, obtains the plain embryo of calcium oxide-based ceramic-mould, and 3D printing technique is that the resin base based on powder bed glues
Connect agent 3D printing technique, its bonding agent is to contain 80% photosensitive tree in photosensitive resin base bonding agent, photosensitive resin base bonding agent
Fat, 10% ethanol, 5% light trigger, 5% colouring agent；
Step 8, calcium oxide ceramics casting mold is placed in vacuum degreasing stove, is heated to 1200 DEG C, is incubated 3h, carries out degreasing
It is pre-sintered；
Step 9, the calcium oxide ceramics casting mold after degreasing and metal magnesium granules are placed in infiltration in vacuum device, are heated to
650 DEG C, infiltration 2h is incubated, completes to carry out vacuum reaction infiltration intensive treatment to the calcium oxide-based ceramic-mould of degreasing；
Step 10, High-Temperature Strengthening sintering is that the calcium oxide ceramics casting mold after infiltration is placed in air sintering furnace to be heated to
1550 DEG C, 3h is incubated, intensified-sintered, the calcium oxide-based ceramic-mould of obtained high intensity is carried out；
Step 11, the calcium oxide-based ceramic-mould that above-mentioned steps are prepared is placed in 180 DEG C of carbon dioxide atmosphere
In case, in the calcium carbonate layer that mo(U)ld face in-situ preparation is fine and close.
Claims (10)
1. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique, it is characterised in that comprise the following steps：
Step one, by 40 μm, 20 μm and 5 μm of calcium oxide ceramics powder according to 50：35：15 mass ratio carry out grain composition and
Surface organic processing；
Step 2, the calcium oxide ceramics powder after organic-treating, mineralizer powder and enhancing chopped fiber are uniformly mixed, obtained
The calcium oxide-based ceramic powder of 3D printing；
Step 3, sets up the three-dimensional CAD model of calcium oxide-based ceramic-mould and sets up the data of layering and scanning pattern；
The making data of calcium oxide-based ceramic-mould are imported 3D printer, and the ceramic powder prepared using step 2 by step 4
End carries out 3D printing shaping, obtains the plain embryo of calcium oxide-based ceramic-mould；
Step 5, vacuum degreasing processing is carried out to the plain embryo of calcium oxide-based ceramic-mould；
Step 6, vacuum reaction infiltration intensive treatment is carried out to the calcium oxide-based ceramic-mould of degreasing；
Step 7, the calcium oxide-based casting mold base substrate after strengthening to infiltration carries out High-Temperature Strengthening sintering in an atmosphere, and high intensity is made
Calcium oxide-based ceramic-mould；
Step 8, surface waterproofing processing is carried out to calcium oxide-based ceramic-mould.
2. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique according to claim 1, its feature
It is, in the step one, the granularity of calcium oxide ceramics powder is 2 μm~40 μm.
3. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique according to claim 1, its feature
It is, in the step one, surface organic processing is to select Kh50 silane couplers to be raw material, in calcium oxide ceramics powder table
Face generates one layer of organic film, and specific method is as follows：
The first step, silane coupler is uniformly mixed with absolute ethyl alcohol, the solution that organises is configured to, and silane is even in the solution that organises
The mass fraction for joining agent is 5%, and the mass fraction of absolute ethyl alcohol is 95%；
Second step, by 3:1 mass ratio will complete the lime powder of grain composition and the solution that organises is full and uniform mixes,
Mixed slurry is made；
3rd step, 3~5h is stood by mixed slurry at room temperature, then is placed in vacuum drying chamber, and powder is obtained after being completely dried
To the calcium oxide ceramics powder of surface organic processing.
4. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique according to claim 1, its feature
It is, in the step 2, mineralizer is nanometer ZrO2, nano-MgO and nanometer Y2O3In a kind of or three kinds of mixture,
Its addition is the 2%~5% of calcium oxide powder weight.
5. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique according to claim 1, its feature
It is, in the step 2, enhancing chopped fiber is ZrO2Fiber, its length is 0.5mm~2mm, and its addition is calcium oxide powder
The 2%~5% of weight.
6. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique according to claim 1, its feature
It is, in the step 4,3D printing technique is the resin base bonding agent 3D printing technique based on powder bed, and its bonding agent is photosensitive
Containing 80% photosensitive resin in resin base bonding agent, photosensitive resin base bonding agent, 10% ethanol, 5% light trigger,
5% colouring agent.
7. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique according to claim 1, its feature
It is, in the step 5, vacuum degreasing is that calcium oxide ceramics casting mold is placed in vacuum degreasing stove, is heated to 1200 DEG C, guarantor
Warm 3h, carries out degreasing pre-sintered.
8. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique according to claim 1, its feature
It is, in the step 6, vacuum reaction infiltration is by the calcium oxide ceramics casting mold after degreasing and calcium metal particle or metal
Magnesium granules are placed in infiltration in vacuum device, are heated to infiltrated metal melting temperature, insulation infiltration 2h.
9. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique according to claim 1, its feature
It is, in the step 7, High-Temperature Strengthening sintering is that the calcium oxide ceramics casting mold after infiltration is placed in air sintering furnace to heat
To 1500 DEG C~1600 DEG C, 3h is incubated, is carried out intensified-sintered.
10. a kind of calcium oxide-based ceramic-mould manufacture method based on 3D printing technique according to claim 1, its feature
It is, in the step 8, carrying out method for waterproofing to calcium oxide-based ceramic-mould surface is：By the oxygen prepared in step 7
Change calcium base ceramic-mould to be placed in 200 DEG C~300 DEG C of carbon dioxide atmosphere case, in the carbonic acid that mo(U)ld face in-situ preparation is fine and close
Calcium layer.
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