CN1229067A - Filtration-type mold and mehtod for producing ceramic sintered body using the mold - Google Patents
Filtration-type mold and mehtod for producing ceramic sintered body using the mold Download PDFInfo
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- CN1229067A CN1229067A CN99100765A CN99100765A CN1229067A CN 1229067 A CN1229067 A CN 1229067A CN 99100765 A CN99100765 A CN 99100765A CN 99100765 A CN99100765 A CN 99100765A CN 1229067 A CN1229067 A CN 1229067A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 32
- 238000000465 moulding Methods 0.000 claims abstract description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 238000007493 shaping process Methods 0.000 claims description 81
- 239000000843 powder Substances 0.000 claims description 79
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 78
- 150000002500 ions Chemical group 0.000 claims description 47
- 230000006837 decompression Effects 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 16
- 239000006259 organic additive Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000003566 sealing material Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 239000002195 soluble material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 239000000565 sealant Substances 0.000 abstract 3
- 239000002002 slurry Substances 0.000 abstract 2
- 238000007789 sealing Methods 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 description 62
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 44
- 238000005238 degreasing Methods 0.000 description 30
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 27
- 239000011230 binding agent Substances 0.000 description 26
- 208000037656 Respiratory Sounds Diseases 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 23
- 239000002253 acid Substances 0.000 description 21
- 239000013530 defoamer Substances 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 20
- 238000007872 degassing Methods 0.000 description 19
- 150000001408 amides Chemical class 0.000 description 18
- 238000007582 slurry-cast process Methods 0.000 description 17
- 230000002950 deficient Effects 0.000 description 15
- 238000011282 treatment Methods 0.000 description 11
- 238000005452 bending Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 235000011194 food seasoning agent Nutrition 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 6
- 239000011505 plaster Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 235000013372 meat Nutrition 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000012279 drainage procedure Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B28B1/26—Producing shaped prefabricated articles from the material by slip-casting, i.e. by casting a suspension or dispersion of the material in a liquid-absorbent or porous mould, the liquid being allowed to soak into or pass through the walls of the mould; Moulds therefor ; specially for manufacturing articles starting from a ceramic slip; Moulds therefor
-
- 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
- C04B35/01—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
- C04B35/453—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 zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
- C04B35/457—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 zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
- 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
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention provides a filtration-type mold and method for producing ceramic sintered body using the mold. Said filtration-type mold made of non-hydrosoluble materials is used for obtaining a molding body by vacuum-draining water in slurry, characterized in that, said mold consists of the following parts: a molding lower mold having at least one drain hole, a water permeable filter mounted on the molding lower mold, and a mold frame for clamping the sealant from above through a sealant for sealing the filter. The molding lower mold, the molding frame, the sealant and the filter are capable of being assembled detachably, wherein water in slurry is drained from only the side of a filter surface by reducing pressure.
Description
Filtering type shaping die, the high purity sputter targets of using when the invention relates to ceramic formation body and being shaped of using when forming nesa coating and be suitable for manufacture method as the high ceramic sintered bodies of the service efficiency of ITO sputtering target with wall thickness difference with sputtering method.
The ito thin film that is made of Indium sesquioxide and stannic oxide is widely used for the nesa coating as liquid-crystal display etc.Ito thin film moulding method commonly used is to use the spatter film forming method of ITO sintered compact as target.
In recent years, along with the increase of liquid-crystal display size, the ITO target develops to the maximization direction gradually.The manufacture method of ITO sintered compact has, and is shaped with the metal pattern pressing, then the method that gained ITO molding is burnt till.But, when adopting the metal pattern pressing, being accompanied by the maximization of molding size, the cost of metal pattern and pressing device expense increase.In addition, in the dry type press forming method of using metal pattern, shaping density is not easy evenly to be easy to generate warpage and crackle on the molding in having the molding of wall thickness difference.
In addition, in the past, the molded article production method that cost of equipment is lower had the ceramic mud castable method of utilizing plaster mould etc.This method is, mud is injected gypsum etc. has absorptive porous matter closed die adding to depress, from the two sides or all surface suction (special fair 6-659) of model.But, when adopting this method, be last meat in the centre of molding, be easy to generate defectives such as the even composition of density unevenness is inhomogeneous, in addition, compare with the metal pattern pressing, the bending strength of molding and shaping density are lower, thereby be easy to generate defectives such as crackle when burning till, and can not guarantee to obtain highdensity sintered compact.In addition, because the slurry casting employed gypsum that is shaped is water miscible, can not prevent that therefore calcium from sneaking in the molding.As the ceramic sintered bodies of the functional material of sputtering target, wish to have high purity, if wherein sneaked into calcium, will produce adverse influence to electroconductibility, the transparency, the erosion of the film of spatter film forming.
Also have a kind of method to be, after slurry casting is shaped, with the method (for example, special fair 8-11711) of calm water pressure engine densification with raising density.But, this method water pressure engine of need cooling down, thereby equipment cost increases.
The objective of the invention is, be provided at that to sneak into impurity in the ceramic sintered bodies manufacturing process less, do not produce subsurface defect, do not have density irregularity and form inhomogenous molding, and the shaping die cheaply that is used to obtain have the molding of wall thickness difference.
Another object of the present invention is, the bending strength that is provided as body is improved, and do not have the manufacture method of high purity ITO sintered compact of the big molded dimension of defectives such as crackle, cracking after burning till.
In addition, a further object of the invention is, provide the mud that will contain Indium sesquioxide and stannic oxide to be shaped, the gained molding is burnt till and the high purity ITO sintered compact that obtains, and as the manufacture method of the high ITO sintered compact with wall thickness difference of sputtering target service efficiency.
The inventor finds, the filtering type shaping die that use is made of non-water soluble material replaces slurry casting in the past to use plaster mould as shaping die, can make folk prescription towards meat, obtain not having density irregularity and form irregularly, do not sneak into the high purity ceramic sintered bodies of impurity.
In addition, the inventor also finds, the structure that the filtering type shaping die is adopted is owing to be shaped less with the load that counterdie bore, can the lower material of working strength, even thereby forming dimension is bigger, also can provide shaping die, simultaneously with lower cost, be processed into concaveconvex shape by being shaped with counterdie, can obtain having the molding of wall thickness difference.
In addition, the inventor also finds, be limited in a certain specified range by specific surface area, the molding intensity that is obtained by the filtering type shaping die is increased, obtain being suitable for forming dimension high density ITO sintered compact that maximize, that do not have defectives such as crackle and cracking Indium sesquioxide and stannic oxide.
Feature of the present invention is as follows:
(1) filtering type shaping die, be to be used for discharging moisture from the decompression of ceramic raw material mud, obtain ceramic formation body, the filtering type shaping die that constitutes by non-water soluble material, it is characterized in that, this shaping die is made of following part: the shaping counterdie with 1 above water vent, this shaping with counterdie on the strainer with water-permeable of mounting, and by be used to seal this strainer sealing material from the shaping of top side clamping type frame, described shaping counterdie, be shaped and use the type frame, sealing material and strainer can fit together with dismantling, only by the moisture in this strainer decompression discharge mud.
(2) the filtering type shaping die described in (1) is characterized in that above, and shaping has concaveconvex shape with the strainer of counterdie.
(3) manufacture method of high purity ceramic sintered bodies, it is characterized in that, the mud that preparation is made of ceramic raw material powder, ion exchanged water and organic additive, this mud is injected the filtering type shaping die described in top (1), only by the moisture in this strainer decompression discharge mud, make molding,, burn till then gained ceramic formation body drying defatted.
(4) has the manufacture method of the ceramic sintered bodies of wall thickness difference, it is characterized in that, the mud that preparation is made of ceramic raw material powder, ion exchanged water and organic additive, this mud is injected the filtering type shaping die described in top (2), only by the moisture in this strainer decompression discharge mud, make molding,, burn till then gained ceramic formation body drying defatted.
(5) manufacture method of high purity ITO sintered compact, it is characterized in that, the mud that preparation is made of Indium sesquioxide powder, putty powder, ion exchanged water and organic additive, this mud is injected the filtering type shaping die described in top (1), only by the moisture in this strainer decompression discharge mud, make molding,, burn till then gained ITO molding drying defatted.
(6) has the manufacture method of the ITO sintered compact of wall thickness difference, it is characterized in that, the mud that preparation is made of Indium sesquioxide powder, putty powder, ion exchanged water and organic additive, this mud is injected the filtering type shaping die described in top (2), only by the moisture in this strainer decompression discharge mud, make molding,, burn till then gained ITO molding drying defatted.
(7) manufacture method of (5) or (6) described ITO sintered compact is characterized in that the specific surface area of Indium sesquioxide powder is 4.6m above
2/ g is above, 14.6m
2Below/the g, the specific surface area of putty powder is 7.2m
2Below/the g.
(8) the ITO molding drying that will make by top (7) described method, in oxygen atmosphere, burn till then make, relative density is at 97.5% (density 6.97g/cm
3) above ITO sintered compact.
Brief description of drawings
Fig. 1 is the synoptic diagram of the structure of explanation filtering type shaping die of the present invention (plate forming mould).
Fig. 2 is the synoptic diagram of the structure of explanation filtering type shaping die of the present invention (concaveconvex shape shaping die).
Fig. 3 is the schematic illustration that the ceramic sintered bodies manufacturing process of filtering type moulding method of the present invention is adopted in explanation.
Fig. 4 is the schematic illustration that the ITO sintered compact manufacturing process of filtering type moulding method of the present invention is adopted in explanation.
The working of an invention scheme
Shown in Fig. 1 (plate forming mould) and Fig. 2 (concaveconvex shape finishing die), filtering type finishing die of the present invention is that ceramic raw material mud 1 is used in the type frame 2 from the top injection molding, from 1 the above osculum 6 that is configured in the bottom draining of reducing pressure, obtain formed body.
It is stacked and consist of with type frame 2 that the filtering type finishing die is the shaping made from counterdie 3 and aluminium being shaped, clip encapsulant 5 between the two, has osculum 6 on the counterdie 3, make with aluminium or resin (polypropylene, nylon etc.), loading filter 4 (for example, the go ア テ that does not see through the ceramic powder in the mud 1 but have water penetration on the counterdie 3ッNetwork ス wet type filter cloth, ヅャパンゴアテ
ッNetwork ス Co., Ltd. makes).
In finishing die of the present invention, the pressure that decompression is born during draining only is added in filter and is shaped with between the counterdie, so can working strength less material is as the shaping counterdie.
The following describes the method that adopts filtering type finishing die of the present invention to make pottery and ITO sintered body. The manufacturing process of ceramic sintered bodies shown in Fig. 3, the manufacturing process of the sintered body of ITO shown in Fig. 4.
(a) adjustment of raw meal
The ceramic raw material powder is burnt processing or pulverization process in advance, adjust primary particle diameter and specific area, can make sliming become easy.
For the ITO sintered body, indium oxide powder and putty powder can use commercially available product, preferably in advance the indium oxide powder are burnt processing in advance, and its particle is grown up. During the primary particle size of indium oxide powder big or small improper, because shaping density is low or Density inhomogeneity can cause degreasing, cracks during sintering or ftracture, warpage increases, and therefore, the diameter of primary particle is advisable in the 0.1-0.5 mu m range.
Particulate occurs and condenses in commercially available indium oxide powder and putty powder easily, therefore, can change its specific area by burning in advance to process. The specific area of indium oxide powder is 4.6-14.6m2/ g. Specific area surpasses 14.6m2During/g, crack easily on the sintered body, otherwise specific area is lower than 4.6m2During/g, take off refer to after bending strength lower, crack easily on formed body and the sintered body and ftracture.
(b) preparation mud
Get one or more ceramic raw material powder, add ion exchange water and organic additive (dispersant, binding agent, defoamer), then ball milling mixes, and makes mud. For the ITO sintered body, with wet ball mill raw material indium oxide powder and putty powder are mixed, pulverize in advance. The proportioning of tin oxide is advisable at 5-10% (weight). At this moment, add 1-5% (weight) ion exchange water, can reduce raw meal adhering on tank skin, can fully mix. Tank in the ball mill preferably adopts resinous tank. In addition, the material of ball preferably adopts than zirconia great, that wearability is good. When adopting the dry type ball milling, in the condensed particles fragmentation, also has the effect that improves the body of powder bulk density.
Subsequently, add ion exchange water and the organic additive (dispersant) of 10-25% (weight) in the above-mentioned ball mill tank, in resinous tank, mix, raw meal is disperseed. Dispersant preferably uses the polycarboxylic-acid dispersant, and its addition is 0.2-1.0% (weight).
Then, be added with organic additive (binding agent) and mix, obtain mud. It is binding agent that binding agent can use wax, and addition is advisable at 0.3-1.0% (weight). During preparation mud, mud viscosity is preferably below 100cp. When mud viscosity was too high, degassed having any problem perhaps owing to be attached on container or the ball surface, caused the mud veclamation rate to reduce.
At last, be added with organic additive (defoamer) in mud, it is degassed to reduce pressure. It is defoamer that defoamer can use acid amides, and its addition is advisable at 0.01-0.5% (weight).
(c) manufacture body with the filtering type finishing die
To make the counterdie one side decompression of strainer through in the above-mentioned mud injection molding mould that outgases, the moisture from strainer one side decompression discharge mud makes its shaping.The decompression preferably than-700mmHg is big.Decompression can use vacuum pump etc. to carry out.
The time of decompression draining can be after meat and finish to proceed to about 30 minutes from molding.The decompression water discharge time too in short-term, molding worsens with release property on the type frame from being shaped, crack sometimes, otherwise when the decompression water discharge time was long, molding was separated from the type frame with shaping in the decompression drainage procedure, form the slit, from the slit, suck air, cause the part of the demoulding on the molding dry rapidly, crack sometimes.
(d) drying of molding, degreasing
The molding that obtains so preferably carries out seasoning.Molding contains the moisture about 10% (weight) when the demoulding, if use moisture eliminator etc. carry out rapid drying to molding, because uneven drying is even, molding warpage takes place sometimes or cracks.
Subsequently, the exsiccant molding is carried out degreasing.If molding does not carry out degreasing, warpage takes place or cracks, ftractures in molding easily when burning till.Degreasing preferably uses heated air circulation type debinding furnace etc. to carry out, and 400-600 ℃ of heating down, removes residual moisture and binding agent.
(e) molding burns till
Molding obtains the high purity ceramic sintered bodies through after burning till.For the ITO sintered compact, firing temperature is advisable at 1400-1600 ℃.Firing atmosphere can adopt atmosphere and oxygen atmosphere, uses oxygen atmosphere can obtain highdensity sintered compact, thereby is preferentially selected for use.
Shaping die of the present invention is with respect to the advantage of prior art shaping die shown in the table 1.Compare with the pressed metal mould with plaster mould in the past, the advantage of shaping die of the present invention is, do not have density unevenness or forms unevenly, can not sneak into impurity, and the expense that maximizes is lower.Also has same advantage when in addition, the molding with wall thickness difference is shaped.
Table 1
| Project | Shaping die of the present invention | Routine in the past | |
| Plaster mould | The pressed metal mould | ||
| Density unevenness is even | ????○ | ????△ | ????△ |
| Form inhomogeneous | ????○ | ????△ | ????○ |
| Sneak into impurity | ????○ | ????× | ????○ |
| The maximization expense | ????○ | ????△ | ????× |
| The wall thickness difference goods | ????○ | ????○ | ????△ |
Embodiment
Further specify the present invention below by embodiment and comparative example.
Embodiment 1
ロ-ソ that 15000g is commercially available-ダ aluminum oxide powder, 3450g ion exchanged water, 150g polycarboxylic acid series dispersion agent, 150g wax be binding agent and contain cored resin balls pack into resinous jar in, ball milling mixed 40 hours.The concentration of this mud is 83%, and median size is 0.76 μ m, and viscosity is 105cp.With the mud decompression degassing, inject shaping die of the present invention then, from strainer one side decompression draining, obtain molding.The shaping of above-mentioned shaping die is made of aluminum with the type frame, and forming dimension is 1050mm * 1100mm * 10mm, is shaped to be formed from a resin with counterdie.
Strainer uses go ア テ
ッNetwork ス wet type filter cloth (ヅ
ャパ Application go ア テ
ッNetwork ス Co., Ltd. makes).This strainer is to adhere to the porous resin film and constitute on a side surface of fabric or felt, and the reverse side of resin is made of fabric or felt, has permeable space, forms path, and water can move freely between porous resin film and counterdie.
Molding carries out skimming treatment under 450 ℃ after seasoning.Can not produce warpage or the crackle that causes because of density irregularity on the molding after the degreasing, it is of a size of 1049mm * 1099mm * 10.2mm, and density is 55% (2.19g/cm
3).
Concentration of hydraulic mixture is defined as follows:
Concentration of hydraulic mixture (%)=solute weight/(solute weight+weight of solvent) * 100
The putty powder that 250g is commercially available, 1.25g ion exchanged water and zirconia ball pack into resinous jar in, ball milling mixed 20 hours.Add 233g ion exchanged water and 2g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 2.5g wax after 1 hour is binding agent, and ball milling mixed 19 hours.The concentration of this mud is 83%, and median size is 1.1 μ m, and viscosity is 71cp.
With the mud decompression degassing, inject except that forming dimension is φ 76mm the shaping die of the present invention of material and structure similarly to Example 1 then, the draining of reducing pressure under the decompression of-760mmHg obtains molding.With the molding seasoning, then 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1500 ℃, burnt till 8 hours subsequently, obtain the stannic oxide sintered compact.Do not produce the warpage or the crackle that cause because of density irregularity on the sintered compact, sintered density is 66.5% (4.6g/cm
3).Do not sneaked into the high purity sintered compact of impurity such as calcium.
With the zirconia ball of 7200g Indium sesquioxide powder, 800g putty powder and 240g ion exchanged water and diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 1440g ion exchanged water and 56 g polycarboxylic acid series dispersion agents then, ball milling mixed 1 hour.Adding 80g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 1.6g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%, and median size is 0.5 μ m, and viscosity is 33cp.It is the shaping die of structure similarly to Example 1 aluminium is made that this mud is injected that to remove forming dimension be 300mm * 700mm, shaping with counterdie, and the draining of reducing pressure under the decompression of-760mmHg obtains molding.
With the molding seasoning, 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then.Do not produce the warpage or the crackle that cause because of density irregularity on the ITO sintered compact.Obtain the high purity ITO sintered compact that do not have the stannic oxide segregation and do not sneak into calcium.The ITO sintered compact is of a size of 247mm * 578mm * 7.3mm, and density is 98.1% (7.01g/cm
3).
Embodiment 4
With the zirconia ball of 18000g Indium sesquioxide powder, 2000g putty powder and 600g ion exchanged water and diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 3592g ion exchanged water and 160g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 200g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 4g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%, and median size is 0.5 μ m, and viscosity is 40cp.It is the shaping die of structure similarly to Example 1 aluminium is made that this mud is injected that to remove forming dimension be 375mm * 1270mm, shaping with counterdie, and the draining of reducing pressure under the decompression of-760mmHg obtains molding.
With the molding seasoning, 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then.Do not produce the warpage or the crackle that cause because of density irregularity on the ITO sintered compact.Obtain the high purity ITO sintered compact that do not have the stannic oxide segregation and do not sneak into calcium.The ITO sintered compact is of a size of 308mm * 1046mm * 7.9mm, and density is 98.8% (7.06g/cm
3).
Embodiment 5
With the zirconia ball of 900g Indium sesquioxide powder, 100g putty powder and 30g ion exchanged water and diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 178g ion exchanged water and 7.9g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 9.9g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 0.2g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%, and median size is 0.46 μ m, and viscosity is 15cp.It is the shaping die of structure similarly to Example 1 aluminium is made that this mud is injected that to remove forming dimension be φ 190mm, shaping with counterdie, and the draining of reducing pressure under the decompression of-760mmHg obtains molding.
With the molding seasoning, 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then.Do not produce the warpage or the crackle that cause because of density irregularity on the ITO sintered compact.Obtain the high purity ITO sintered compact that do not have the stannic oxide segregation and do not sneak into calcium.The ITO sintered compact is of a size of φ 57mm * 7.9mm, and density is 99.5% (7.11g/cm
3).
Embodiment 6
With the zirconia ball of 720g Indium sesquioxide powder, 80g putty powder and 24g ion exchanged water and diameter 10mm pack into resinous jar in, ball milling mixed 20 hours.Add 128g ion exchanged water and 6.4g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 8.0g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 0.4g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%, and median size is 0.53 μ m, and viscosity is 28cp.With this mud inject except that forming dimension be that φ 190mm, strainer are that the degree of depth of concentric circles is the shaping die of structure similarly to Example 1 the recess of 5mm, wide 30mm, the draining of reducing pressure under the decompression of-760mmHg obtains molding.
With the molding seasoning, 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then.Do not produce the warpage or the crackle that cause because of density irregularity on the ITO sintered compact.The ITO sintered compact is of a size of φ 56.6mm * 3.52mm (thinner wall section) " 6.56mm (heavy section) ", and density is 99.3% (7.10g/cm
3).
Comparative example 1
With 6930g Indium sesquioxide powder, 770g putty powder and zirconia ball pack into resinous jar in, ball milling mixed 20 hours.From jar, take out raw material powder, in this raw material powder, add the polyvinyl alcohol water solution 6.0% (weight) of 4% (weight), mix.At 500kgf/cm
2Following this raw material powder of compacting of pressure, pulverize then, be adjusted to the following granularity of 60 orders.This powder is put into the metal pattern that forming dimension is 200mm * 980mm, use 1000kgf/cm
2Pressure forming.
Do not produce the crackle that causes because of density irregularity on the molding.Molding is of a size of 201.0mm * 982.0mm * 9.26mm, and density is 61.0% (4.36g/cm
3).
Comparative example 2
With the mud of embodiment 5 with 1.0kgf/cm
2Pressure pouring be in the plaster mould of φ 190mm * 8.5mm, to obtain molding to forming dimension.After the body seasoning to be formed, 600 ℃ of following degreasings 3 hours.
In oxygen atmosphere, burnt till 8 hours under 1550 ℃, obtain the ITO sintered compact then.At this moment, the density of ITO sintered compact is 97.2% (6.95g/cm
3).In the middle body of ITO sintered compact inside, find the defective of muscle shape, analyze, observe the stannic oxide segregation by EPMA.In addition, detect the calcium impurities of 35ppm.
As mentioned above; adopt the embodiment 1-6 of filtering type shaping die of the present invention to compare with 2 with the comparative example 1 that adopts plaster mould or pressed metal mould; embodiments of the invention only in one direction meat; molding inside does not produce density irregularity and forms defectives such as irregular; do not have impurity to sneak into, can obtain having the high purity molding of wall thickness difference.
Embodiment 7
With 900g specific surface area 8.07m
2The Indium sesquioxide powder of/g, 100g specific surface area 2.2m
2The zirconia ball of the putty powder of/g, 30g ion exchanged water and diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 178.3g ion exchanged water and 7.9g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 9.9g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, in this mud, add 0.2g acid amides defoamer, the degassing of reducing pressure.The concentration of this mud is 83%.
With this slurry casting to structure shown in Figure 2, forming dimension be the shaping of φ 190mm with in the model, the draining of reducing pressure under the decompression of-760mmHg obtains molding.Molding is dry under 25 ℃, then 600 ℃ of following degreasings 9 hours.Bending strength after the degreasing is 0.94kgf/cm
2Molding after the degreasing burnt till 8 hours in oxygen atmosphere and under 1550 ℃, obtained the ITO sintered compact.The size of ITO sintered compact is φ 57.3mm * 6.1mm, and density is 99.4% (7.11g/cm
3).
Embodiment 8
With 7200g specific surface area 8.52m
2The Indium sesquioxide powder of/g, 800g specific surface area 2.95m
2The putty powder of/g and 240g ion exchanged water with the zirconia ball of diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 1440g ion exchanged water and 64g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 80g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 1.6g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%.With this slurry casting to structure shown in Figure 2, forming dimension be the shaping of 700mm * 300mm with in the model, the draining of reducing pressure under the decompression of-760mmHg obtains molding.With the molding drying, then 600 ℃ of following degreasings 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then, obtain the ITO sintered compact.The size of ITO sintered compact is 578mm * 247mm * 6.9mm, and density is 97.7% (6.99g/cm
3).There are not defectives such as crackle or cracking on the sintered compact.
Embodiment 9
With 7200g specific surface area 8.07m
2The Indium sesquioxide powder of/g, 800g specific surface area 2.68m
2The putty powder of/g and 240g ion exchanged water with the zirconia ball of diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 1440g ion exchanged water and 64g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 80g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 1.6g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%.With this slurry casting to structure shown in Figure 2, forming dimension be the shaping of 700mm * 800mm with in the model, the draining of reducing pressure under the decompression of-760mmHg obtains molding.After the molding drying, 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then, obtain the ITO sintered compact.The size of ITO sintered compact is 578mm * 247mm * 7.3mm, and density is 98.1% (7.01g/cm
3).There are not defectives such as crackle or cracking on the sintered compact.
Embodiment 10
With 6750g specific surface area 6.86m
2The Indium sesquioxide powder of/g, 750g specific surface area 3.38m
2The putty powder of/g and 225g ion exchanged water with the zirconia ball of diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 1348.2g ion exchanged water and 60g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 75g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 1.4g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%.With this slurry casting to structure shown in Figure 2, forming dimension be the shaping of 700mm * 300mm with in the model, the draining of reducing pressure under the decompression of-760mmHg obtains molding.After the molding drying, 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours, obtain the ITO sintered compact.The size of ITO sintered compact is 565mm * 242mm * 7.1mm, and density is 98.7% (7.05g/cm
3).There are not defectives such as crackle or cracking on the sintered compact.
Embodiment 11
With 7200g specific surface area 6.54m
2The Indium sesquioxide powder of/g, 800g specific surface area 2.49m
2The putty powder of/g and 240g ion exchanged water with the zirconia ball of diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 1440g ion exchanged water and 64g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 80g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 1.6g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%.With this slurry casting to structure shown in Figure 2, forming dimension be the shaping of 700mm * 300mm with in the model, the draining of reducing pressure under the decompression of-760mmHg obtains molding.After the molding drying, 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours, obtain the ITO sintered compact.The size of ITO sintered compact is 572mm * 245mm * 7.3mm, and density is 98.6% (7.03g/cm
3).There are not defectives such as crackle or cracking on the sintered compact.
Embodiment 12
With 18000g specific surface area 6.64m
2The Indium sesquioxide powder of/g, 2000g specific surface area 3.11m
2The zirconia ball of the putty powder of/g, 600g ion exchanged water and diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.
Add 3592g ion exchanged water and 160g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 200g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 4g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%.With this slurry casting to structure shown in Figure 2, forming dimension be the shaping of 1270mm * 375mm with in the model, draining under the decompression of-760mmHg obtains molding.Molding is dry under 25 ℃, then 600 ℃ of following degreasings 3 hours, in oxygen atmosphere and under 1550 ℃, burnt till 8 hours, obtain the ITO sintered compact.The size of ITO sintered compact is 1046mm * 308mm * 7.9mm, and density is 98.8% (7.06g/cm
3).Can obtain major axis is the above large-scale ITO sintered compact of 1000mm.
Comparative example 3
With 900g specific surface area 4.22m
2The Indium sesquioxide powder of/g, 100g specific surface area 2.2m
2The putty powder of/g, 7.9g alcohol be the zirconia ball of binding agent and diameter 10mm pack into resinous jar in, ball milling mixed 20 hours.At 1000kgf/cm
2Pressure under should handle the powder press forming, forming dimension is φ 190mm.Then with molding 600 ℃ of following degreasings 3 hours.Bending strength after the degreasing is 0.72kgf/cm
2Molding after the degreasing burnt till 8 hours in oxygen atmosphere and under 1550 ℃, obtained the high density ITO sintered compact.The size of ITO sintered compact is φ 66.0mm * 5.7mm, and density is 99.0% (7.08g/cm
3).
Comparative example 4
With 900g specific surface area 4.53m
2The Indium sesquioxide powder of/g, 100g specific surface area 2.2m
2The zirconia ball of the putty powder of/g, 30g ion exchanged water and diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 128.7g ion exchanged water and 4.5g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 9.9g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 0.4g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 86%.With this slurry casting to structure shown in Figure 1, forming dimension be the shaping of φ 90mm with in the model, draining under the decompression of-760mmHg obtains molding.Molding is dry under 25 ℃, then 600 ℃ of following degreasings 3 hours.
Bending strength is 0.60kgf/mm after the degreasing
2Molding after the degreasing burnt till 8 hours in oxygen atmosphere and under 1550 ℃, obtained the ITO sintered compact.The size of ITO sintered compact is φ 160.6mm * 5.9mm, and density is 99.7% (7.13g/cm
3).
Comparative example 5
With 900g specific surface area 4.22m
2The Indium sesquioxide powder of/g, 100g specific surface area 2.2m
2The zirconia ball of the putty powder of/g, 30g ion exchanged water and diameter 5mm pack into resinous jar in, ball milling mixed 20 hours.Add 108.9g ion exchanged water and 4.7g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 7.9g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 0.5g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 87%.With this slurry casting to structure shown in Figure 1, forming dimension be the shaping of φ 90mm with in the model, draining under the decompression of-760mmHg obtains molding.Molding is dry under 25 ℃, then 600 ℃ of following degreasings 3 hours.Bending strength is 0.50kgf/mm after the degreasing
2Molding after the degreasing burnt till 8 hours in oxygen atmosphere and under 1550 ℃, obtained the ITO sintered compact.The size of ITO sintered compact is φ 166.0mm * 5.5mm, and density is 99.9% (7.14g/cm
3).
Comparative example 6
With 7200g specific surface area 14.7m
2The Indium sesquioxide powder of/g, 800g specific surface area 2.482m
2The putty powder of/g, 240g ion exchanged water are packed in resinous jar with the zirconia ball of diameter 5mm, and ball milling mixed 20 hours.Add 2000g ion exchanged water and 64g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 80g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 1.6g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration degree of this mud is 76%.With this slurry casting to structure shown in Figure 1, forming dimension be the shaping of 700mm * 300mm with in the model, draining under the decompression of-760mmHg obtains molding.After the molding drying, 600 ℃ of following degreasings 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours, obtain the ITO sintered compact.The size of ITO sintered compact is 522mm * 224mm * 7.1mm, and density is 98.5% (7.04g/cm
3).Produce the crackle of 6 10mm-20mm on the sintered compact.
Comparative example 7
With 7200g specific surface area 7.73m
2The Indium sesquioxide powder of/g, 800g specific surface area 7.62m
2The putty powder of/g, 400g ion exchanged water are packed in resinous jar with the zirconia ball of diameter 5mm, and ball milling mixed 20 hours.Add 1440g ion exchanged water and 80g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 80g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 1.6g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 82%.With this slurry casting to structure shown in Figure 1, forming dimension be the shaping of 700mm * 300mm with in the model, draining under the decompression of-760mmHg obtains molding.After the molding drying, 600 ℃ of following degreasings 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then, obtain the ITO sintered compact.The size of ITO sintered compact is 575mm * 246mm * 7.4mm, and density is 97.8% (6.99g/cm
3).Produce the crackle of 19 length 4-26mm on the sintered compact.
Comparative example 8
With 8100g specific surface area 7.73m
2The Indium sesquioxide powder of/g, 900g specific surface area 7.23m
2The putty powder of/g, 450g ion exchanged water are packed in resinous jar with the zirconia ball of diameter 5mm, and ball milling mixed 20 hours.Add 1710g ion exchanged water and 94g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 90g wax after 1 hour is binding agent, and ball milling mixed 19 hours.The concentration of this mud is 81%.With this slurry casting to structure shown in Figure 1, forming dimension be the shaping of 700mm * 300mm with in the model, draining under the decompression of-760mmHg obtains molding.After the molding drying, 600 ℃ of following degreasings 3 hours.Density after the degreasing is 63% (4.5g/cm
3).Molding cracks into two at middle body after degreasing.
Comparative example 9
With 8100g specific surface area 4.53m
2The Indium sesquioxide powder of/g, 900g specific surface area 2.68m
2The putty powder of/g, 270g ion exchanged water are packed in resinous jar with the zirconia ball of diameter 5mm, and ball milling mixed 20 hours.Add 1170g ion exchanged water and 41g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 90g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 4.5g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 86%.With this slurry casting to structure shown in Figure 1, forming dimension be the shaping of 700mm * 300mm with in the model, draining under the decompression of-760mmHg obtains molding.After the molding drying, 600 ℃ of following degreasings 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then, obtain the ITO sintered compact.The size of ITO sintered compact is 593mm * 254mm * 7.7mm, and density is 98.6% (7.05g/cm
3).Produce the crackle of 20mm on the sintered compact.
Comparative example 10
With 7200g specific surface area 4.50m
2The Indium sesquioxide powder of/g, 800g specific surface area 7.62m
2The putty powder of/g, 240g ion exchanged water are packed in resinous jar with the zirconia ball of diameter 5mm, and ball milling mixed 20 hours.Add 1440g ion exchanged water and 64g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 80g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 1.6g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 83%.With this slurry casting to structure shown in Figure 1, forming dimension be the shaping of 700mm * 300mm with in the model, draining under the decompression of-760mmHg obtains molding.After the molding drying, 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then, obtain the ITO sintered compact.The size of ITO sintered compact is 588mm * 251mm * 7.1mm, and density is 97.9% (7.00g/cm
3).Produce the crackle of 12mm and 17mm on the sintered compact.
Comparative example 11
With 8100g specific surface area 3.68m
2The Indium sesquioxide powder of/g, 900g specific surface area 2.65m
2The putty powder of/g, 270g ion exchanged water are packed in resinous jar with the zirconia ball of diameter 5mm, and ball milling mixed 20 hours.Add 1170g ion exchanged water and 41g polycarboxylic acid series dispersion agent then, ball milling mixed 1 hour.Adding 90g wax after 1 hour is binding agent, and ball milling mixed 19 hours.
Then, adding the 4.5g acid amides in this mud is defoamer, the degassing of reducing pressure.The concentration of this mud is 86%.With this slurry casting to structure shown in Figure 1, forming dimension be the shaping of 700mm * 300mm with in the model, draining under the decompression of-760mmHg obtains molding.After the molding drying, 600 ℃ of following skimming treatments 3 hours.In oxygen atmosphere and under 1550 ℃, burnt till 8 hours then, obtain the ITO sintered compact.The size of ITO sintered compact is 597mm * 255mm * 7.5mm, and density is 98.6% (7.05g/cm
3).Produce the crackle of 15mm on the sintered compact.
Indium sesquioxide specific surface area and ITO target bending strength when the specific surface area of table 2 expression stannic oxide immobilizes.Under the equal situation of the specific surface area of Indium sesquioxide, the ITO molding that forms with the filtering type moulding method is lower than the bending strength of the ITO molding that is pressed into shape, still, by improving the specific surface area of Indium sesquioxide, can improve bending strength.
The specific surface area of table 2 Indium sesquioxide and intensity
| Example | Specific surface area (m 2/g) | 25 ℃ of drying (kgf/mm 2) | 600 ℃ of degreasing (kgf/mm 2) |
| Embodiment 7 | ??8.07 | ???0.27 | ????0.94 |
| Comparative example 3 (press forming) | ??4.22 | ???0.35 | ????0.72 |
| Comparative example 4 | ??4.53 | ???0.20 | ????0.60 |
| Comparative example 5 | ??4.22 | ???0.31 | ????0.50 |
The density of the ITO molding that is shaped by inside dimension 700mm * 300mm shown in the table 3 and zero defect is arranged.When the specific surface area of employed Indium sesquioxide, stannic oxide raw material powder exceeds outside the institute of the present invention restricted portion, crack, defective such as degreasing cracking.
The density of table 3 ITO molding
| Example | Indium sesquioxide (m 2/g) | Stannic oxide (m 2/g) | Shaping density % | Burn till density % | Defective |
| Embodiment 8 | ??8.52 | ??2.95 | ????60.0 | ??97.7 | Do not have |
| Embodiment 9 | ??8.07 | ??2.68 | ????60.1 | ??98.1 | Do not have |
| Embodiment 10 | ??6.86 | ??3.38 | ????56.0 | ??98.7 | Do not have |
| Embodiment 11 | ??6.54 | ??2.49 | ????54.9 | ??98.6 | Do not have |
| Comparative example 6 | ??14.7 | ??2.48 | ????50.24 | ??98.5 | Crackle |
| Comparative example 7 | ??7.73 | ??7.62 | ????59.2 | ??97.8 | Crackle |
| Comparative example 8 | ??7.73 | ??7.23 | ????63.0 | ???- | The degreasing cracking |
| Comparative example 9 | ??4.53 | ??2.68 | ????63.7 | ??98.6 | Crackle |
| Comparative example 10 | ??4.50 | ??7.62 | ????61.8 | ??97.6 | Crackle |
| Comparative example 11 | ??3.68 | ??2.65 | ????63.6 | ??98.6 | Crackle |
Shown in top embodiment 7-12 and comparative example 3-11, adopt the present invention, be chosen in the specified range by specific surface area Indium sesquioxide and stannic oxide raw material powder, compared with the past, can obtain large-scale and do not have the high density ITO sintered compact of defective.
Use filtering type shaping die of the present invention, can be made into body with the filter type of only discharging the moisture the mud from side decompression, therefore, can be only in one direction meat, molding inside does not produce density irregularity and forms defectives such as irregular.In addition, adopt filtering type shaping die of the present invention can obtain having the molding of wall thickness difference.
In addition, press forming method in the past and pressure casting method along with the maximization of forming dimension, must improve the intensity of equipment such as shaping die material and pressing machine, cause cost of equipment to increase.Adopt shaping die of the present invention, the pressure during the decompression draining only is added in strainer and is shaped with between the counterdie, therefore can use counterdie as being shaped by the lower material of working strength, even forming dimension increases, it is lower that Master Cost also can keep.
Adopt the moulding method of filtering type shaping die of the present invention, compared with the past by the specific surface area of selective oxidation indium in proper range and stannic oxide raw material powder, can obtain large-scale and do not have the high density ITO sintered compact of defective.
Claims (8)
1. filtering type shaping die, be to be used for discharging moisture from the decompression of ceramic raw material mud, obtain ceramic formation body, the filtering type shaping die that constitutes by non-water soluble material, it is characterized in that, this shaping die is made of following part: the shaping counterdie with 1 above water vent, this shaping with counterdie on the strainer with water-permeable of mounting, and by be used to seal this strainer sealing material from the shaping of top side clamping type frame, described shaping counterdie, be shaped and use the type frame, sealing material and strainer can fit together with dismantling, only by the moisture in this strainer decompression discharge mud.
2. the described filtering type shaping die of claim 1 is characterized in that, shaping has concaveconvex shape with the strainer of counterdie.
3. the manufacture method of high purity ceramic sintered bodies, it is characterized in that, the mud that preparation is made of ceramic raw material powder, ion exchanged water and organic additive, this mud is injected the described filtering type shaping die of claim 1, only by the moisture in this strainer decompression discharge mud, make molding,, burn till then gained ceramic formation body drying defatted.
4. the manufacture method that has the ceramic sintered bodies of wall thickness difference, it is characterized in that, the mud that preparation is made of ceramic raw material powder, ion exchanged water and organic additive, this mud is injected the described filtering type shaping die of claim 2, only by the moisture in this strainer decompression discharge mud, make molding,, burn till then gained ceramic formation body drying defatted.
5. the manufacture method of high purity ITO sintered compact, it is characterized in that, the mud that preparation is made of Indium sesquioxide powder, putty powder, ion exchanged water and organic additive, this mud is injected the described filtering type shaping die of claim 1, only by the moisture in this strainer decompression discharge mud, make molding,, burn till then gained ITO molding drying defatted.
6. the manufacture method that has the ITO sintered compact of wall thickness difference, it is characterized in that, the mud that preparation is made of Indium sesquioxide powder, putty powder, ion exchanged water and organic additive, this mud is injected the described filtering type shaping die of claim 2, only by the moisture in this strainer decompression discharge mud, make molding,, burn till then gained ITO molding drying defatted.
7. the manufacture method of claim 5 or 6 described ITO sintered compacies is characterized in that, the specific surface area of Indium sesquioxide powder is 4.6m
2/ g is above, 14.6m
2Below/the g, the specific surface area of putty powder is 7.2m
2Below/the g.
8. the ITO molding drying that will make by the described method of claim 7, in oxygen atmosphere, burn till then make, relative density is at 97.5% (density 6.97g/cm
3) above ITO sintered compact.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23257/1998 | 1998-02-04 | ||
| JP23257/98 | 1998-02-04 | ||
| JP2325798 | 1998-02-04 | ||
| JP27177/98 | 1998-02-09 | ||
| JP27177/1998 | 1998-02-09 | ||
| JP10027177A JPH11228220A (en) | 1998-02-09 | 1998-02-09 | Production of ito sintered compact by slurry casting process |
| JP24490098A JP3571540B2 (en) | 1998-02-04 | 1998-08-31 | Filtration mold and method for producing ceramic sintered body using the mold |
| JP244900/1998 | 1998-08-31 | ||
| JP244900/98 | 1998-08-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1229067A true CN1229067A (en) | 1999-09-22 |
| CN1121358C CN1121358C (en) | 2003-09-17 |
Family
ID=27284182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99100765A Expired - Lifetime CN1121358C (en) | 1998-02-04 | 1999-02-04 | Filtration-type mold and mehtod for producing ceramic sintered body using the mold |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100453621B1 (en) |
| CN (1) | CN1121358C (en) |
| TW (1) | TW548256B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104290179A (en) * | 2014-10-16 | 2015-01-21 | 福建省诺希新材料科技有限公司 | Suction filtration slip casting plaster mold |
| CN111609698A (en) * | 2020-06-03 | 2020-09-01 | 福建阿石创新材料股份有限公司 | ITO target blank drying and degreasing device and method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102254541B1 (en) | 2020-01-23 | 2021-05-20 | 최염 | water bottle cap |
| KR102444634B1 (en) | 2022-05-03 | 2022-09-19 | 주식회사 한주글로벌 | water bottle cap |
-
1999
- 1999-02-02 TW TW088101590A patent/TW548256B/en not_active IP Right Cessation
- 1999-02-04 KR KR10-1999-0003841A patent/KR100453621B1/en not_active IP Right Cessation
- 1999-02-04 CN CN99100765A patent/CN1121358C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104290179A (en) * | 2014-10-16 | 2015-01-21 | 福建省诺希新材料科技有限公司 | Suction filtration slip casting plaster mold |
| CN104290179B (en) * | 2014-10-16 | 2017-02-22 | 福建省诺希科技园发展有限公司 | Manufacturing method of suction filtration slip casting plaster mold |
| CN111609698A (en) * | 2020-06-03 | 2020-09-01 | 福建阿石创新材料股份有限公司 | ITO target blank drying and degreasing device and method |
Also Published As
| Publication number | Publication date |
|---|---|
| TW548256B (en) | 2003-08-21 |
| KR100453621B1 (en) | 2004-10-20 |
| CN1121358C (en) | 2003-09-17 |
| KR19990072433A (en) | 1999-09-27 |
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