EP1938918A1 - Mold, method for manufacture of the mold, and molded article using the mold - Google Patents
Mold, method for manufacture of the mold, and molded article using the mold Download PDFInfo
- Publication number
- EP1938918A1 EP1938918A1 EP06797631A EP06797631A EP1938918A1 EP 1938918 A1 EP1938918 A1 EP 1938918A1 EP 06797631 A EP06797631 A EP 06797631A EP 06797631 A EP06797631 A EP 06797631A EP 1938918 A1 EP1938918 A1 EP 1938918A1
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- EP
- European Patent Office
- Prior art keywords
- mold
- initial layer
- titanium
- molded article
- forming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 123
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 51
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 49
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011230 binding agent Substances 0.000 claims abstract description 46
- 239000000945 filler Substances 0.000 claims abstract description 38
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 32
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 32
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010410 layer Substances 0.000 claims description 178
- 238000005266 casting Methods 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 16
- 239000002344 surface layer Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 230000009257 reactivity Effects 0.000 abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 34
- 239000000047 product Substances 0.000 description 22
- 239000000155 melt Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- OQPDWFJSZHWILH-UHFFFAOYSA-N [Al].[Al].[Al].[Ti] Chemical compound [Al].[Al].[Al].[Ti] OQPDWFJSZHWILH-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910021324 titanium aluminide Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/005—Castings of light metals with high melting point, e.g. Be 1280 degrees C, Ti 1725 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/04—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for protection of the casting, e.g. against decarbonisation
- B22C1/06—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for protection of the casting, e.g. against decarbonisation for casting extremely oxidisable metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/08—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for decreasing shrinkage of the mould, e.g. for investment casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
- B22C1/186—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents contaming ammonium or metal silicates, silica sols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
- B22C9/04—Use of lost patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
Definitions
- the present invention relates to a mold used for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, a method for manufacturing the same, and a molded article using the mold.
- Titanium-aluminum alloys composed of titanium aluminide (TiAl), which is an intermetallic compound of Ti and Al have features such as small weight and high strength. For this reason, titanium-aluminum alloys are promising materials for turbochargers for automobile engines and rotary member for gas turbine engines or aircraft jet engines.
- titanium alloys have good corrosion resistance, small weight and biocompatibility, they have been widely used for automobiles, motorcycles, sports and leisure goods, artificial bones, artificial teeth, and the like.
- ⁇ case a needle-like modified layer (oxygen-rich layer, surface hardened layer) that is called ⁇ case is sometimes formed in the surface layer portion of the obtained molded articles.
- the ⁇ case has higher hardness and lower machinability than the ⁇ phase of the matrix phase. Therefore, where the ⁇ case layer is too thick, a long time is required for chemical milling or mechanical cutting, causing increase in production cost and decrease in productivity.
- molds described in Patent Documents 1 to 4 above were designed for titanium alloys, and these molds have been often diverted as molds for titanium-aluminum alloys.
- titanium-aluminum alloys and titanium alloys Because of high activity to titanium-aluminum alloys and titanium alloys, the reaction of molten alloy and mold has to be taken into account. In particular, because titanium-aluminum alloys have higher reactivity with molds. than titanium alloys, it is important to inhibit this reactivity. This is because, both Ti and Al are active metals, but the activity of Al is higher than that of Ti, and also because titanium-aluminum alloys have a melting point higher than titanium alloys.
- the mold is composed of a ceramic and mainly comprises a filler and a binder for increasing bonding between the filler particles.
- constituent materials with low reactivity include zirconium oxide (zirconia), yttrium oxide (yttria), and calcium oxide (calcia) as the filler, and zirconia sol and organic binders (for example, resins) as the binder.
- Zirconia sol is expensive to be used as the binder on the industrial scale and has low strength at a temperature close to room temperature. Therefore, a separate binder is required to maintain the strength at room temperature. Further, organic binders are decomposed at a high temperature, and a separate binder has to be used to maintain the strength at a high temperature. As a result, the mold cost rises.
- the mold in accordance with the present invention that attains the above-described object is a mold for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, wherein at least an initial layer of a cavity surface of a mold body is formed of a calcined product of a slurry comprising a filler having cerium oxide as a main component and a binder having silica sol as a main component.
- the initial layer and a second layer of the cavity surface of the mold body be formed from the calcined product of the slurry.
- the mold is a shell mold or a solid mold.
- a method for manufacturing a mold in accordance with the present invention is for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, comprising:
- the step of forming the initial layer slurry film is preferably repeated again as a step for forming the second slurry film.
- the method for manufacturing a mold in accordance with the present invention is for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, comprising:
- the method for manufacturing a mold in accordance with the present invention is for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, comprising:
- the step of forming the initial layer slurry film be repeated again after the step of forming the initial layer slurry film, and the block body of the last layer slurry be formed around the initial layer slurry film having a two-layer structure.
- the titanium-aluminum alloy molded article in accordance with the present invention is formed by casting in use of the above-described shell mold or solid mold.
- the titanium-aluminum alloy molded article in accordance with the present invention is a titanium alloy molded article that is formed by casting in use of the above-described shell mold or solid mold, wherein a thickness of an ⁇ case layer in the surface layer portion of the as-cast material is less than 300 ⁇ m.
- the mold in accordance with the present invention demonstrates an excellent effect in making it possible to obtain a molded article of a titanium-aluminum alloy with good surface state even as-cast material or a molded article of a titanium alloy with reduced occurrence of ⁇ case in the surface layer.
- colloidal silica (silica sol) has been used as a binder for casting molds for Ni-based alloys, Co-based alloys, and Fe-based alloys.
- Silica sol features chemical stability (low activity), low industrial cost, and a high strength from room temperature to a high temperature.
- silica sol is highly reactive with titanium-aluminum alloys and titanium alloys. For this reason, silica sol has been conventionally considered unsuitable for use as a binder for molds for titanium-aluminum alloys and titanium alloys.
- FIG. 4 A cross sectional view of a mold of one preferred embodiment of the present invention is shown in Fig. 4 .
- a mold (shell mold) 40 of the present embodiment at least an initial layer (in Fig. 4 , two layers, that is, an initial layer 44a and a second layer 44b of a cavity surface 43) of a surface (referred to hereinbelow as "cavity surface") 43 adjacent to a cavity 32 of a mold body 41 is formed from a calcined product (referred to hereinbelow as a cerium oxide - silica sol calcined product) of a slurry composed of a filler comprising cerium oxide as the main component and a binder comprising silica sol as the main component.
- a calcined product referred to hereinbelow as a cerium oxide - silica sol calcined product
- the mold body 41 has a multilayer structure comprising the initial layer (surfacemost layer) 44a, the second layer 44b, a third layer 44c ... .
- the slurry calcined product constituting the third layer 44c and subsequent layers may be the same as, or different from the cerium oxide - silica sol calcined product constituting the initial layer 44a and second layer 44b.
- a composition identical to that of the usual mold for example, a calcined product of a slurry composed of a filler comprising at least one selected from zirconia, alumina, silica, mullite, zircon, and yttria as the main component and a binder comprising zirconia sol as the main component
- a composition identical to that of the usual mold for example, a calcined product of a slurry composed of a filler comprising at least one selected from zirconia, alumina, silica, mullite, zircon, and yttria as the main component and a binder comprising zirconia sol as the main component
- the major part for example, 75 wt.% or more, preferably 80 wt.% or more of the filler of the initial layer, is cerium oxide, and the remainder is composed of at least one oxide selected from zirconia, alumina, silica mullite, zircon, or yttria. It goes without saying, that the filler may be composed only of cerium oxide (filler containing 100 wt.% cerium oxide).
- the binder for example comprises silica sol (20 to 50% aqueous solution of silica sol) at 10 to 100 wt.%, preferably 50 to 100 wt.% of the entire binder, the remainder being composed of zirconia sol, yttria sol, alumina sol, or an organic binder.
- At least the viscosity of the initial layer slurry is adjusted by the filler (gram) / binder (gram) ratio to a range of 2-4, preferably 2.5 to 3.5. Where the slurry viscosity is low, the slurry does not remain in the mold (the below-described wax mold 10) and peeling occurs.
- Fig. 19 shows that when the filler/binder ratio is 1.8, peeling occurs
- Fig. 20 shows that when the filler/binder ratio is 2.0, peeling is about to start.
- Fig. 21 when the filler/binder ratio is 3.0, peeling does not occur and a uniform film is obtained.
- the filler/binder ratio is taken to be equal to or below 4.0.
- the explanation is conducted with respect to the case in which the mold body 41 has a three-layer structure, but the present invention is not limited to such configuration.
- the mold body 41 can have a two-layer structure or a structure comprising four or more layers.
- the explanation is conducted with respect to the case in which the initial layer 44a and the second layer 44b are composed of the cerium oxide - silica sol calcined product (materials of the same type), but the present invention is not limited to such configuration.
- the thickness of the initial layer 44a is sufficiently large (for example, in the case where the thickness of the initial layer 44a is 500 ⁇ m or more), it is preferred that only the initial layer 44a be formed from cerium oxide - silica sol calcined product, and that the second and subsequent layers be from the same material as the usual molds (for example, a calcined product of a slurry composed of a filler comprising zirconium oxide as the main component and a binder comprising zirconia sol as the main component), and with consideration for coating workability, a slurry may be used in which the filler/binder ratio is decreased and viscosity is reduced by comparison with those of the initial layer.
- a wax mold 10 of the same shape and size as a target precision molded article is prepared in advance.
- an initial layer slurry is coated around the wax mold 10, then the initial layer stucco is coated, and then dried, to form an initial layer slurry film 24a, as shown in Fig. 2 .
- a second layer slurry is coated around the initial layer slurry film 24a, the second layer stucco is coated, and then dried, to form the second layer slurry film 24b.
- the initial layer slurry and the second layer slurry are identical.
- the initial layer slurry film 24a and the second layer slurry film 24b constitute a two-layer structure of the initial layer slurry film 24a.
- the initial layer slurry and the second layer slurry are prepared, for example, by mixing 1 kg of a binder comprising silica sol as the main component with 2 to 4 kg of a filler comprising cerium oxide as the main component.
- a binder comprising silica sol as the main component
- a filler comprising cerium oxide
- at least one compound selected from zirconia, alumina, silica, mullite, and yttria of about #60 to 160 mesh can be used as the stucco (refractory particles that are scattered over, and caused to adhere to the slurry surface) of the initial layer and second layer, but no specific limitation is placed on the particle size and material thereof.
- a dipping method, a blowing method, and a coating method can be used for applying the slurry, but the dipping method is preferred.
- a third layer slurry is then coated around the second layer slurry film 24b, then the third layer stucco is coated, and then dried to form a third layer slurry film 24c.
- the steps of forming the slurry films of the third and subsequent layers are performed appropriately and repeatedly as necessary. As a result, the thickness of the entire slurry film is controlled to the desired thickness. No specific limitation is placed on the third layer slurry and the slurry of subsequent layers, and also on the constituent materials of the third layer stucco and the stucco of subsequent layers, and any slurry and stucco that have been usually used for shell molds can be applied.
- the wax of the wax pattern 10 is then removed using steam, whereby a mold precursor 30 is obtained, as shown in Fig. 3 .
- the mold precursor 30 has a cavity 32 inside the precursor body 31 configured of three layers of slurry films 24a, 24b, 24c.
- the mold (shell mold) 40 of the present embodiment is then obtained, as shown in Fig. 4 , by subjecting the mold precursor 30 to calcination treatment.
- the shell mold 40 has the cavity 32 inside the mold body 41 configured of three layers: initial layer 44a, second layer 44b, and third layer 44c.
- a melt 50 of a titanium-aluminum alloy or titanium alloy is poured into the cavity 32 of the shell mold 40 and casting is performed.
- the shell mold 40 is then cooled to solidify the melt 50, thereby completing the casting process.
- a cast body is formed inside the shell mold 40.
- the shell mold 40 is then dipped into a high-temperature alkali bath or the like, the shell, that is, the mold body 41 is dissolved and removed, and knockout is performed to obtain a molded article 60 of a titanium-aluminum alloy or a titanium alloy, as shown in Fig. 6 .
- a physical method for example, blast cleaning
- Sandblasting, shot blasting, or water jet (blowing of high-pressure water) may be used for blast cleaning.
- Shakeout may be also used as a physical method other than blast cleaning.
- the initial layer 44a and the second layer 44b of the cavity surface 43 of the mold body 41 that comes into direct contact with the melt 50 of titanium-aluminum alloy is formed from the cerium oxide - silica sol calcined product.
- cerium oxide used as the main component of the filler of the shell mold 40 is hardly a stable oxide in comparison with zirconia or yttria. This is also clear from the comparison of free energies.
- cerium oxide demonstrates excellent stability with respect to Ti and neither reacts directly with Ti nor is reduced by the melt 50 of titanium-aluminum alloy poured into the cavity 32 of the shell mold 40.
- the inventors noticed this specific feature of cerium oxide.
- cerium oxide as the main component of the filler of the mold body 41, it is possible to prevent the melt 50 of titanium-aluminum alloy from reacting with the mold body 41 and oxidizing inside the cavity 32.
- silica sol that is used as the main component of the binder of the mold body 41 usually reacts vigorously with the melt 50 of titanium-aluminum alloy.
- cerium oxide as the main component of the filler, as in the shell mold 40 of the present embodiment, it is possible to prevent a vigorous reaction between silica sol and titanium-aluminum alloy even when silica sol is used for the binder.
- silica sol is chemically stable (low activity), industrially inexpensive, and has a high strength within a range from room temperature to a high temperature, when silica sol is used, the strength is maintained with single sol and it is not necessary to use other sols or organic binders for the binder.
- cerium oxide is less expensive than zirconia or yttria
- using cerium oxide as the main component of the filler of the shell mold 40 makes it possible to reduce the cost of materials for the mold.
- silica sol has been used as a binder for the usual molds (for example, molds for Ni-based alloys)
- silica sol is used as the main component of the binder for the shell mold 40, it is possible to expect a significant cost reduction since the binder can be shared. Because of these factors, an inexpensive shell mold 40 can be obtained.
- the initial layer 44a and second layer 44b of the cavity surface 43 of the mold body 41 By forming the initial layer 44a and second layer 44b of the cavity surface 43 of the mold body 41 from the cerium oxide - silica sol calcined product, it is possible to suppress reliably (or almost reliably) the oxidation of titanium-aluminum alloy and the reaction between silica sol and titanium-aluminum alloy, to suppress the formation of a layer containing a large amount of oxygen on the surface of the molded article 60, and to inhibit the adhesion (baking) of the mold body 41 to the surface of the molded article 60.
- the titanium-aluminum alloy molded article 150 that was formed by casting using the shell mold 40 of the present embodiment, practically no baking of the mold body to the surface of the molded article was observed.
- the titanium-aluminum alloy molded article 150 had beautiful surface appearance and a smooth surface.
- the titanium-aluminum alloy molded article 160 formed by casting using zirconia as the main component of the filler and silica sol as the main component of the binder of the mold a large amount of baked material 161 of the mold body appeared on the surface of the molded article.
- the titanium-aluminum alloy molded article 160 had poor surface appearance, a rough surface, and poor surface state.
- the titanium-aluminum alloy molded article 150 formed by casting using the shell mold 40 of the present embodiment practically no mold body is baked to the molded article surface. Therefore, good surface state can be obtained by simple blast cleaning.
- the titanium-aluminum alloy molded article 150 has an average surface roughness of an as-molded article of 200 ⁇ m or less, preferably 50 ⁇ m or less. Therefore, even the as-cast titanium-aluminum alloy molded article 150 has a sufficiently good surface state and does not require surface finishing treatment such as chemical milling or mechanical cutting (or required only very small surface finishing). Therefore, the titanium-aluminum alloy molded article 150 makes it possible to reduce the number of production steps, reduce the production cost, and improve productivity in comparison with the conventional titanium-aluminum alloy molded article 160.
- the shell mold 40 of the present embodiment can be manufactured by changing the formation steps of the initial layer slurry film 24a and the second layer slurry film 24b (or only the initial layer slurry film 24a). Therefore, the shell mold 40 of the present embodiment can be manufactured without substantial changes in the already existing production line for the conventional shell mold and, as a consequence, the increase in production cost can be suppressed.
- the melt 50 of a titanium alloy in the shell mold 40 of the present embodiment it is possible to inhibit the occurrence of a hardened layer ( ⁇ case) comprising a large amount of oxygen in the surface layer portion of the molded article 60.
- the thickness of the ⁇ case layer occurring in the surface layer portion of the obtained molded article 60 is thin, which is less than 300 ⁇ m, preferably less than 250 ⁇ m.
- the thickness of the ⁇ case layer occurring in the surface layer portion was about 220 ⁇ m.
- the thickness of the ⁇ case layer occurring in the surface layer portion was about 500 ⁇ m. Therefore, it is clear that the thickness of the ⁇ case layer in the titanium alloy molded article 220 is less than half that in the titanium alloy molded article 230.
- the occurrence of the ⁇ case layer in the surface layer portion is reduced. Therefore, a time required for surface treatment (chemical milling, mechanical cutting, or the like) is shortened in comparison with that for the conventional titanium alloy molded article 230. Accordingly, productivity of the titanium alloy molded article 220 is increased and the production cost of the titanium alloy molded article 220 can be reduced. Further, because no significant surface treatment is required for the titanium alloy molded article 220 to obtain the final product and the difference in dimensions between the titanium alloy molded article 220 and the final product is small, the material yield is good and the material cost of the titanium alloy molded article 220 can be reduced.
- the mold 40 of the present embodiment is suitable as a mold for precision molded articles.
- titanium-aluminum alloy precision molded articles include rotary members for turbochargers for automobile engines, gas turbine engines, and aircraft jet engines, and also heat-resistant tools.
- titanium alloy precision molded articles include automobile and motorcycle parts, sports and leisure articles, artificial bones, artificial teeth, and heat exchangers.
- FIG. 12 A cross sectional view of the mold of another preferred embodiment of the present invention is shown in Fig. 12 .
- the initial layer in the mold (solid mold) 120 of the present embodiment, at least the initial layer (in Fig. 12 , two layers: an initial layer 44a and a second layer 44b of a cavity surface 123) of the cavity surface 123 of a mold body 121 is formed from a cerium oxide - silica sol calcined product.
- the mold body 121 is configured by a block-shaped body portion 124 and a layer portion 125 adjacent to a cavity 112.
- the layer portion 125 has a two-layer structure comprising the initial layer 44a and the second layer 44b.
- the slurry calcined product constituting the body portion 124 may be same as, or different from the cerium oxide - silica sol calcined product constituting the initial layer 44a and the second layer 44b.
- a composition identical to that of the usual mold for example, a calcined product of a slurry composed of a filler comprising at least one selected from zirconia, alumina, silica, mullite, zircon, and yttria as the main component and a binder comprising zirconia sol as the main component
- a composition identical to that of the usual mold for example, a calcined product of a slurry composed of a filler comprising at least one selected from zirconia, alumina, silica, mullite, zircon, and yttria as the main component and a binder comprising zirconia sol as the main component
- the cavity surface 123 of the mold body 121 in the shell mold 120 of the present embodiment may also have a one-layer structure or a structure comprising three or more layers.
- the initial layer 44a in the solid mold 120 of the present embodiment may be formed from the cerium oxide - silica sol calcined product, and the second layer 44b may be from the same material as the body portion 124.
- a wax mold of the same shape and size as a target precision case article is prepared in advance.
- an initial layer slurry is coated around the wax mold 70, then the initial layer stucco is coated, and then dried, to form an initial layer slurry film 24a, as shown in Fig. 8 .
- a second layer slurry is coated around the initial layer slurry film 24a, the second layer stucco is coated, and then dried, to form the second layer slurry film 24b.
- the initial layer slurry and the second layer slurry are identical.
- the initial layer slurry film 24a and the second layer slurry film 24b constitute a two-layer structure of the initial layer slurry film 24a.
- the wax mold 70 provided with the slurry films 24a, 24b is disposed in a space 92 of a mold box 91, and a last layer slurry 93 is injected into the space 92.
- the last layer slurry 93 is of a type that cures naturally with the passage of time and may appropriately contain an organic compound (for example, a phenolic resin), a curing agent, and a refractory material. Natural curing of the last layer slurry 93 forms, as shown in Fig. 10 , a block body 103 of the last layer slurry 93 around the wax mold 70 provided with the slurry layers 24a, 24b.
- the wax of the wax mold 70 is then removed using steam and a mold precursor 110 is obtained, as shown in Fig. 11 .
- the mold precursor 110 has a cavity 112 inside a precursor body 111.
- the precursor body 111 is composed of a block body 103, which is a body portion, and slurry films 24a, 24b adjacent to the cavity 112.
- a mold (solid mold) 120 of the present embodiment is then obtained, as shown in Fig. 12 , by performing calcination treatment of the mold precursor 110.
- the solid mold 120 has the cavity 112 inside the mold body 121 composed of the body portion 124 and the layer portion 125.
- the melt 50 of a titanium-aluminum alloy or a titanium alloy is poured into the cavity 112 of the solid mold 120 and casting is performed.
- the solid mold 120 is thereafter cooled to solidify the melt 50, and the casting process is completed. As a result, a cast body is formed inside the solid mold 120.
- a molded article 140 of titanium-aluminum alloy or titanium alloy is obtained by removing the cast body from the solid mold 120.
- the block body 103 of a last layer slurry 93 is formed around the slurry films 24a, 24b of a two-layer structure, but this configuration is not limiting.
- the block body may be directly formed around the wax mold 70 in one manufacturing process.
- the last layer slurry 93 is identical to the initial layer slurry.
- the effect obtained with the mold 120 of the present embodiment is identical to that obtained with the mold 40 of the above-described embodiment.
- the thickness of the ⁇ case layer is thin, which is less than 300 ⁇ m.
- the thickness of the ⁇ case layer occurring in the surface layer portion was about 280 ⁇ m.
- the thickness of the ⁇ case layer occurring in the surface layer portion was about 500 ⁇ m. Therefore, it is clear that the thickness of the ⁇ case layer in the titanium alloy molded article 240 is about half that in the titanium alloy molded article 250.
- the mold 120 of the present embodiment is suitable as a mold for ultralarge molded articles, decorative articles, artificial teeth, and artificial bones than the molds for precision molded articles. Because the mold 120 has high endurance and small number of layers, it simplifies the manufacturing steps and, therefore, demonstrates excellent cost performance.
Abstract
Description
- The present invention relates to a mold used for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, a method for manufacturing the same, and a molded article using the mold.
- Titanium-aluminum alloys composed of titanium aluminide (TiAl), which is an intermetallic compound of Ti and Al have features such as small weight and high strength. For this reason, titanium-aluminum alloys are promising materials for turbochargers for automobile engines and rotary member for gas turbine engines or aircraft jet engines.
- Further, because titanium alloys have good corrosion resistance, small weight and biocompatibility, they have been widely used for automobiles, motorcycles, sports and leisure goods, artificial bones, artificial teeth, and the like.
- In order to employ titanium-aluminum alloys or titanium alloys for the aforementioned members, in particular to commercial products, they have to be molded articles to reduce cost. Molds are required to manufacture molded articles, and a variety of molds therefor have been suggested (see, for example, Patent Documents 1 to 4).
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- Patent Document 1: Japanese Patent Application Laid-open No.
H5-123820 - Patent Document 2: Japanese Patent Application Laid-open No.
2003-225738 - Patent Document 3: Japanese Patent Application Laid-open No.
H 5-277624 - Patent Document 4: Japanese Patent Application Laid-open No.
H 6-292940 - However, because titanium alloys have high activity, a needle-like modified layer (oxygen-rich layer, surface hardened layer) that is called α case is sometimes formed in the surface layer portion of the obtained molded articles. The α case has higher hardness and lower machinability than the α phase of the matrix phase. Therefore, where the α case layer is too thick, a long time is required for chemical milling or mechanical cutting, causing increase in production cost and decrease in productivity.
- Further, molds described in Patent Documents 1 to 4 above were designed for titanium alloys, and these molds have been often diverted as molds for titanium-aluminum alloys.
- Because of high activity to titanium-aluminum alloys and titanium alloys, the reaction of molten alloy and mold has to be taken into account. In particular, because titanium-aluminum alloys have higher reactivity with molds. than titanium alloys, it is important to inhibit this reactivity. This is because, both Ti and Al are active metals, but the activity of Al is higher than that of Ti, and also because titanium-aluminum alloys have a melting point higher than titanium alloys.
- Accordingly, the selection of constituent materials is important for molds designed for titanium-aluminum alloys and titanium alloys. The mold is composed of a ceramic and mainly comprises a filler and a binder for increasing bonding between the filler particles. Examples of constituent materials with low reactivity include zirconium oxide (zirconia), yttrium oxide (yttria), and calcium oxide (calcia) as the filler, and zirconia sol and organic binders (for example, resins) as the binder.
- However, zirconia and yttria are expensive to be used as the fillers on the industrial scale. Calcia is difficult to handle because it decomposes on reaction with water.
- Zirconia sol is expensive to be used as the binder on the industrial scale and has low strength at a temperature close to room temperature. Therefore, a separate binder is required to maintain the strength at room temperature. Further, organic binders are decomposed at a high temperature, and a separate binder has to be used to maintain the strength at a high temperature. As a result, the mold cost rises.
- It is an object of the present invention, which has been created with the foregoing in view, to provide an inexpensive mold that has low reactivity with molten alloys, a method for manufacturing such mold and a molded article using the mold.
- The mold in accordance with the present invention that attains the above-described object is a mold for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, wherein at least an initial layer of a cavity surface of a mold body is formed of a calcined product of a slurry comprising a filler having cerium oxide as a main component and a binder having silica sol as a main component.
- It is preferred that the initial layer and a second layer of the cavity surface of the mold body be formed from the calcined product of the slurry. Further, the mold is a shell mold or a solid mold.
- On the other hand, a method for manufacturing a mold in accordance with the present invention is for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, comprising:
- a step of forming an initial layer slurry film by applying an initial layer slurry comprising a filler having cerium oxide as a main component and a binder having silica sol as a main component to a surface of a wax mold that is an evaporative pattern mold and by drying thereof;
- a step of successively forming slurry films of second and subsequent layers on a surface of the initial layer slurry film;
- a step of forming a mold precursor having a cavity inside the initial layer slurry film by performing a wax removal treatment with respect to the wax mold that has been coated with at least two layers of slurry films; and
- a step of forming a shell mold by performing a calcination treatment with respect to the mold precursor to solidify each slurry film.
- Here, the step of forming the initial layer slurry film is preferably repeated again as a step for forming the second slurry film.
- Further, the method for manufacturing a mold in accordance with the present invention is for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, comprising:
- a step of forming a block body of an initial layer slurry by applying an initial layer slurry comprising a filler having cerium oxide as a main component and a binder having silica sol as a main component to a surface of a wax mold that is an evaporative pattern mold and by drying thereof;
- a step of forming a mold precursor having a cavity inside the block body by performing a wax removal treatment with respect to the wax mold having the block body; and
- a step of forming a solid mold by performing a calcination treatment with respect to the mold precursor to solidify the block body.
- Further, the method for manufacturing a mold in accordance with the present invention is for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, comprising:
- a step of forming an initial layer slurry film by applying an initial layer slurry comprising a filler having cerium oxide as a main component and a binder having silica sol as a main component to a surface of a wax mold that is an evaporative pattern mold and by drying thereof;
- a step of forming a block body of the last layer slurry around the initial layer slurry film;
- a step of forming a mold precursor having a cavity inside the initial layer slurry film by performing a wax removal treatment with respect to the wax mold that has the initial layer slurry film and the block body; and
- a step of forming a solid mold by performing a calcination treatment with respect to the mold precursor to solidify the initial layer slurry film and the block body.
- Here, it is preferred that the step of forming the initial layer slurry film be repeated again after the step of forming the initial layer slurry film, and the block body of the last layer slurry be formed around the initial layer slurry film having a two-layer structure.
- The titanium-aluminum alloy molded article in accordance with the present invention is formed by casting in use of the above-described shell mold or solid mold.
- Further, the titanium-aluminum alloy molded article in accordance with the present invention is a titanium alloy molded article that is formed by casting in use of the above-described shell mold or solid mold, wherein a thickness of an α case layer in the surface layer portion of the as-cast material is less than 300 µm.
- The mold in accordance with the present invention demonstrates an excellent effect in making it possible to obtain a molded article of a titanium-aluminum alloy with good surface state even as-cast material or a molded article of a titanium alloy with reduced occurrence of α case in the surface layer.
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Fig. 1 is a cross-sectional view of a wax mold for use in the manufacture of a mold of one preferred embodiment of the present invention. -
Fig. 2 illustrates a state after a slurry film has been formed around the wax mold in the process for manufacturing the mold of one preferred embodiment of the present invention. -
Fig. 3 illustrates the state after wax removal in the process for manufacturing the mold of one preferred embodiment of the present invention. -
Fig. 4 is a cross sectional view of the mold in one preferred embodiment of the present invention. -
Fig. 5 illustrates the state in which a melt is poured into a mold cavity shown inFig. 4 . -
Fig. 6 is a cross sectional view of a molded article formed by casting using the mold shown inFig. 4 . -
Fig. 7 is a cross-sectional view of a wax mold used in the manufacture of a mold of another preferred embodiment of the present invention. -
Fig. 8 illustrates a state after a slurry film has been formed around the wax mold in the process for manufacturing the mold of another preferred embodiment of the present invention. -
Fig. 9 illustrates the formation of a slurry block body around a slurry film in the process for manufacturing the mold of another preferred embodiment of the present invention. -
Fig. 10 illustrates a state after the slurry block body has been formed in the process for manufacturing the mold of another preferred embodiment of the present invention. -
Fig. 11 illustrates a state after the wax has been removed in the process for manufacturing the mold of another preferred embodiment of the present invention. -
Fig. 12 is a cross sectional view of a mold of another preferred embodiment of the present invention. -
Fig. 13 illustrates a state in which a melt has been poured into the cavity of the mold shown inFig. 12 -
Fig. 14 is a cross sectional view of a molded article that is formed by casting using the mold shown inFig. 12 . -
Fig. 15 is a planar observation view of a portion of a titanium-aluminum alloy molded article formed by casting by using a mold of one preferred embodiment of the present invention. -
Fig. 16 is an enlarged view of themain portion 16 shown inFig. 15 . -
Fig. 17 is a planar observation view of a portion of a titanium-aluminum alloy molded article formed by casting by using the conventional mold. -
Fig. 18 is an enlarged view of themain portion 18 shown inFig. 17 . -
Fig. 19 is a cross-sectional view illustrating an adhesion state of the initial layer slurry and the wax mold when the filler/binder ratio in the initial layer slurry is 1.8. -
Fig. 20 is a cross-sectional view illustrating an adhesion state of the initial layer slurry and the wax mold when the filler/binder ratio in the initial layer slurry is 2.0. -
Fig. 21 is a cross-sectional view illustrating an adhesion state of the initial layer slurry and the wax mold when the filler/binder ratio in the initial layer slurry is 3.0. -
Fig. 22 is a cross-sectional observation view of a titanium alloy molded article formed by casting using a shell mold of one preferred embodiment of the present invention. -
Fig. 23 is a cross-sectional observation view of a titanium alloy molded article formed by casting using a conventional shell mold. -
Fig. 24 is a cross-sectional observation view of a titanium alloy molded article formed by casting using a solid mold of another preferred embodiment of the present invention. -
Fig. 25 is a cross-sectional observation view of a titanium alloy molded article formed by casting using a conventional solid mold. -
- 40
- shell mold (mold)
- 41
- mold body
- 43
- cavity surface
- 44a
- initial layer
- 60
- molded article
- Colloidal silica (silica sol) has been used as a binder for casting molds for Ni-based alloys, Co-based alloys, and Fe-based alloys. Silica sol features chemical stability (low activity), low industrial cost, and a high strength from room temperature to a high temperature. However, silica sol is highly reactive with titanium-aluminum alloys and titanium alloys. For this reason, silica sol has been conventionally considered unsuitable for use as a binder for molds for titanium-aluminum alloys and titanium alloys.
- However, the results of a keen study performed by the inventors demonstrated that by adjusting the constituent materials of a filler for a mold for a titanium-aluminum alloy or a titanium alloy, it is possible to prevent a vigorous reaction with the titanium-aluminum alloy or titanium alloy even when silica sol is used as a binder.
- One preferred embodiment of the present invention will be described below with reference to the appended drawings.
- A cross sectional view of a mold of one preferred embodiment of the present invention is shown in
Fig. 4 . - As shown in
Fig. 4 , in a mold (shell mold) 40 of the present embodiment, at least an initial layer (inFig. 4 , two layers, that is, an initial layer 44a and a second layer 44b of a cavity surface 43) of a surface (referred to hereinbelow as "cavity surface") 43 adjacent to acavity 32 of amold body 41 is formed from a calcined product (referred to hereinbelow as a cerium oxide - silica sol calcined product) of a slurry composed of a filler comprising cerium oxide as the main component and a binder comprising silica sol as the main component. - The
mold body 41 has a multilayer structure comprising the initial layer (surfacemost layer) 44a, the second layer 44b, athird layer 44c ... . The slurry calcined product constituting thethird layer 44c and subsequent layers may be the same as, or different from the cerium oxide - silica sol calcined product constituting the initial layer 44a and second layer 44b. For thethird layer 44c and subsequent layers, a composition identical to that of the usual mold (for example, a calcined product of a slurry composed of a filler comprising at least one selected from zirconia, alumina, silica, mullite, zircon, and yttria as the main component and a binder comprising zirconia sol as the main component) can be applied as the slurry calcined product different from the cerium oxide - silica sol calcined product. - The major part, for example, 75 wt.% or more, preferably 80 wt.% or more of the filler of the initial layer, is cerium oxide, and the remainder is composed of at least one oxide selected from zirconia, alumina, silica mullite, zircon, or yttria. It goes without saying, that the filler may be composed only of cerium oxide (filler containing 100 wt.% cerium oxide).
- Further, the binder for example comprises silica sol (20 to 50% aqueous solution of silica sol) at 10 to 100 wt.%, preferably 50 to 100 wt.% of the entire binder, the remainder being composed of zirconia sol, yttria sol, alumina sol, or an organic binder.
- At least the viscosity of the initial layer slurry is adjusted by the filler (gram) / binder (gram) ratio to a range of 2-4, preferably 2.5 to 3.5. Where the slurry viscosity is low, the slurry does not remain in the mold (the below-described wax mold 10) and peeling occurs.
Fig. 19 shows that when the filler/binder ratio is 1.8, peeling occurs, andFig. 20 shows that when the filler/binder ratio is 2.0, peeling is about to start. As shown inFig. 21 , when the filler/binder ratio is 3.0, peeling does not occur and a uniform film is obtained. When the slurry viscosity is too high, the slurry film becomes too thick, a long time is required for drying, and uniform drying is not attained, thereby causing "non-uniformity". For this reason the filler/binder ratio is taken to be equal to or below 4.0. - In the
shell mold 40 of this embodiment, the explanation is conducted with respect to the case in which themold body 41 has a three-layer structure, but the present invention is not limited to such configuration. For example, themold body 41 can have a two-layer structure or a structure comprising four or more layers. - In the
shell mold 40 of this embodiment, the explanation is conducted with respect to the case in which the initial layer 44a and the second layer 44b are composed of the cerium oxide - silica sol calcined product (materials of the same type), but the present invention is not limited to such configuration. For example, when the thickness of the initial layer 44a is sufficiently large (for example, in the case where the thickness of the initial layer 44a is 500 µm or more), it is preferred that only the initial layer 44a be formed from cerium oxide - silica sol calcined product, and that the second and subsequent layers be from the same material as the usual molds (for example, a calcined product of a slurry composed of a filler comprising zirconium oxide as the main component and a binder comprising zirconia sol as the main component), and with consideration for coating workability, a slurry may be used in which the filler/binder ratio is decreased and viscosity is reduced by comparison with those of the initial layer. - A method for manufacturing the mold of the present embodiment will be explained below with reference to the appended drawings.
- First, as shown in
Fig. 1 , awax mold 10 of the same shape and size as a target precision molded article (see the below-describedFig. 6 ) is prepared in advance. - Then, an initial layer slurry is coated around the
wax mold 10, then the initial layer stucco is coated, and then dried, to form an initiallayer slurry film 24a, as shown inFig. 2 . Then, a second layer slurry is coated around the initiallayer slurry film 24a, the second layer stucco is coated, and then dried, to form the secondlayer slurry film 24b. The initial layer slurry and the second layer slurry are identical. In other words, the initiallayer slurry film 24a and the secondlayer slurry film 24b constitute a two-layer structure of the initiallayer slurry film 24a. - Here, the initial layer slurry and the second layer slurry are prepared, for example, by mixing 1 kg of a binder comprising silica sol as the main component with 2 to 4 kg of a filler comprising cerium oxide as the main component. For example, at least one compound selected from zirconia, alumina, silica, mullite, and yttria of about #60 to 160 mesh can be used as the stucco (refractory particles that are scattered over, and caused to adhere to the slurry surface) of the initial layer and second layer, but no specific limitation is placed on the particle size and material thereof. A dipping method, a blowing method, and a coating method can be used for applying the slurry, but the dipping method is preferred.
- A third layer slurry is then coated around the second
layer slurry film 24b, then the third layer stucco is coated, and then dried to form a thirdlayer slurry film 24c. Here, the steps of forming the slurry films of the third and subsequent layers are performed appropriately and repeatedly as necessary. As a result, the thickness of the entire slurry film is controlled to the desired thickness. No specific limitation is placed on the third layer slurry and the slurry of subsequent layers, and also on the constituent materials of the third layer stucco and the stucco of subsequent layers, and any slurry and stucco that have been usually used for shell molds can be applied. - The wax of the
wax pattern 10 is then removed using steam, whereby amold precursor 30 is obtained, as shown inFig. 3 . Themold precursor 30 has acavity 32 inside the precursor body 31 configured of three layers ofslurry films - The mold (shell mold) 40 of the present embodiment is then obtained, as shown in
Fig. 4 , by subjecting themold precursor 30 to calcination treatment. Theshell mold 40 has thecavity 32 inside themold body 41 configured of three layers: initial layer 44a, second layer 44b, andthird layer 44c. - Then, as shown in
Fig. 5 , amelt 50 of a titanium-aluminum alloy or titanium alloy is poured into thecavity 32 of theshell mold 40 and casting is performed. Theshell mold 40 is then cooled to solidify themelt 50, thereby completing the casting process. As a result, a cast body is formed inside theshell mold 40. - The
shell mold 40 is then dipped into a high-temperature alkali bath or the like, the shell, that is, themold body 41 is dissolved and removed, and knockout is performed to obtain a moldedarticle 60 of a titanium-aluminum alloy or a titanium alloy, as shown inFig. 6 . A physical method (for example, blast cleaning) can used for the knockout. Sandblasting, shot blasting, or water jet (blowing of high-pressure water) may be used for blast cleaning. Shakeout may be also used as a physical method other than blast cleaning. - The effect of the
mold 40 of the present embodiment will be explained below. - In the mold (shell mold) 40 of the present embodiment, the initial layer 44a and the second layer 44b of the
cavity surface 43 of themold body 41 that comes into direct contact with themelt 50 of titanium-aluminum alloy is formed from the cerium oxide - silica sol calcined product. - Here, cerium oxide used as the main component of the filler of the
shell mold 40 is hardly a stable oxide in comparison with zirconia or yttria. This is also clear from the comparison of free energies. - However, cerium oxide demonstrates excellent stability with respect to Ti and neither reacts directly with Ti nor is reduced by the
melt 50 of titanium-aluminum alloy poured into thecavity 32 of theshell mold 40. The inventors noticed this specific feature of cerium oxide. Thus, by using cerium oxide as the main component of the filler of themold body 41, it is possible to prevent themelt 50 of titanium-aluminum alloy from reacting with themold body 41 and oxidizing inside thecavity 32. - Further, silica sol that is used as the main component of the binder of the
mold body 41 usually reacts vigorously with themelt 50 of titanium-aluminum alloy. However, by using cerium oxide as the main component of the filler, as in theshell mold 40 of the present embodiment, it is possible to prevent a vigorous reaction between silica sol and titanium-aluminum alloy even when silica sol is used for the binder. Further, because silica sol is chemically stable (low activity), industrially inexpensive, and has a high strength within a range from room temperature to a high temperature, when silica sol is used, the strength is maintained with single sol and it is not necessary to use other sols or organic binders for the binder. - Further, because cerium oxide is less expensive than zirconia or yttria, using cerium oxide as the main component of the filler of the
shell mold 40 makes it possible to reduce the cost of materials for the mold. On the other hand, because silica sol has been used as a binder for the usual molds (for example, molds for Ni-based alloys), by using silica sol as the main component of the binder for theshell mold 40, it is possible to expect a significant cost reduction since the binder can be shared. Because of these factors, aninexpensive shell mold 40 can be obtained. - By forming the initial layer 44a and second layer 44b of the
cavity surface 43 of themold body 41 from the cerium oxide - silica sol calcined product, it is possible to suppress reliably (or almost reliably) the oxidation of titanium-aluminum alloy and the reaction between silica sol and titanium-aluminum alloy, to suppress the formation of a layer containing a large amount of oxygen on the surface of the moldedarticle 60, and to inhibit the adhesion (baking) of themold body 41 to the surface of the moldedarticle 60. - For example, as shown in
Fig. 15 and Fig. 16 , in the titanium-aluminum alloy moldedarticle 150 that was formed by casting using theshell mold 40 of the present embodiment, practically no baking of the mold body to the surface of the molded article was observed. Thus, the titanium-aluminum alloy moldedarticle 150 had beautiful surface appearance and a smooth surface. By contrast, as shown inFig. 17 and Fig. 18 , in the titanium-aluminum alloy moldedarticle 160 formed by casting using zirconia as the main component of the filler and silica sol as the main component of the binder of the mold, a large amount ofbaked material 161 of the mold body appeared on the surface of the molded article. Thus, the titanium-aluminum alloy moldedarticle 160 had poor surface appearance, a rough surface, and poor surface state. - Thus, in the titanium-aluminum alloy molded
article 150 formed by casting using theshell mold 40 of the present embodiment, practically no mold body is baked to the molded article surface. Therefore, good surface state can be obtained by simple blast cleaning. For example, the titanium-aluminum alloy moldedarticle 150 has an average surface roughness of an as-molded article of 200 µm or less, preferably 50 µm or less. Therefore, even the as-cast titanium-aluminum alloy moldedarticle 150 has a sufficiently good surface state and does not require surface finishing treatment such as chemical milling or mechanical cutting (or required only very small surface finishing). Therefore, the titanium-aluminum alloy moldedarticle 150 makes it possible to reduce the number of production steps, reduce the production cost, and improve productivity in comparison with the conventional titanium-aluminum alloy moldedarticle 160. - The
shell mold 40 of the present embodiment can be manufactured by changing the formation steps of the initiallayer slurry film 24a and the secondlayer slurry film 24b (or only the initiallayer slurry film 24a). Therefore, theshell mold 40 of the present embodiment can be manufactured without substantial changes in the already existing production line for the conventional shell mold and, as a consequence, the increase in production cost can be suppressed. - By performing casting using the
melt 50 of a titanium alloy in theshell mold 40 of the present embodiment, it is possible to inhibit the occurrence of a hardened layer (α case) comprising a large amount of oxygen in the surface layer portion of the moldedarticle 60. The thickness of the α case layer occurring in the surface layer portion of the obtained moldedarticle 60 is thin, which is less than 300 µm, preferably less than 250 µm. - For example, as shown in
Fig. 22 , in a titanium alloy moldedarticle 220 formed by casting using theshell mold 40 of the present embodiment, the thickness of the α case layer occurring in the surface layer portion was about 220 µm. By contrast, as shown inFig. 23 , in the titanium alloy moldedarticle 230 formed by casting using zirconia as the main component of the filler and silica sol as the main component of the binder of the mold, the thickness of the α case layer occurring in the surface layer portion was about 500 µm. Therefore, it is clear that the thickness of the α case layer in the titanium alloy moldedarticle 220 is less than half that in the titanium alloy moldedarticle 230. - Thus, in the titanium alloy molded
article 220 formed by casting using theshell mold 40 of the present embodiment, the occurrence of the α case layer in the surface layer portion is reduced. Therefore, a time required for surface treatment (chemical milling, mechanical cutting, or the like) is shortened in comparison with that for the conventional titanium alloy moldedarticle 230. Accordingly, productivity of the titanium alloy moldedarticle 220 is increased and the production cost of the titanium alloy moldedarticle 220 can be reduced. Further, because no significant surface treatment is required for the titanium alloy moldedarticle 220 to obtain the final product and the difference in dimensions between the titanium alloy moldedarticle 220 and the final product is small, the material yield is good and the material cost of the titanium alloy moldedarticle 220 can be reduced. - The
mold 40 of the present embodiment is suitable as a mold for precision molded articles. Examples of titanium-aluminum alloy precision molded articles include rotary members for turbochargers for automobile engines, gas turbine engines, and aircraft jet engines, and also heat-resistant tools. Examples of titanium alloy precision molded articles include automobile and motorcycle parts, sports and leisure articles, artificial bones, artificial teeth, and heat exchangers. - Another embodiment of the present invention will be described below with reference to the appended drawings.
- A cross sectional view of the mold of another preferred embodiment of the present invention is shown in
Fig. 12 . - As shown in
Fig. 12 , in the mold (solid mold) 120 of the present embodiment, at least the initial layer (inFig. 12 , two layers: an initial layer 44a and a second layer 44b of a cavity surface 123) of thecavity surface 123 of amold body 121 is formed from a cerium oxide - silica sol calcined product. - The
mold body 121 is configured by a block-shapedbody portion 124 and a layer portion 125 adjacent to acavity 112. The layer portion 125 has a two-layer structure comprising the initial layer 44a and the second layer 44b. The slurry calcined product constituting thebody portion 124 may be same as, or different from the cerium oxide - silica sol calcined product constituting the initial layer 44a and the second layer 44b. For thebody portion 124, a composition identical to that of the usual mold (for example, a calcined product of a slurry composed of a filler comprising at least one selected from zirconia, alumina, silica, mullite, zircon, and yttria as the main component and a binder comprising zirconia sol as the main component) can be applied as the slurry calcined product different from the cerium oxide - silica sol calcined product. - The
cavity surface 123 of themold body 121 in theshell mold 120 of the present embodiment may also have a one-layer structure or a structure comprising three or more layers. - When the thickness of the initial layer 44a in the
solid mold 120 of the present embodiment is sufficiently large, only the initial layer 44a may be formed from the cerium oxide - silica sol calcined product, and the second layer 44b may be from the same material as thebody portion 124. - A method for manufacturing the mold of the present embodiment will be explained below with reference to
Fig. 7 to Fig. 14 . Components identical to those shown inFig. 1 to Fig. 6 are denoted by identical reference numerals and the explanation of these components is omitted. - First, as shown in
Fig. 7 , a wax mold of the same shape and size as a target precision case article (see the below-describedFig. 14 ) is prepared in advance. - Then, an initial layer slurry is coated around the
wax mold 70, then the initial layer stucco is coated, and then dried, to form an initiallayer slurry film 24a, as shown inFig. 8 . Then, a second layer slurry is coated around the initiallayer slurry film 24a, the second layer stucco is coated, and then dried, to form the secondlayer slurry film 24b. The initial layer slurry and the second layer slurry are identical. In other words, the initiallayer slurry film 24a and the secondlayer slurry film 24b constitute a two-layer structure of the initiallayer slurry film 24a. - Then, as shown in
Fig. 9 , thewax mold 70 provided with theslurry films space 92 of amold box 91, and alast layer slurry 93 is injected into thespace 92. Thelast layer slurry 93 is of a type that cures naturally with the passage of time and may appropriately contain an organic compound (for example, a phenolic resin), a curing agent, and a refractory material. Natural curing of thelast layer slurry 93 forms, as shown inFig. 10 , ablock body 103 of thelast layer slurry 93 around thewax mold 70 provided with theslurry layers - The wax of the
wax mold 70 is then removed using steam and amold precursor 110 is obtained, as shown inFig. 11 . Themold precursor 110 has acavity 112 inside aprecursor body 111. Theprecursor body 111 is composed of ablock body 103, which is a body portion, andslurry films cavity 112. - A mold (solid mold) 120 of the present embodiment is then obtained, as shown in
Fig. 12 , by performing calcination treatment of themold precursor 110. Thesolid mold 120 has thecavity 112 inside themold body 121 composed of thebody portion 124 and the layer portion 125. - Then, as shown in
Fig. 13 , themelt 50 of a titanium-aluminum alloy or a titanium alloy is poured into thecavity 112 of thesolid mold 120 and casting is performed. Thesolid mold 120 is thereafter cooled to solidify themelt 50, and the casting process is completed. As a result, a cast body is formed inside thesolid mold 120. - Then, as shown in
Fig. 14 , a moldedarticle 140 of titanium-aluminum alloy or titanium alloy is obtained by removing the cast body from thesolid mold 120. - In the method for manufacturing the
mold 120 of the present embodiment, the case is explained in which theblock body 103 of alast layer slurry 93 is formed around theslurry films wax mold 70 in one manufacturing process. Thus, it is possible to dispose thewax mold 70 inside thespace 92 of themold box 91, then pour thelast layer slurry 93 into thespace 92, and form the block body composed of only thelast layer slurry 93 directly around thewax mold 70. Thelast layer slurry 93 is identical to the initial layer slurry. - The effect obtained with the
mold 120 of the present embodiment is identical to that obtained with themold 40 of the above-described embodiment. - By performing casting using the
melt 50 of a titanium alloy in thesolid mold 120 of the present embodiment, it is possible to inhibit the occurrence of a hardened layer (α case) comprising a large amount of oxygen in the surface layer portion of the moldedarticle 140, and the thickness of the α case layer is thin, which is less than 300 µm. For example, as shown inFig. 24 , in a titanium alloy moldedarticle 240 formed by casting using thesolid mold 120 of the present embodiment, the thickness of the α case layer occurring in the surface layer portion was about 280 µm. By contrast, as shown inFig. 25 , in the titanium alloy moldedarticle 250 formed by casting using zirconia as the main component of the filler and silica sol as the main component of the binder of the mold, the thickness of the α case layer occurring in the surface layer portion was about 500 µm. Therefore, it is clear that the thickness of the α case layer in the titanium alloy moldedarticle 240 is about half that in the titanium alloy moldedarticle 250. - The
mold 120 of the present embodiment is suitable as a mold for ultralarge molded articles, decorative articles, artificial teeth, and artificial bones than the molds for precision molded articles. Because themold 120 has high endurance and small number of layers, it simplifies the manufacturing steps and, therefore, demonstrates excellent cost performance. - It goes without saying that the present invention is not limited to the above-described embodiments and may be modified in a variety of ways.
Claims (11)
- A mold for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, wherein
at least an initial layer of a cavity surface of a mold body is formed of a calcined product of a slurry comprising a filler having cerium oxide as a main component and a binder having silica sol as a main component. - The mold according to claim 1, wherein the initial layer and a second layer of the cavity surface of the mold body are formed from the calcined product of the slurry.
- The mold according to claim 1 or 2, wherein the mold is a shell mold.
- The mold according to claim 1 or 2, wherein the mold is a solid mold.
- A method for manufacturing a mold for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, comprising:a step of forming an initial layer slurry film by applying an initial layer slurry comprising a filler having cerium oxide as a main component and a binder having silica sol as a main component to a surface of a wax mold that is an evaporative pattern mold, and by drying thereof;a step of successively forming slurry films of second and subsequent layers on a surface of the initial layer slurry film;a step of forming a mold precursor having a cavity inside the initial layer slurry film by performing a wax removal treatment with respect to the wax mold that has been coated with at least two slurry films; anda step of forming a shell mold by performing a calcination treatment with respect to the mold precursor to solidify each slurry film.
- The method for manufacturing a mold according to claim 5, wherein the step of forming the initial layer slurry film is repeated again as a step for forming the second slurry film.
- A method for manufacturing a mold for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, comprising:a step of forming a block body of an initial layer slurry by applying the initial layer slurry comprising a filler having cerium oxide as a main component and a binder having silica sol as a main component to a surface of a wax mold that is an evaporative pattern mold, and by drying thereof;a step of forming a mold precursor having a cavity inside the block body by performing a wax removal treatment with respect to the wax mold having the block body; anda step of forming a solid mold by performing a calcination treatment with respect to the mold precursor to solidify the block body.
- A method for manufacturing a mold for manufacturing a molded article of a titanium-aluminum alloy or a titanium alloy, comprising:a step of forming an initial layer slurry film by applying an initial layer slurry comprising a filler having cerium oxide as a main component and a binder having silica sol as a main component to a surface of a wax mold that is an evaporative pattern mold, and by drying;a step of forming a block body of a last layer slurry around the initial layer slurry film;a step of forming a mold precursor having a cavity inside the initial layer slurry film by performing a wax removal treatment with respect to the wax mold that has the initial layer slurry film and the block body; anda step of forming a solid mold by performing a calcination treatment with respect to the mold precursor to solidify the initial layer slurry film and the block body.
- The method for manufacturing a mold according to claim 8, wherein the step of forming the initial layer slurry film is repeated again after the step of forming the initial layer slurry film to form the block body of the last layer slurry around the initial layer slurry film having a two-layer structure.
- A titanium-aluminum alloy molded article that is formed by casting in use of the mold according to claim 3 or 4.
- A titanium alloy molded article that is formed by casting in use of the mold according to claim 3 or 4, wherein a thickness of an α case layer in the surface layer portion of the as-cast material is less than 300 µm.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005259218 | 2005-09-07 | ||
JP2005259219 | 2005-09-07 | ||
PCT/JP2006/317771 WO2007029785A1 (en) | 2005-09-07 | 2006-09-07 | Mold, method for manufacture of the mold, and molded article using the mold |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1938918A1 true EP1938918A1 (en) | 2008-07-02 |
EP1938918A4 EP1938918A4 (en) | 2008-08-27 |
EP1938918B1 EP1938918B1 (en) | 2016-03-16 |
Family
ID=37835900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06797631.6A Active EP1938918B1 (en) | 2005-09-07 | 2006-09-07 | Mold, method for manufacture of the mold, and molded article using the mold |
Country Status (5)
Country | Link |
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US (2) | US20090169415A1 (en) |
EP (1) | EP1938918B1 (en) |
JP (1) | JP4451907B2 (en) |
KR (1) | KR101364563B1 (en) |
WO (1) | WO2007029785A1 (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7302993B1 (en) * | 2006-09-28 | 2007-12-04 | Ethicon Endo-Surgery, Inc. | Cast parts with improved surface properties and methods for their production |
GB0623048D0 (en) * | 2006-11-18 | 2006-12-27 | Bentley Motors Ltd | Improvements in or relating to ceramic tooling |
US8858697B2 (en) | 2011-10-28 | 2014-10-14 | General Electric Company | Mold compositions |
US9011205B2 (en) | 2012-02-15 | 2015-04-21 | General Electric Company | Titanium aluminide article with improved surface finish |
US8932518B2 (en) | 2012-02-29 | 2015-01-13 | General Electric Company | Mold and facecoat compositions |
US8906292B2 (en) | 2012-07-27 | 2014-12-09 | General Electric Company | Crucible and facecoat compositions |
US8708033B2 (en) | 2012-08-29 | 2014-04-29 | General Electric Company | Calcium titanate containing mold compositions and methods for casting titanium and titanium aluminide alloys |
JP6199019B2 (en) * | 2012-10-09 | 2017-09-20 | 三菱日立パワーシステムズ株式会社 | Precision casting mold manufacturing method |
JP6095933B2 (en) * | 2012-10-09 | 2017-03-15 | 三菱日立パワーシステムズ株式会社 | Precision casting mold manufacturing method |
JP6199018B2 (en) * | 2012-10-09 | 2017-09-20 | 三菱日立パワーシステムズ株式会社 | Precision casting mold manufacturing method |
JP6095934B2 (en) * | 2012-10-09 | 2017-03-15 | 三菱日立パワーシステムズ株式会社 | Precision casting mold manufacturing method |
JP6095935B2 (en) * | 2012-10-09 | 2017-03-15 | 三菱日立パワーシステムズ株式会社 | Precision casting mold manufacturing method |
US8992824B2 (en) | 2012-12-04 | 2015-03-31 | General Electric Company | Crucible and extrinsic facecoat compositions |
US9592548B2 (en) | 2013-01-29 | 2017-03-14 | General Electric Company | Calcium hexaluminate-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys |
US9511417B2 (en) | 2013-11-26 | 2016-12-06 | General Electric Company | Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys |
US9192983B2 (en) | 2013-11-26 | 2015-11-24 | General Electric Company | Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys |
US20150183026A1 (en) * | 2013-12-27 | 2015-07-02 | United Technologies Corporation | Investment mold having metallic donor element |
US10391547B2 (en) | 2014-06-04 | 2019-08-27 | General Electric Company | Casting mold of grading with silicon carbide |
JP6276717B2 (en) * | 2015-01-30 | 2018-02-07 | 三菱重工航空エンジン株式会社 | Precision casting mold and method for producing precision casting mold |
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GB536857A (en) * | 1939-03-31 | 1941-05-29 | Titanium Alloy Mfg Co | Improvements in and relating to refractories and refractory moulds for casting metallic articles |
US5492957A (en) * | 1991-04-04 | 1996-02-20 | Shin-Etsu Chemical Co., Ltd. | Face coat composition for casting mold and method for the preparation of casting mold having face coat layer |
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JPH05212489A (en) * | 1991-04-09 | 1993-08-24 | Kawasaki Steel Corp | Slurry for casting high fusing point active metal and production of casting by casting mold formed by using this slurry |
JPH05123820A (en) * | 1991-11-07 | 1993-05-21 | Hitachi Metals Ltd | Mold for precision casting of titanium or tianium alloy |
JP2003225738A (en) | 2002-02-04 | 2003-08-12 | Daido Steel Co Ltd | Method for preparing mold for precision casting |
KR100581198B1 (en) * | 2003-08-19 | 2006-05-17 | 한국생산기술연구원 | Process of diecasting titanium and titanium-alloy mould |
-
2006
- 2006-09-07 US US12/065,692 patent/US20090169415A1/en not_active Abandoned
- 2006-09-07 EP EP06797631.6A patent/EP1938918B1/en active Active
- 2006-09-07 KR KR1020087004616A patent/KR101364563B1/en active IP Right Grant
- 2006-09-07 WO PCT/JP2006/317771 patent/WO2007029785A1/en active Application Filing
- 2006-09-07 JP JP2007534474A patent/JP4451907B2/en active Active
-
2010
- 2010-02-23 US US12/710,680 patent/US20100147485A1/en not_active Abandoned
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GB536857A (en) * | 1939-03-31 | 1941-05-29 | Titanium Alloy Mfg Co | Improvements in and relating to refractories and refractory moulds for casting metallic articles |
US5944088A (en) * | 1987-01-28 | 1999-08-31 | Remet Corporation | Ceramic shell molds and cores for casting of reactive metals |
US5492957A (en) * | 1991-04-04 | 1996-02-20 | Shin-Etsu Chemical Co., Ltd. | Face coat composition for casting mold and method for the preparation of casting mold having face coat layer |
US5947187A (en) * | 1994-01-21 | 1999-09-07 | The Boeing Company | Method for protecting a die |
JP2002336276A (en) * | 2001-05-21 | 2002-11-26 | Dia-Iatron Co Ltd | Dental casting implant material |
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Also Published As
Publication number | Publication date |
---|---|
WO2007029785A1 (en) | 2007-03-15 |
KR101364563B1 (en) | 2014-02-18 |
KR20080046169A (en) | 2008-05-26 |
EP1938918A4 (en) | 2008-08-27 |
EP1938918B1 (en) | 2016-03-16 |
JP4451907B2 (en) | 2010-04-14 |
JPWO2007029785A1 (en) | 2009-03-19 |
US20090169415A1 (en) | 2009-07-02 |
US20100147485A1 (en) | 2010-06-17 |
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