US20090218067A1 - Lost-wax method associated with piezocrystallization and a device for carrying out said method - Google Patents
Lost-wax method associated with piezocrystallization and a device for carrying out said method Download PDFInfo
- Publication number
- US20090218067A1 US20090218067A1 US12/278,780 US27878008A US2009218067A1 US 20090218067 A1 US20090218067 A1 US 20090218067A1 US 27878008 A US27878008 A US 27878008A US 2009218067 A1 US2009218067 A1 US 2009218067A1
- Authority
- US
- United States
- Prior art keywords
- melt
- lined
- pressure
- insert
- thimble
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 57
- 239000000155 melt Substances 0.000 claims abstract description 33
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 230000008025 crystallization Effects 0.000 claims abstract description 27
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000011819 refractory material Substances 0.000 claims 1
- 238000005266 casting Methods 0.000 abstract description 9
- 239000000919 ceramic Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 238000004512 die casting Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 238000005495 investment casting Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- 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
- B22D18/00—Pressure casting; Vacuum casting
- B22D18/02—Pressure casting making use of mechanical pressure devices, e.g. cast-forging
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D18/00—Pressure casting; Vacuum casting
- B22D18/04—Low pressure casting, i.e. making use of pressures up to a few bars to fill the mould
Definitions
- the present invention relates to a lost-wax method associated with piezocrystallization and a device for carrying out said method.
- a casting method by squeezing a metal into a mold associated with piezocrystallization is known from RU 2015829, wherein a molten metal is poured into a squeezing chamber for steel overheated substantially by 30-60° C. above a liquidus temperature and prior to squeezing is held until a metal skin freezes out on the squeezing chamber walls.
- the disadvantage of this method consists in that holding metal in the squeezing chamber may bring the melt to the liquid-solid phase. Pressure is known to be most efficient when transferred in the liquid phase. Therefore, the pressure efficiency drops as the already cooled metal is poured from the squeezing chamber into the mold and further crystallization is under way. This may result in insufficiently poured-in thin areas of the cast, corrugated surface of the cast due to a loss of flowability or shrinkage cavities due to a shortage of the liquid phase for feeding, and in general in a significant loss of the cast product quality.
- the prior art closest to the inventive method is a lost-wax method associated with piezocrystallization according to RU 2048954, wherein a pre-shaped investment mold is fixed on an upper table above a metal reservoir, and the melt is extruded at a melt crystallization temperature with a melt pressure being further maintained at 0.3-0.5 MPa until crystallization of the cast, wherein the mold filling rate and time is controlled by means of keeping the mass flow rate of the melt within 2 to 5 kg/s.
- the disadvantage of the prior art method consists in a low strength of ceramic investment molds suitable for gravity die casting rather than pressure die casting if manufactured according to the common technique.
- the strength of the investment molds and accordingly the maximum possible operating pressure depends on the number of layers applied when manufacturing the multilayer molds, main materials and binders used, accurate adherence to the manufacturing conditions thereof, forming conditions thereof in a casting container, cast size and material, casting modes and other parameters. Therefore, the pressure value in the investment mold is difficult to calculate theoretically and an experimental check of the approved pressure is required based on the actual mold strength every time a new product is manufactured by this method.
- microfissures may form on the shells in the process of manufacturing the investment molds, for example, during baking of the same, which do not affect the cast product quality in case of gravity die casting but may cause the mold to crack when pressure is applied thereto.
- a device is known from RU 2116865, comprising a metal reservoir mounted on a bottom table, a container with a investment mold fixed on an upper table, said metal reservoir being arranged as a base and a replaceable insert with a heat-insulating layer between their bottoms, and a container comprising a housing, a cover and a neck. Gas release openings are provided at the base of said replaceable insert.
- the disadvantage of the prior art device consists in that after metal is poured into the metal reservoir a crystallized layer of the melt (metal skin) begins to form throughout the height of its side walls preventing the punch to move into the metal reservoir and feeding the melt through the container neck to the mold which may in turn lead to incomplete filling of the mold.
- the unique technical problem to be solved by the claimed group of inventions is to improve the cast product quality by enabling more pressure to be applied to the melt within the reinforced investment mold obtained as a result of forming a crystallized layer of melt butting against its inner walls (metal sheath) along with reducing a negative effect of the skin crystallization process within the metal reservoir preventing the melt from being extruded into the investment mold.
- the unique technical effect of the method according to the claimed group of inventions is achieved by extruding the melt into the cavity of the shaped investment mold at a temperature above liquidus and a pressure enabling a maximum splash-free liquid metal flow rate as the investment mold is being filled, said pressure, after the investment mold has been filled with the melt, being maintained at a level obtained in the process of extrusion during crystallization of the melt layer butting against the investment mold walls, and whereafter said pressure being smoothly increased during crystallization of the entire melt to a pressure sufficient for further filling the mold in proportion to the amount of cast shrinkage.
- the unique technical effect of the device according to the claimed group of inventions is achieved by providing the outer surface of the container neck with a removable thimble and mounting at the exposed edge of the metal reservoir insert a lined annular flange matching along its inner diameter with the outer diameter of said thimble, said lined flange having an inner diameter smaller than an inner diameter of said lined insert.
- the radial difference between the inner diameters of said lined insert and said thimble is greater that the total thickness of the single-side melt layer crystallized on the lined insert wall and the thimble wall in the process of pouring-in and holding the melt till the end of crystallization.
- the above combination of features of the claimed method is novel and inventive in view of the following.
- the melt is extruded into the cavity of the shaped investment mold at a temperature above liquidus thereby enabling good flowability and contact of the melt with the mold walls for creating favorable heat transfer conditions as a metal sheath is formed on the inner surface of the investment mold.
- the pressure is determined by the absence of liquid metal splashing within the mold as it is filled at a certain rate.
- the maximum flow rate and thereby the pouring rate of liquid metal may be calculated theoretically [Borisov G. P., Pressure in Casting Control, Kyiv. Nauk. Dumka, 1988, page 121, Formula IV-18].
- this calculated pressure may be determined by hardware and monitored using a pressure gauge on the hydraulic drive for moving the metal reservoir.
- a pressure gauge on the hydraulic drive for moving the metal reservoir.
- the thickness of said metal sheath is proportional to the cast crystallization time, and its value for the abutting layer may be taken as 5% to 10% of the crystallization time of the thinnest cast areas. Then, during the remaining crystallization time of the entire melt within the investment mold, pressure is smoothly increased to a level sufficient for further filling the mold in proportion to the amount of cast shrinkage. By smoothly increasing the pressure the risk of damaging the ceramic mold is reduced. Sufficient pressure is a pressure at which feeding the cast from the butt-end into the metal reservoir is ensured in proportion to the amount of shrinkage during crystallization. The amount of shrinkage for most of the conventional casting alloys is a known characteristic.
- the sufficiency of pressure may be determined by the motion of the metal reservoir relative to the mold during crystallization, which is proportional to the amount of shrinkage, or by the absence of shrinkage defects when the cast product quality is tested.
- the metallic sheath on the inner surface of the investment mold enables the operating pressure to be increased thereby ensuring a higher cast product quality.
- the above combination of features of the claimed device is novel and inventive in view of the outer surface of the container neck being provided with a removable thimble enabling the same to be positioned within the metal reservoir without contacting the wall of the lined insert poured with the melt. As this takes place, the crystallized melt layer forming during pouring-in on the cool walls both of the lined insert and thimble will not prevent the same from moving relative to each other if a gap is provided between them.
- This gap is formed by the lined flange mounted at the upper edge of the removable lined insert and having an inner diameter smaller than an inner diameter of the lined insert.
- the thimble has an outer diameter matching by clearance fit with an inner diameter of the lined flange thereby providing a closed space as the melt is extruded into the investment mold.
- the gap width is selected once by experiment based on the longest process of pouring-in and holding the cast till the end of crystallization. It is taken radially greater than the total thickness of the single-side melt layer crystallized on the lined insert wall and the thimble wall in the process of pouring-in and holding the melt till the end of crystallization.
- the crystallized melt layer under the lower plane of the lined flange exhibits no significant resistance to the motion as it has no support provided under the same.
- the thimble is arranged to be removable since at the end of pouring-in process it is grasped along its lateral surface by the solidified butt-end and, as the bottom table is lowered with the metal reservoir, is removed from the container neck to stay within the metal reservoir. Therefore, the above combination of features of the claimed device enables unimpeded motion of the metal reservoir within the container neck under various rates and with possible stops for solving the technical problem of reinforcement of the investment mold by providing an additional metal sheath on the inner surface of the ceramic investment mold during crystallization of the melt layer butting against its inner walls.
- FIG. 1 show a lost-wax casting device associated with piezocrystallization used in the proposed casting method.
- the lost-wax casting device associated with piezocrystallization comprises a frame 1 with a stationary upper table 2 and a movable bottom table 3 driven by a hydraulic drive 4 .
- a container 5 with an investment mold 6 molded into a filler is rigidly fixed to the upper table.
- a removable thimble 8 is mounted in the neck 7 of the container 5 , said thimble being retained on the lower plane of the neck 7 by a seal 9 .
- the seal 9 also holds the filler within the container 5 and a pouring head with an opening 10 of the investment mold 6 .
- On the bottom table 3 a metal reservoir 11 is mounted comprising a base 12 with grooves 13 wherein a removable insert 14 with a gas-proof lining 15 is disposed with a minimum positive allowance.
- the seal 9 and the lining 15 may be made of a core sand mixture, for example, water glass mixture. Openings 16 for release of gas are provided in the upper part of the lateral element of the removable insert 14 .
- a flange 18 lined on a side of its cavity is mounted on the upper edge of the insert 14 .
- a running fit matched pair is formed by the thimble 8 and a central opening of the lined flange 18 along their outer and inner surfaces, respectively.
- Lead-in chamfers are provided on the thimble 8 and the flange 18 for mutual centering the lined flange 18 and the thimble 8 .
- the value “E” shown in the Drawing is greater that the total thickness of the single-side melt layer crystallized on the wall of the lined insert 14 and the wall of thimble 8 in the process of pouring-in and holding the melt till the end of crystallization.
- the bottom table 3 is mounted on the hydraulic drive 4 rod rigidly fixed to the frame 1 .
- the device is also provided with standard automatic means for monitoring and controlling the hydraulic drive 4 operating parameters: travel, time, rod velocity, pressure (not shown).
- the ceramic investment mold 6 is produced, baked according to a batch process and then placed into the container 5 with filler therein so that the filling opening 10 has its edge at the level of the end surface of the container 5 neck 7 .
- the thimble 8 is placed on the neck 7 , and the end surface of the neck 7 is molded with a water glass mixture leaving the filling opening to form the seal 9 .
- the container 5 is fixed on the upper table 2 of the frame 1 such that the neck 7 is disposed in axial alignment with the metal reservoir 11 .
- the removable insert 14 Before the inner cavity of the removable insert 14 is mounted on the base 12 of the metal reservoir 11 , it is lined by a water glass mixture.
- the flange 18 lined by a water glass mixture is fixed on the top end of the insert 14 .
- the insert 14 mounted on the base 12 is centered relatively to the neck 7 .
- the pouring rate of 0.15-0.2 m/s and the pressure within 0.2-0.3 MPa is initially set by the hydraulic drive equipment based on the calculated melt flow rate of 7-8 kg/s.
- Casting is performed for rust-resisting austenitic steel.
- the melt is poured in the metal reservoir 11 at a temperature 25 ⁇ 1 C.° above the liquidus temperature to the level close to the flange 18 lining with the hydraulic drive 4 being immediately switched on and the liquid metal poured from the metal reservoir 11 into the mold 6 .
- the hydraulic drive 4 rod stops in up position.
- the melt is held under the predetermined pressure of 0.2-0.3 MPa for 6 to 8 seconds.
- the pressure is uniformly increased to 5-6 MPa, a pressure generated by the hydraulic drive.
- the rod has moved by a small amount proportional to the amount of the metal shrinkage of 2% to 2.5%, however, it is this motion for feeding the cast at a relatively high pressure that eliminates shrinkage defects, ensure high density, mechanical characteristics, and ultimately high cast product quality.
- the device operates as follows. Prior to pouring-in, the container 5 with the investment mold 6 molded therein and the removable thimble 8 placed onto its neck 7 is rigidly fixed to the upper table 2 of the frame. As this takes place, the container 8 filler and the thimble 8 are retained by the seal 9 .
- the pre-lined removable insert 14 is mounted on the bottom table 3 into the grooves 13 of the base 12 of the metal reservoir.
- the lined flange 18 is mounted on the upper end of the insert 14 .
- the metal reservoir 11 is caused to rise to the neck 7 with the thimble 8 thereon, which is centered relatively to the lined flange 18 by causing the insert 14 to move in a horizontal plane due to the minimum positive allowance in the grooves 13 of the base 12 . Then, the metal reservoir 11 is lowered into initial position. The device is ready to be operated.
- Liquid metal is poured into the reservoir 11 approximately to the lower plane level of the flange 18 lining.
- the hydraulic drive 4 is switched on.
- the metal reservoir 11 with the insert 14 rises and enters with its flange 18 into the thimble 8 on the neck 7 , which through the filling opening 10 extrudes the liquid metal into the investment mold 6 .
- gas air
- the hydraulic drive 4 rod stops in up position and is held for a few seconds.
- the liquid metal layer in the metal reservoir 11 will crystallize along the walls of the insert 14 lining 15 , the flange 18 lining and on the neck 7 with the thimble 8 .
- the pressure in the hydraulic drive 4 increases to the operating pressure till the end of crystallization of the liquid metal within the whole cast space. Due to the difference “E” between the inner diameters of the lined insert 14 and the flange 18 , no grasping thereof occurs by the solidified metal layer so that the hydraulic drive 4 rod may move to provide feeding the cast with a liquid metal from the metal reservoir 11 till the end of crystallization.
- the hydraulic drive 4 is switched to reverse operation.
- the metal reservoir 11 lowers to initial position entraining the thimble 8 due to the crystallized metal having been formed therein. Easy separation of the butt-end is facilitated from the bottom end of the neck 7 by the weakness of the seal 9 lining.
- the container 5 with the finished cast is removed from the upper table 2 of the frame 1 for extracting the cast.
- the insert 14 of the metal reservoir 11 is removed for replacing the lining.
- Another set comprising the container 5 with the thimble 8 mounted on the neck and the insert 14 of the metal reservoir 11 is fixed to the device, and the cycle is repeated.
- the invention is applicable in foundry industry, namely, for lost-wax casting associated with piezocrystallization, substantially, metal ware casting.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
- Casting Devices For Molds (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Measuring Fluid Pressure (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Continuous Casting (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2006103902/02A RU2312738C1 (ru) | 2006-02-09 | 2006-02-09 | Способ литья по выплавляемым моделям с кристаллизацией под давлением и устройство для его осуществления |
| RU2006103902 | 2006-02-09 | ||
| PCT/RU2006/000452 WO2007091915A1 (fr) | 2006-02-09 | 2006-08-29 | Procédé de coulage à partir de modèles à couler avec cristallisation sous pression et dispositif de sa mise en oeuvre |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20090218067A1 true US20090218067A1 (en) | 2009-09-03 |
Family
ID=38345424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US12/278,780 Abandoned US20090218067A1 (en) | 2006-02-09 | 2006-08-29 | Lost-wax method associated with piezocrystallization and a device for carrying out said method |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20090218067A1 (ru) |
| JP (1) | JP2009525878A (ru) |
| KR (1) | KR101302637B1 (ru) |
| CN (1) | CN101365552B (ru) |
| DE (1) | DE112006003535B4 (ru) |
| GB (1) | GB2448847A (ru) |
| RU (1) | RU2312738C1 (ru) |
| UA (1) | UA87085C2 (ru) |
| WO (1) | WO2007091915A1 (ru) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2517220B (en) * | 2013-08-13 | 2017-08-30 | Liopleurodon Capital Ltd | Method for HIP can manufacture, and can |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179497B (zh) * | 2011-04-13 | 2013-01-02 | 清华大学 | 一种负压条件下的铸造工艺方法 |
| JP6775780B2 (ja) * | 2016-07-22 | 2020-10-28 | 株式会社アクセル技研 | 低圧鋳造用溶湯保持炉 |
| DE102019209389A1 (de) * | 2019-06-27 | 2020-12-31 | Fraunhofer Gesellschaft zur Förderung der angewandten Forschung e.V. | Anordnung für den Niederdruckguss von hochschmelzenden Metallen |
| CN110328351B (zh) * | 2019-08-13 | 2021-06-04 | 西安西工大超晶科技发展有限责任公司 | 一种反重力浇注熔模铸件免水玻璃砂造型的工艺方法 |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5935874A (ja) * | 1982-08-24 | 1984-02-27 | Toyota Motor Corp | 低圧鋳造方法 |
| JPS6046860A (ja) * | 1983-08-24 | 1985-03-13 | Kawasaki Heavy Ind Ltd | 繊維強化複合金属からなる鋳造品の製造方法 |
| RU2015829C1 (ru) * | 1985-08-21 | 1994-07-15 | Караник Юрий Апполинарьевич | Способ литья выжиманием металла в форму с кристаллизацией под давлением |
| GB8604386D0 (en) * | 1986-02-21 | 1986-03-26 | Cosworth Res & Dev Ltd | Casting |
| US5010945A (en) * | 1988-11-10 | 1991-04-30 | Lanxide Technology Company, Lp | Investment casting technique for the formation of metal matrix composite bodies and products produced thereby |
| DE68903103T2 (de) * | 1989-03-07 | 1993-04-15 | Pechiney Aluminium | Verfahren zum vollformgiessen von metallischen gegenstaenden unter druck. |
| RU2048954C1 (ru) * | 1989-12-11 | 1995-11-27 | Караник Юрий Апполинарьевич | Способ литья по выплавляемым моделям с кристаллизацией под давлением |
| RU2116865C1 (ru) * | 1994-06-24 | 1998-08-10 | Новосибирское авиационное производственное объединение | Устройство для литья с кристаллизацией под давлением |
| RU2111085C1 (ru) * | 1996-06-13 | 1998-05-20 | Владимирский государственный технический университет | Способ изготовления инструмента для горячего и холодного прессования и штамповки |
| EP0971805B2 (de) * | 1997-04-03 | 2009-06-03 | Christian Reiter | Verfahren und giesseinrichtung für feinguss |
| JP2004122146A (ja) * | 2002-09-30 | 2004-04-22 | Aisin Keikinzoku Co Ltd | 厚肉製品の高圧鋳造法 |
| RU2245215C1 (ru) * | 2003-08-14 | 2005-01-27 | Караник Юрий Апполинарьевич | Устройство для литья выжиманием с кристаллизацией под давлением (лвкд) |
| DE10352179B4 (de) * | 2003-11-05 | 2007-09-06 | Dihag Deutsche Giesserei- Und Industrie-Holding Ag | Niederdruckgießverfahren zur Herstellung eines Gußteils |
-
2006
- 2006-02-09 RU RU2006103902/02A patent/RU2312738C1/ru not_active IP Right Cessation
- 2006-08-29 JP JP2008554174A patent/JP2009525878A/ja active Pending
- 2006-08-29 WO PCT/RU2006/000452 patent/WO2007091915A1/ru not_active Ceased
- 2006-08-29 DE DE112006003535T patent/DE112006003535B4/de not_active Expired - Fee Related
- 2006-08-29 UA UAA200810186A patent/UA87085C2/ru unknown
- 2006-08-29 US US12/278,780 patent/US20090218067A1/en not_active Abandoned
- 2006-08-29 KR KR1020087022045A patent/KR101302637B1/ko not_active Expired - Fee Related
- 2006-08-29 CN CN2006800525520A patent/CN101365552B/zh not_active Expired - Fee Related
-
2008
- 2008-08-28 GB GB0815680A patent/GB2448847A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2517220B (en) * | 2013-08-13 | 2017-08-30 | Liopleurodon Capital Ltd | Method for HIP can manufacture, and can |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112006003535B4 (de) | 2010-11-25 |
| WO2007091915A1 (fr) | 2007-08-16 |
| JP2009525878A (ja) | 2009-07-16 |
| DE112006003535T5 (de) | 2009-02-12 |
| WO2007091915A8 (fr) | 2008-09-12 |
| CN101365552B (zh) | 2011-03-09 |
| RU2312738C1 (ru) | 2007-12-20 |
| UA87085C2 (ru) | 2009-06-10 |
| KR101302637B1 (ko) | 2013-09-04 |
| CN101365552A (zh) | 2009-02-11 |
| GB0815680D0 (en) | 2008-10-08 |
| RU2006103902A (ru) | 2007-08-20 |
| GB2448847A (en) | 2008-10-29 |
| KR20080104295A (ko) | 2008-12-02 |
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