EP1011897A1 - Semi-solid metal forming process - Google Patents
Semi-solid metal forming processInfo
- Publication number
- EP1011897A1 EP1011897A1 EP98901901A EP98901901A EP1011897A1 EP 1011897 A1 EP1011897 A1 EP 1011897A1 EP 98901901 A EP98901901 A EP 98901901A EP 98901901 A EP98901901 A EP 98901901A EP 1011897 A1 EP1011897 A1 EP 1011897A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- billet
- semi
- temperature
- heated
- solid metal
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000007787 solid Substances 0.000 title claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 238000001953 recrystallisation Methods 0.000 claims abstract description 9
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 238000004512 die casting Methods 0.000 claims description 23
- 230000006698 induction Effects 0.000 claims description 11
- 238000005242 forging Methods 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 3
- 238000002224 dissection Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000243 solution Substances 0.000 description 27
- 238000001125 extrusion Methods 0.000 description 19
- 238000005266 casting Methods 0.000 description 12
- 241000237858 Gastropoda Species 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000010116 semi-solid metal casting Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 229910021323 Mg17Al12 Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QZIQJVCYUQZDIR-UHFFFAOYSA-N mechlorethamine hydrochloride Chemical compound Cl.ClCCN(C)CCCl QZIQJVCYUQZDIR-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/004—Thixotropic process, i.e. forging at semi-solid state
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/12—Making non-ferrous alloys by processing in a semi-solid state, e.g. holding the alloy in the solid-liquid phase
Definitions
- This invention relates generally to semi-solid metal forming and more particularly to the formation and use of magnesium billets in semi- solid metal die casting and semi-solid forging processes.
- Metal die casting is a process in which molten metal is caused to flow into a cavity defined by a mold.
- molten metal is injected into the cavity.
- semi-solid metal die casting processes a metal billet is pre-heated to a point of softening, to a temperature above the solidus and below the liquidus to produce a partially solid, partially liquid consistency prior to placing the billet or "slug" in a shot sleeve in the casting machine.
- Semi-solid metal die casting enables control of the microstructure of the finished part to a degree which produces a stronger part than is possible with conventional molten metal die-casting processes. As compared with conventional metal die-casting processes, semi-solid metal casting produces parts of improved casting quality in that they exhibit lower porosity, parts shrink less upon cooling enabling closer tolerances and physical properties are better. In addition, semi-solid metal casting has a reduced cycle time and the lower temperatures utilized result in decreased die wear. Because of the absence of molten metal there is less pollution and safety hazards are reduced.
- a billet is first formed which is treated to form fine grained equiaxed crystals as opposed to a dentritic structure.
- the grain structure of a billet must exhibit the necessary degree of lubricity and viscosity to give good laminar flow in the die cavity.
- an untreated DC cast billet will shear along its dentritic axis rather than flow hence the need for fine grained equiaxed crystals.
- Metal forging is another process in which metal is caused to flow into a cavity defined by a mold. Unlike die casting, metal is not injected as a liquid into the cavity, but rather a solid billet or slug is placed between dies which are subsequently forced together to squeeze the billet or slug into the cavity as the die is closed. In semi-solid metal forging, the metal billet is pre- heated to a partially solid, partially liquid consistency prior to forging. The consistency is similar to that used for semi-solid metal die casting.
- the billet should consist of fine grained equiaxed crystals rather than a dendritic structure to optimize the flow of metal between the dies and to optimize the physical characteristics of the finished parts.
- An earlier process for forming a treated billet involves the use of magnetic stirring during the cooling of a cast billet to break up and avoid the formation of a dentritic structure. Magnetic stirring is however a relatively slow and expensive process.
- the ingot produced according to the process described in Young may then be subsequently heated to semi-solid casting temperature and formed into a part in a die casting process.
- Figure IA is a schematic representation of the process of the present invention
- Figure IB is a schematic representation of an alternate embodiment process according to the present invention
- Figures 2 through 30 are photomicrographs of billets cut from extruded cast billets and are individually described in Example 1 below;
- Figure 31 illustrates sample locations in a test plate which were tested in Example 3;
- Figure 32 illustrates the locations at which photomicrographs were taken in Example 3 below.
- Figures 33 through 36 are photomicrographs individually described in
- molten metal 10 is poured from a ladle into a mold 12 and allowed to solidify into a cast billet 14.
- the cast billet 14 is heated, for example by inductive heating coil 16 to a temperature above its recrystallization temperature and below its solidus temperature.
- the heated cast billet 14 is then extruded through an extruding die 18 to form an extruded column 20.
- the extruded column 20 is cut to a suitable length billet 22 for use in a semi-solid metal die casting process.
- the billet 22 is heated to a forming temperature corresponding to a semi-solid state, for example by induction coils 24, and transferred to a die casting apparatus 26.
- the heated billet 22 is squeezed by the die casting apparatus into a cavity 28 between mold parts 30 and 32 to form a part 34 conforming in shape to that of the cavity 28.
- the heated billet 22 may be transferred to a forging apparatus 40 where it is squeezed into a cavity defined between a movable die 42 and a fixed die 44.
- the billets were produced initially as an 8 1/2 in. direct chill cast billet.
- the billets were cooled at a high chill rate utilizing copper molds and a water spray to provide a chill rate of at least 2°C per second at the billet centre.
- the billets were cut into 2 ft. long sections and the diameter machined down to 8 in. to remove imperfections to the outside edge.
- Grain sizing of the 8 inch billet perpendicular to the extrusion axis was 38 microns at the outside, 48 microns at the half radius and 48 microns at the center. As expected, the grain size in the longitudinal or extrusion direction was somewhat larger being approximately 51 microns at the outside, 64 microns at the half radius and 74 microns at the center.
- the billets were then heated in 4-6 minute intervals in three induction furnaces.
- the furnaces heated the billets to 100°C, 200°C, 300°C (total heating time approximately 15 minutes.)
- the billet was then placed in the extrusion chamber, which was at 380°C and the billet was extruded at between 330°C and 350°C, in one stage down to a 3 in. diameter extrusion billet.
- the first 14 ft. of extrusion and the last few feet were discarded.
- the remainder of the extrusion was cut into 7 in. sections or "slugs".
- billet 1 and billet 2 Two of the sections of the extrusion billet referred to as billet 1 and billet 2, in AZ61 alloy were examined in the "as extruded" condition by sectioning a 0.5 in. section off the end of each billet, (billets were randomly selected.) A micro was taken perpendicular to the axis of the billet from the centre and from the outside edge. The micros were polished and etched using 2% nitol etchant. The micros were examined at various magnifications to observe grain structure. A photomicrograph was taken at each magnification and the grain size estimated.
- the purpose for solution heat treating the extrusion billets and analyzing the samples was to determine the effect on grain size and shape resulting from heating and extruding the DC cast billet.
- the solution heat treating was not carried out under the optimum circumstances as equipment availability necessitated the use of convection heating rather than induction heating.
- the heating cycle should not exceed 20 minutes and accordingly multi-state induction heating would be preferable over convection heating. Nevertheless the results were quite favourable as set out below.
- Figure 2 is a photomicrograph of the outside edge of billet 1, as extruded, at 200 x magnification.
- Figure 3 is a photomicrograph of the outside edge of billet 1, as extruded at 400 x magnification;
- Figure 4 is a photomicrograph of the centre of billet 1, as extruded under 100 x magnification
- Figure 5 is a photomicrograph of the centre of billet 1, as extruded under 200 x magnification
- Figure 6 is a photomicrograph of the outside edge of billet 2, as extruded, at 200 x magnification
- Figure 7 is a photomicrograph of the outside edge of billet 2, as extruded, at 400 x magnification
- Figure 8 is a photomicrograph of the centre of billet 1, as extruded, at 400 x magnification
- Figure 9 is a photomicrograph of the centre of billet 2, as extruded, at 200 x magnification
- Figure 10 is a photomicrograph of the centre of billet 2, as extruded, at 400 x magnification;
- Figure 11 is a photomicrograph of the outside edge of billet 1, extruded and solution heat treated, at 50 x magnification;
- Figure 12 is a photomicrograph of the outside edge of billet 1, extruded and solution heat treated, at 100 x magnification;
- Figure 13 is a photomicrograph of the outside edge of billet 1, extruded and solution heat treated, at 200 x magnification;
- Figure 14 is a photomicrograph of the centre of billet 1, extruded and solution heat treated at 50 x magnification
- Figure 15 is a photomicrograph of the centre of billet 1, extruded and solution heat treated at 100 x magnification;
- Figure 16 is a photomicrograph of the centre of billet 1, extruded and solution heat treated, at 200 x magnification;
- Figure 17 is a photomicrograph of the outside edge of billet 2, extruded and solution heat treated, at 50 x magnification;
- Figure 18 is a photomicrograph of the outside edge of billet 2, extruded and solution heat treated, at 100 x magnification;
- Figure 19 is a photomicrograph of the outside edge of billet 2, extruded and solution heat treated, at 200 x magnification;
- Figure 20 is a photomicrograph of the centre of billet 2, extruded and solution heat treated, at 50 x magnification
- Figure 21 is a photomicrograph of the centre of billet 2, extruded and solution heat treated, at 100 x magnification
- Figure 22 is a photomicrograph of the centre of billet 2, extruded and solution heat treated, at 200 x magnification;
- Figure 23 is a photomicrograph of the centre of billet 1, as extruded, parallel to the extrusion axis, at 100 x magnification;
- Figure 24 is a photomicrograph of the centre of billet 1, as extruded, parallel to the extrusion axis, at 200 x magnification;
- Figure 25 is a photomicrograph of the centre of billet 2, as extruded, parallel to the extrusion axis, at 100 x magnification;
- Figure 26 is a photomicrograph of the centre of billet 2, as extruded, parallel to the extrusion axis, at 200 x magnification;
- Figure 27 is a photomicrograph of the centre of billet 1 parallel to the extrusion axis, after solution heat treatment, at 100 x magnification;
- Figure 28 is a photomicrograph of the centre of billet 1 parallel to the extrusion axis, after solution heat treatment, at 200 x magnification;
- Figure 29 is a photomicrograph of the centre of billet 2 parallel to the extrusion axis, after solution heat treatment, at 100 x magnification;
- Figure 30 is a photomicrograph of the centre of billet 2 parallel to the extrusion axis, after solution heat treatment, at 200 x magnification; Grain Size Determination
- microstructure observed consists of magnesium primary magnesium and aluminum solid solution crystals and eutectic consisting of two phases, secondary magnesium solid solution crystals and Mg 17 Al 12 intermetallic compound.
- the structure was quite broken up in the "as cast" specimens and grain size measurement is only approximate.
- Recrystallized grain structure in the solution heat treated specimens was more accurate and well defined in the microstructure.
- micros taken in the direction of the extrusion axis of the "as extruded" specimens showed long stringers in the microstructure.
- the corresponding micros taken from the heat treated specimens showed a more evenly distributed recrystallized structure.
- the amount of breakdown that the grain structure of the as-cast billet will undergo is likely a function of the amount of reduction. In the present case 7 to 1 reduction was used. Some sources suggest that the optimum degree of reduction should be on the order of from 10:1 to 17:1. In practice however the degree of reduction required may be less if the starting alloy is relatively fine grained.
- a welding test plate die was chosen, heated by oil to approximately 220°C.
- the material was SSM-castable, but different than other magnesium alloys.
- the thickwall part (10mm thick) was perhaps not ideal for magnesium casting.
- Slug heating was performed in a single coil induction heater and optimized such that the slugs were removed from the coil just prior to the onset of burning which corresponded to a softness which allowed dissection with a knife. Total heating time was approximately 230 seconds. Very little metal run-off was obtained during the heating process.
- a single stage induction heater was utilized for the test as multi-stage induction heating was not available at the test facility. It is expected that better heating would have been obtained with multi-stage induction heating. Ideally at the end of the heating cycle the billet should have a uniform temperature throughout with a well controlled solid to liquid ratio.
- the first parts were cast using a plunger velocity of 0.3 to 0.8 meters per second. These conditions barely filled the die and visual laps were apparent at the end of the part.
- the heat treated slugs appeared lighter in color after heating and had less tendency to burn.
- the SSM parts produced from these slugs also appeared lighter in color.
- the only parameter varied in making the test plates was the gate or plunger velocity. Accordingly none of the resulting plates could be considered high quality castings. It is expected that much better results would have been obtained if the die temperature had been increased to approximately 300°C and the slugs were heated in the multi-stage induction heater.
- the cast plates show good physical properties.
- the casting machine was a single cylinder unit having servo control to carefully control the force driving the slug into the closed die. Optimally the casting process will cause the outer skin of the slug which contains surface oxides resulting from the heating process to be removed from the virgin metal.
- Plates 34 and 35 were sectioned into six sections as illustrated in Figure 30. One quarter inch (1/4 in.) round samples were removed from the sections and tested for mechanical properties. The plates were not heat treated and the results are tabulated in Table 1 below. TABLE 1
- Plates 34 and 35 were subsequently solution heat treated for 12 hours at 426°C and still air cooled.
- One quarter inch (1/4 in.) round samples were cut from the plates and the mechanical properties of those samples were tested. The results of the tests are tabulated in Table 2 below.
- Table 2 below the sample plan for the heat treated plates is the same as illustrated in Figure 31.
- Photomicrographs of one of the plates were taken at locations Ml and M2 as illustrated in Figure 32.
- the photomicrographs are reproduced in Figures 33 through 36 as follows.:
- Figure 33 is a photomicrograph of sample Ml at 50x magnification
- Figure 34 is a photomicrograph of sample Ml at lOOx magnification
- Figure 35 is a photomicrograph of sample M2 at 50x magnification
- Figure 36 is a photomicrograph of sample M2 at lOOx magnification.
- AZ61 magesium alloy was utilized in the tests no doubt other magesium alloys could be used.
- the process can also be adapted to metal systems other than magesium where the metal is capable of forming a two-phase system comprising a solid particles in a lower melting matrix.
- the process will work with aluminum and may also work with other similar metal systems such as copper. It is intended that any such variations be deemed as within the scope of the present patent as long as such are within the spirit and scope of the claims set out below.
- heating of the billet 22 prior to forming should be carried out at a rate of no greater than 30°C per second and even more preferably at a rate of no greater than 20°C per second if aluminum is being used. Heating at a rate greater than 30°C per second may result in the precipitation of silicon from the resulting stresses thereby deleteriously affecting machinability of the finished part. It has been found that a three stage induction heater is particularly well suited to maintaining a desirable heating rate.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Forging (AREA)
- Extrusion Of Metal (AREA)
Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002196479A CA2196479A1 (en) | 1997-01-31 | 1997-01-31 | Semi-solid metal casting process |
CA2196479 | 1997-01-31 | ||
CA002227828A CA2227828C (en) | 1997-01-31 | 1998-01-23 | Semi-solid metal forming process |
CA2227828 | 1998-01-23 | ||
PCT/CA1998/000062 WO1998033610A1 (en) | 1997-01-31 | 1998-02-02 | Semi-solid metal forming process |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1011897A1 true EP1011897A1 (en) | 2000-06-28 |
EP1011897B1 EP1011897B1 (en) | 2003-09-17 |
Family
ID=25679021
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98901901A Expired - Lifetime EP1011897B1 (en) | 1997-01-31 | 1998-02-02 | Semi-solid metal forming process |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1011897B1 (en) |
JP (1) | JP2001509085A (en) |
AU (1) | AU5850098A (en) |
CA (1) | CA2227828C (en) |
DE (1) | DE69818282D1 (en) |
WO (1) | WO1998033610A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6120625A (en) * | 1998-06-10 | 2000-09-19 | Zhou; Youdong | Processes for producing fine grained metal compositions using continuous extrusion for semi-solid forming of shaped articles |
JP3503521B2 (en) * | 1999-03-31 | 2004-03-08 | マツダ株式会社 | Method for forming forging material, forming apparatus, and method for manufacturing forged member using the above material |
EP1274525A2 (en) * | 1999-08-24 | 2003-01-15 | Smith & Nephew, Inc. | Combination of processes for making wrought components |
DE19956478C2 (en) * | 1999-11-24 | 2001-10-18 | Hengst Walter Gmbh & Co Kg | Process and apparatus for making castings |
CN100347331C (en) * | 2005-03-28 | 2007-11-07 | 南昌大学 | Method for AZ61 magnesium alloy semi-solid blank |
JP4558818B2 (en) | 2008-06-27 | 2010-10-06 | ダイキン工業株式会社 | Semi-molten or semi-solid molding method and molding equipment |
CN102139337A (en) * | 2011-02-22 | 2011-08-03 | 重庆大学 | Dual-controlled composite forming method for casting and forging of magnesium alloy |
CN112872270A (en) * | 2020-12-28 | 2021-06-01 | 哈尔滨工业大学 | Semi-solid thixotropic-solid plastic deformation composite forming device for 6A02 aluminum alloy U-shaped parts and using method thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4415374A (en) * | 1982-03-30 | 1983-11-15 | International Telephone And Telegraph Corporation | Fine grained metal composition |
-
1998
- 1998-01-23 CA CA002227828A patent/CA2227828C/en not_active Expired - Fee Related
- 1998-02-02 EP EP98901901A patent/EP1011897B1/en not_active Expired - Lifetime
- 1998-02-02 DE DE69818282T patent/DE69818282D1/en not_active Expired - Lifetime
- 1998-02-02 JP JP53240798A patent/JP2001509085A/en active Pending
- 1998-02-02 AU AU58500/98A patent/AU5850098A/en not_active Abandoned
- 1998-02-02 WO PCT/CA1998/000062 patent/WO1998033610A1/en active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO9833610A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU5850098A (en) | 1998-08-25 |
JP2001509085A (en) | 2001-07-10 |
CA2227828C (en) | 2002-11-12 |
WO1998033610A1 (en) | 1998-08-06 |
CA2227828A1 (en) | 1998-07-31 |
DE69818282D1 (en) | 2003-10-23 |
EP1011897B1 (en) | 2003-09-17 |
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