EP1066134A1 - Abrasive tools - Google Patents
Abrasive toolsInfo
- Publication number
- EP1066134A1 EP1066134A1 EP99906733A EP99906733A EP1066134A1 EP 1066134 A1 EP1066134 A1 EP 1066134A1 EP 99906733 A EP99906733 A EP 99906733A EP 99906733 A EP99906733 A EP 99906733A EP 1066134 A1 EP1066134 A1 EP 1066134A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- abrasive
- wheel
- grinding
- segments
- core
- 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
- 238000000227 grinding Methods 0.000 claims abstract description 109
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 68
- 239000000919 ceramic Substances 0.000 claims abstract description 39
- 239000000945 filler Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 20
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000006061 abrasive grain Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 229910003460 diamond Inorganic materials 0.000 claims description 28
- 239000010432 diamond Substances 0.000 claims description 28
- 239000011159 matrix material Substances 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000906 Bronze Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000010974 bronze Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- 239000010434 nepheline Substances 0.000 claims description 3
- 229910052664 nepheline Inorganic materials 0.000 claims description 3
- 239000008262 pumice Substances 0.000 claims description 3
- 239000010435 syenite Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 229920006332 epoxy adhesive Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 66
- 235000012431 wafers Nutrition 0.000 abstract description 7
- 230000002093 peripheral effect Effects 0.000 abstract description 6
- 239000011162 core material Substances 0.000 description 50
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 229910010293 ceramic material Inorganic materials 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- 230000006378 damage Effects 0.000 description 6
- 229920006333 epoxy cement Polymers 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 239000002826 coolant Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000010980 sapphire Substances 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 titanium hydride Chemical compound 0.000 description 3
- 229910000853 7075 T6 aluminium alloy Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 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 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001104 4140 steel Inorganic materials 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010010144 Completed suicide Diseases 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000001995 intermetallic alloy Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D5/00—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting only by their periphery; Bushings or mountings therefor
- B24D5/06—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting only by their periphery; Bushings or mountings therefor with inserted abrasive blocks, e.g. segmental
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/04—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic
- B24D3/06—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic metallic or mixture of metals with ceramic materials, e.g. hard metals, "cermets", cements
- B24D3/08—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic metallic or mixture of metals with ceramic materials, e.g. hard metals, "cermets", cements for close-grained structure, e.g. using metal with low melting point
Definitions
- the invention relates to abrasive tools suitable for precision grinding of hard brittle materials, such as ceramics and composites comprising ceramics, at peripheral wheel speeds up to 160 meters/second, and suitable for surface grinding of ceramic wafers.
- the abrasive tools comprise a wheel core or hub attached to a metal bonded superabrasive rim with a bond which is thermally stable during grinding operations.
- These abrasive tools grind ceramics at high material removal rates (e.g., 19-380 cm 3 /min/cm) , with less wheel wear and less workpiece damage than conventional abrasive tools.
- abrasive tool suitable for grinding sapphire and other ceramic materials is disclosed in U. S . -A-5, 607, 489 to Li.
- the tool is described as containing metal clad diamond bonded in a vitrified matrix comprising 2 to 20 volume % of solid lubricant and at least 10 volume % porosity.
- An abrasive tool containing diamond bonded in a metal matrix with 15 to 50 volume % of selected fillers, such as graphite, is disclosed in U. S . -A-3 , 925 , 035 to Keat .
- the tool is used for grinding cemented carbides .
- a cutting-off wheel made with metal bonded diamond abrasive grain is disclosed in U.S . -A-2 , 238, 351 to Van der Pyl .
- the bond consists of copper, iron, tin, and, optionally, nickel and the bonded abrasive grain is sintered onto a steel core, optionally with a soldering step to insure adequate adhesion. The best bond is reported to have a Rockwell B hardness of 70.
- An abrasive tool containing fine diamond grain (bort) bonded in a relatively low melting temperature metal bond, such as a bronze bond, is disclosed in U.S. -Re-21, 165. The low melting bond serves to avoid oxidation of the fine diamond grain.
- An abrasive rim is constructed as a single, annular abrasive segment and then attached to a central disk of aluminum or other material .
- the invention is a surface grinding abrasive tool comprising a core, having a minimum specific strength parameter of 2.4 MPa-cm /g, a core density of 0.5 to 8.0 g/cm3 , a circular perimeter, and an abrasive rim defined by a plurality of abrasive segments; wherein the abrasive segments comprise, in amounts selected to total a maximum of 100 vol %, from 0.05 to 10 vol % superabrasive grain, from 10 to 35 vol % friable filler, and from 55 to 89.95 vol % metal bond matrix having a fracture toughness of 1.0 to 3.0 MPa M 1/2.
- the specific strength parameter is defined as the ratio of the lesser of the yield strength or the fracture strength of the material divided by the density of the material.
- the friable filler is selected from the group consisting of graphite, hexagonal boron nitride, hollow ceramic spheres, feldspar, nepheline syenite, pumice, calcined clay and glass spheres, and combinations thereof.
- the metal bond matrix comprises a maximum of 5 vol % porosity. Description of the Drawings
- Figure 1 illustrates a continuous rim of abrasive segments bonded to the perimeter of a metal core to form a type 1A1 abrasive grinding wheel.
- Figure 2 illustrates a discontinuous rim of abrasive segments bonded to the perimeter of a metal core to form a cup wheel .
- Figure 3 illustrates the relationship between quantity of stock removed and normal force during grinding of an AlTiC workpiece with the abrasive grinding wheels of Example 5.
- the abrasive tools of the invention are grinding wheels comprising a core having a central bore for mounting the wheel on a grinding machine, the core being designed to support a metal bonded superabrasive rim along the periphery of the wheel. These two parts of the wheel are held together with a bond which is thermally stable under grinding conditions, and the wheel and its components are designed to tolerate stresses generated at wheel peripheral speeds of up to at least 80 m/sec, preferably up to 160 m/sec.
- Preferred tools are type 1A wheels, and cup wheels, such as type 2 or type 6 wheels or type 11V9 bell shaped cup wheels.
- the core is substantially circular in shape.
- the core may comprise any material having a minimum specific strength of 2.4 MPa-cm 3 /g, preferably 40-185 MPa-cm 3 /g-
- the core material has a density of 0.5 to 8.0 g/cm , preferably 2.0 to 8.0 g/cm .
- suitable materials are steel, aluminum, titanium and bronze, and their composites and alloys and combinations thereof.
- Reinforced plastics having the designated minimum specific strength may be used to construct the core.
- Composites and reinforced core materials typically have a continuous phase of a metal or a plastic matrix, often in powder form, to which fibers or grains or particles of harder, more resilient, and/or less dense, material is added as a discontinuous phase.
- reinforcing materials suitable for use in the core of the tools of the invention are glass fiber, carbon fiber, aramid fiber, ceramic fiber, ceramic particles and grains, and hollow filler materials such as glass, mullite, alumina and Zeolite® spheres.
- Steel and other metals having densities of 0.5 to 8.0 g/cm may be used to make the cores for the tools of the invention.
- light weight metals in powder form i.e., metals having densities of about 1.8 to 4.5 g/cm 3
- aluminum, magnesium and titanium, and alloys thereof, and mixtures thereof are preferred.
- Aluminum and aluminum alloys are especially preferred.
- Metals having sintering temperatures between 400 and 900° C, preferably 570-650°C, are selected if a co-sintering assembly process is used to make the tools.
- Low density filler materials may be added to reduce the weight of the core.
- Porous and/or hollow ceramic or glass fillers such as glass spheres and mullite spheres are suitable materials for this purpose. Also useful are inorganic and nonmetallic fiber materials. When indicated by processing conditions, an effective amount of lubricant or other processing aids known in the metal bond and superabrasive arts may be added to the metal powder before pressing and sintering.
- the tool should be strong, durable and dimensionally stable in order to withstand the potentially destructive forces generated by high speed operation.
- the core must have a minimum specific strength to operate grinding wheels at the very high angular velocity needed to achieve tangential contact speed between 80 and 160 m/s.
- the minimum specific strength parameter needed for the core materials used in this invention is 2.4 MPa-cm 3 /g-
- the specific strength parameter is defined as the ratio of core material yield (or fracture) strength divided by core material density. In the case of brittle materials, having a lower fracture strength than yield strength, the specific strength parameter is determined by using the lesser number, the fracture strength.
- the yield strength of a material is the minimum force applied in tension for which strain of the material increases without further increase of force.
- .ANSI 4140 steel hardened to above about 240 has a tensile strength in excess of 700 MPa . Density of this steel is about 7.8 g/cm 3 . Thus, its specific strength parameter is about 90 MPa-cm 3 /g.
- certain aluminum alloys for example, Al 2024, Al 7075 and Al 7178, that are heat treatable to Brinell hardness above about 100 have tensile strengths higher than about 300 MPa. Such aluminum alloys have low density of about 2.7 g/cm 3 and thus exhibit a specific strength parameter of more than 110 MPa-cm 3 /g. Titanium alloys and bronze composites and alloys fabricated to have a density no greater than 8.0 g/cm , are also suitable for use .
- the core material should be tough, thermally stable at temperatures reached in the grinding zone (e.g., about 50 to 200 °C) , resistant to chemical reaction with coolants and lubricants used in grinding and resistant to wear by erosion due to the motion of cutting debris in the grinding zone.
- temperatures reached in the grinding zone e.g., about 50 to 200 °C
- some alumina and other ceramics have acceptable failure values (i.e., in excess of 60 MPa-cm 3 /g) , they generally are too brittle and fail structurally in high speed grinding due to fracture. Hence, ceramics are not suitable for use in the tool core.
- Metal, especially hardened, tool quality steel, is preferred.
- the abrasive segment of the grinding wheel for use with the present invention is a segmented or continuous rim mounted on a core.
- a segmented abrasive rim is shown in Fig. 1.
- the core 2 has a central bore 3 for mounting the wheel to an arbor of a power drive (not shown) .
- the abrasive rim of the wheel comprises superabrasive grains 4 embedded (preferably in uniform concentration) in a metal matrix bond 6.
- a plurality of abrasive segments 8 make up the abrasive rim shown in Fig.
- An individual abrasive segment as shown in Fig. 1, has a truncated, rectangular ring shape (an arcurate shape) characterized by a length, 1, a width, w, and a depth, d.
- a grinding wheel shown in Fig. 1 is considered representative of wheels which may be operated successfully according to the present invention, and should not be viewed as limiting.
- the numerous geometric variations for segmented grinding wheels deemed suitable include cup- shaped wheels, as shown in Fig. 2, wheels with apertures through the core and/or gaps between consecutive segments, and wheels with abrasive segments of different width than the core. Apertures or gaps are sometimes used to provide paths to conduct coolant to the grinding zone and to route cutting debris away from the zone. A wider segment than the core width is occasionally employed to protect the core structure from erosion through contact with swarf material as the wheel radially penetrates the work piece.
- the wheel can be fabricated by first forming individual segments of preselected dimension and then attaching the preformed segments to the circumference 9 of the core with an appropriate adhesive.
- Another preferred fabrication method involves forming segment precursor units of a powder mixture of abrasive grain and bond, molding the composition around the circumference of the core, and applying heat and pressure to create and attach the segments, in si tu (i.e., co-sintering the core and the rim) .
- a co-sintering process is preferred for making surface grinding cup wheels used to backgrind wafers and chips of hard ceramics such as AlTiC.
- the abrasive rim component of the abrasive tools of the invention can be a continuous rim or a discontinuous rim, as shown in Figures 1 and 2, respectively.
- the continuous abrasive rim may comprise one abrasive segment, or at least two abrasive segments, sintered separately in molds, and then individually mounted on the core with a thermally stable bond (i.e., a bond stable at the temperatures encountered during grinding at the portion of the segments directed away from the grinding face, typically about 50-350° C) .
- a thermally stable bond i.e., a bond stable at the temperatures encountered during grinding at the portion of the segments directed away from the grinding face, typically about 50-350° C.
- a continuous rim, type 1A wheel is preferred for high speed grinding. Segmented continuous abrasive rims are preferred over a single continuous abrasive rim, molded as a single piece in a ring shape, due to the greater ease of achieving a truly round, planar shape during manufacture of a tool from multiple abrasive segments.
- discontinuous abrasive rims e.g., the cup wheel shown in Figure 2 are preferred. Because surface quality is critical in low speed surface finishing operations, slots may be formed in the segments, or some segments may be omitted from the rim to aid in removal of waste material which could scratch the workpiece surface.
- the abrasive rim component contains superabrasive grain held in a metal matrix bond, typically formed by sintering a mixture of metal bond powder and the abrasive grain in a mold designed to yield the desired size and shape of the abrasive rim or the abrasive rim segments.
- the superabrasive grain used in the abrasive rim may be selected from diamond, natural and synthetic, CBN, and combinations of these abrasives. Grain size and type selection will vary depending upon the nature of the workpiece and the type of grinding process. For example, in the grinding and polishing of sapphire or AlTiC, a superabrasive grain size ranging from 2 to 300 micrometers is preferred. For grinding other alumina, a superabrasive grain size of about 125 to 300 micrometers (60 to 120 grit; Norton Company grit size) is generally preferred. For grinding silicon nitride, a grain size of about 45 to 80 micrometers (200 to 400 grit) , is generally preferred.
- the tools comprise 0.05 to 10 volume % superabrasive grain, preferably 0.5 to 5 volume %.
- a minor amount of a friable filler material having a hardness less than that of the metal bond matrix, may be added as bond filler to increase the wear rate of the bond.
- the filler may be used at 10 to 35 volume %, preferably 15 to 35 volume %.
- Suitable friable filler material must be characterized by suitable thermal and mechanical properties to survive the sintering temperature and pressure conditions used to manufacture the abrasive segments and assemble the wheel.
- Graphite, hexagonal boron nitride, hollow ceramic spheres, feldspar, nepheline syenite, pumice, calcined clay and glass spheres, and combinations thereof, are examples of . useful friable filler materials.
- K lc is the fracture toughness
- ⁇ f is the stress applied at fracture
- c is one-half of the crack length.
- the bond wear rate should be equal to or slightly higher than the wear rate of the abrasive grain during grinding operations. Fillers, such as are mentioned above, may be added to the metal bond to decrease the wheel wear rate.
- Metal powders such as are mentioned above, may be added to the metal bond to decrease the wheel wear rate.
- Materials useful in the metal bond of the rim include, but are not limited to, bronze, copper and zinc alloys (brass) , cobalt and iron, and their alloys and mixtures thereof. These metals optionally may be used with titanium or titanium hydride, or other superabrasive reactive (i.e., active bond components) material capable of forming a carbide or nitride chemical linkage between the grain and the bond at the surface of the superabrasive grain under the selected sintering conditions to strengthen the grain/bond posts. Stronger grain/bond interactions will limit premature loss of grain and workpiece damage and shortened tool life caused by premature grain loss.
- the metal matrix comprises 55 to 89.95 volume % of the rim, more preferably 60 to 84.5 volume %.
- the friable filler comprises 10 to 35 volume % of the abrasive rim, preferably 15 to 35 volume %. Porosity of the metal matrix bond should be maintained at a maximum of 5 volume % during manufacture of the abrasive segment.
- the metal bond preferably has a Knoop hardness of 2 to 3 GPa.
- the core is made of aluminum and the rim contains a bronze bond made from copper and tin powders (80/20 wt . %) , and, optionally with the addition of 0.1 to 3.0 wt %, preferably 0.1 to 1.0 wt %, of phosphorus in the form of a phosphorus/copper powder.
- the metal powders of this composition are mixed with 100 to 400 grit (160 to 45 microns) diamond abrasive grain, molded into abrasive rim segments and sintered or densified in the range of 400-550° C at 20 to 33 MPa to yield a dense abrasive rim, preferably having a density of at least 95 % of the theoretical density (i.e., comprising no more than about 5 volume % porosity) .
- the metal powder of the core is poured into a steel mold and cold pressed at 80 to 200 kN (about 10-50 MPa pressure) to form a green part having a size approximately 1.2 to 1.6 times the desired final thickness of the core.
- the green core part is placed in a graphite mold and a mixture of the abrasive grain (2 to 300 micrometers grit size) and the metal bond powder blend is added to the cavity between the core and the outer rim of the graphite mold.
- a setting ring may be used to compact the abrasive and metal bond powders to the same thickness as the core preform.
- the graphite mold contents are then hot pressed at 370 to 410°C under 20 to 48 MPa of pressure for 6 to 10 minutes.
- the temperature may be ramped up (e.g., from 25 to 410°C for 6 minutes; held at 410°C for 15 minutes) or increased gradually prior to applying pressure to the mold contents.
- the graphite mold is stripped from the part, the part is cooled and the part is finished by conventional techniques to yield an abrasive rim having the desired dimensions and tolerances.
- the part may be finished to size using vitrified grinding wheels on grinding machines or carbide cutters on a lathe.
- any thermally stable adhesive having the strength to withstand peripheral wheel speeds up to 160 m/sec may be used.
- Thermally stable adhesives are stable to grinding process temperatures likely to be encountered at the portion of the abrasive segments directed away from the grinding face . Such temperatures typically range from about 50-350° C.
- the adhesive bond should be very strong mechanically to withstand the destructive forces existing during rotation of the grinding wheel and during the grinding operation.
- 10 part epoxy resin cements are preferred.
- a preferred epoxy cement, Technodyne® HT-18 epoxy resin (obtained from Taoka Chemicals, Japan) , and its modified amine hardener, may be mixed in the ratio of 100 parts resin to 19 parts hardener.
- Filler, such as fine silica powder, may be added at a ratio of 3.5 parts per 100 parts resin to increase cement viscosity.
- Segments may be mounted about the complete circumference of grinding wheel cores, or a partial circumference of the core, with the cement .
- the perimeter of the metal cores may be sandblasted to obtain a degree of roughness prior to attachment of the segments.
- the thickened epoxy cement is applied to the ends and bottom of segments which are positioned around the core substantially as shown in Fig.
- the epoxy cement is allowed to cure (e.g., at room temperature for 24 hours followed by 48 hours at 60°C) . Drainage of the cement during curing and movement of the segments is minimized during cure by the addition of sufficient filler to optimize the viscosity of the epoxy cement.
- Adhesive bond strength may be tested by spin testing at acceleration of 45 rev/min, as is done to measure the burst speed of the wheel .
- the wheels need demonstrated burst ratings equivalent to at least 271 m/s tangential contact speeds to qualify for operation under currently applicable safety standards 160 m/s tangential contact speed in the United States.
- the abrasive tools of the invention are particularly designed for precision grinding and finishing of brittle materials, such as advanced ceramic materials, glass, and components containing ceramic materials and ceramic composite materials.
- the tools of the invention are preferred for grinding ceramic materials including, but not limited to, silicon, mono- and polycrystalline oxides, carbides, borides and suicides; polycrystalline diamond; glass; and composites of ceramic in a non-ceramic matrix; and combinations thereof.
- typical workpiece materials include, but are not . limited to, AlTiC, silicon nitride, silicon oxynitride, stabilized zirconia, aluminum oxide (e.g., sapphire), boron
- ceramic parts improved by using the abrasive tools of the invention are ceramic engine valves and rods, pump seals, ball bearings and fittings, cutting tool inserts, wear parts, drawing dies for metal forming, refractory components, visual display windows, flat glass for windshields, doors and windows, insulators and electrical parts, and ceramic electronic components, including, but not limited to, silicon wafers, AlTiC chips, read-write heads magnetic heads, and substrates.
- Abrasive wheels of the invention were prepared in the form of 1A1 metal bonded diamond wheels utilizing the materials and processes described below.
- a blend of 43.74 wt % copper powder (Dendritic FS grade, particle size +200/-325 mesh, obtained from Sintertech International Marketing Corp., Ghent, NY); 6.24 wt% phosphorus/copper powder (grade 1501, +100/-325 mesh particle size, obtained from New Jersey Zinc Company, Palmerton, PA) ; and 50.02 wt% tin powder (grade MD115, +325 mesh, 0.5% maximum, particle size, obtained from Alcan Metal Powders, Inc., Elizabeth, New Jersey) was prepared.
- Diamond abrasive grain (320 grit size synthetic diamond obtained from General Electric, Worthington, Ohio) was added to the metal powder blend and the combination was mixed until it was uniformly
- the segments were ground to the required arcurate geometry to match the periphery of a machined aluminum core (7075 T6 aluminum, obtained from Yarde Metals, Tewksbury, MA) , yielding a wheel with an outer diameter of about 393 mm, and segments 0.62 cm thick.
- a machined aluminum core 7075 T6 aluminum, obtained from Yarde Metals, Tewksbury, MA
- the abrasive segments and the aluminum core were assembled with a silica filled epoxy cement system (Technodyne HT-18 adhesive, obtained from Taoka Chemicals, Japan ) to make grinding wheels having a continuous rim consisting of multiple abrasive segments.
- the contact surfaces of the core and the segments were degreased and sandblasted to insure adequate adhesion.
- full size wheels were purposely spun to destruction to determine the burst strength and rated maximum operating speed according to the Norton Company maximum operating speed test method.
- the table below summarizes the burst test data for typical examples of the 393 -mm diameter experimental metal bonded wheels .
- the resin wheel was tested at all three speeds.
- the vitrified wheel was tested at 32 m/s (6252 sfpm) only, due to speed tolerance considerations.
- Machine Studer Grinder Model S40 CNC Wheel Specifications: SD320-R4BX619C, SD320-N6V10, Size : 393mm diameter, 15 mm thickness and
- Wheel Speed 32, 56, and 80 m/s (6252, 11000, and 15750 sfpm)
- Coolant Inversol 22 @60% oil and 40% water Coolant Pressure: 270 psi (19 kg/cm2)
- Si 3 N 4 (rods made of NT551 silicon nitride, obtained from Norton Advanced Ceramics, Northboro, Massachusetts) 25.4 mm (1 in.) diameter X 88.9 mm (3.5 in.) long
- Wheel 5SG46IVS (obtained from Norton Company) Wheel Size: 152 mm diameter (6 inches) Wheel Speed: 3000 rpm; at +0.8 ratio relative to the grinding wheel
- Tests were performed in a cylindrical outer diameter plunge mode in grinding the silicon nitride rods.
- the 88.9 mm (3.5 in.) samples were held in a chuck with approximately 31 mm (1-1/4 in.) exposed for grinding.
- Each set of plunge grind tests started from the far end of each rod.
- the wheel made a 6.35 mm (1/4 in.) wide and 3.18 mm (1/8 in.) radial depth of plunge to complete one test .
- the work rpm was then re-adjusted to compensate for the loss of work speed due to reduced work diameter.
- Two more similar plunges were performed at the same location to reduce the work diameter from 25.4 mm (1 in.) to 6.35 mm (1/4 in.) .
- the wheel was then laterally moved 6.35 mm (1/4 in.) closer to the chuck to perform next three plunges.
- Four lateral movements were performed on the same side of a sample to complete the twelve plunges on one end of a sample .
- the sample was then reversed to expose the other end for another twelve grinds. A total of 24 plunge grinds was done on each sample.
- the initial comparison tests for the metal bonded wheels of the invention and the resin and vitrified wheels were conducted at 32 m/s peripheral speed at three material removal rates (MRR') from approximately 3.2 mm 3 /s/mm (0.3 in 3 /min/in) to approximately 10.8 mm /s/mm (1.0 in /min/in) .
- Table 1 shows the performance differences, as depicted by G-ratios, among the three different types of wheels after twelve plunge grinds.
- G-ratio is the unit-less ratio of volume material removed over volume of wheel wear.
- the data showed that the N grade vitrified wheel had better G ratios than the R grade resin wheel at the higher material removal rates, suggesting that a softer wheel performs better in grinding a ceramic workpiece.
- the harder, experimental, metal bonded wheel (#6) was far superior to the resin wheel and the vitrified wheel at all material removal rates.
- Table 1 shows the estimated G-ratios for the resin wheel and the new metal bonded wheel (#6) at all material removal rate conditions . Since there was no measurable wheel wear after twelve grinds at each material removal rate for the metal bonded wheel, a symbolic value of 0.01 mil (0.25 ⁇ m)
- the metal bond wheel of the invention contained 75 diamond concentration (about 18.75 volume % abrasive grain in the abrasive segment) , and the resin and vitrified wheels were 100 concentration and 150 concentration (25 volume % and 37.5 volume %) , respectively, the wheel of the invention still exhibited superior grinding performance. At these relative grain concentrations, one would expect superior grinding performance from the control wheels containing a higher volume % of abrasive grain. Thus, these results were unexpected.
- Table 1 shows the surface finish (Ra) and waviness (Wt) data measured on samples ground by the three wheels at the low test speed.
- the waviness value, Wt is the maximum peak to valley height of the waviness profile. All surface finish data were measured on surfaces created by cylindrical plunge grinding without spark-out. These surfaces normally would be rougher than surfaces created by traverse grinding.
- Table 1 shows the difference in grinding power consumption at various material removal rates for the three wheel types .
- the resin wheel had lower power consumption than the other two wheels; however, the experimental metal bonded wheel and vitrified wheel had comparable power consumption.
- the experimental wheel drew an acceptable amount of power for ceramic grinding operations, particularly in view of the favorable G-ratio and surface finish data observed for the wheels of the invention. In general, the wheels of the invention demonstrated power draw proportional to material removal rates .
- the metal bonded wheel power draw was roughly proportional to the MRR.
- the highest MRR achieved in this study was 47.3 mm 3 /s/mm (28.4cm 3 /min/cm) .
- Table 2 data are averages of twelve grinding passes . Individual power readings for each of the twelve passes remained remarkably consistent for the experimental wheel within each material removal rate. One would normally observe an increase of power as successive grinding passes are carried and the abrasive grains in the wheel begins to dull or the face of the wheel becomes loaded with workpiece material. This is often observed as the MRR is increased. However, the steady power consumption levels observed within each MRR during the twelve grinds demonstrates, unexpectedly, that the experimental wheel maintained its sharp cutting points during the entire length of the test at all MRRs.
- Table 2 shows that the samples ground by the experimental metal bonded wheel at all 14 material removal rates maintained constant surface finishes between 0.4 ⁇ m (16 ⁇ in.) and 0.5 ⁇ m (20 ⁇ in.), and had waviness values between 1.0 ⁇ m (38 ⁇ in.) and 1.7 ⁇ m (67 ⁇ in.) .
- the resin wheel was not tested at these high material removal rates. However, at about 8.6 mm 3 /s/mm (0.8 in /min/in) material removal rate, the ceramic bars ground by the resin wheel had slightly better but comparable surface finishes (0.43 versus 0.5 ⁇ m, and poorer waviness (1.73 versus 1.18 ⁇ m) .
- Table 2 shows the improvement in surface finishes and waviness on the ground samples at higher wheel speed.
- the samples ground by the new metal bonded wheel had the lowest measured waviness under all wheel speeds and material removal rates tested.
- a cup shaped abrasive tool was prepared and tested in the grinding of sapphire on a vertical spindle "blanchard type" machine.
- the cup wheel was used successfully to grind the surface of a work material consisting of a 100 mm diameter sapphire solid cylinder yielding acceptable surface flatness under favorable grinding conditions of G-ratio, MRR and power consumption.
- Type 2A2 cup shaped abrasive tools (280 mm in diameter) suitable for backgrinding AlTiC or silicon wafers were prepared with the abrasive segments described in Table 3 below. Except as noted below, the segment sizes were 139.3 mm radius length, 3.13 mm wide and 5.84 mm deep.
- abrasive containing bond batch mixes sufficient to manufacture 16 segments per wheel in the proportions given in Table 3 were prepared by screening the weighed components through a U.S. Mesh 140/170 screen, and mixing the components to uniformly blend them. Powder needed for each segment was weighed, introduced into a graphite mold, leveled and compacted. The graphite segment molds were hot pressed at 405° C for 15 minutes at 3000 psi (2073 N/cm2) . Upon cooling, segments were removed from the mold. Assembly of a wheel by adhering the segments onto a machined 7075 T6 aluminum core was carried out as in Example 1. Segments were degreased, sandblasted, coated with adhesive and placed in cavities machined to conform to the wheel periphery. After curing the adhesive, the wheel was machined to size, balanced and speed tested.
- a. 2a is sample 2 from Table 3 with an abrasive segment rim width of 3.13 mm.
- 25 b. 2b is sample 2 from Table 3 with an abrasive segment rim width of 2.03 mm.
- Example 5 of the invention (samples 2a, 2b and 4) needed significantly less normal force during grinding.
- the force needed to remove an equivalent amount of stock at a MRR of 2 micron/second for the inventive wheel was equivalent to that needed at a MRR of 1 micron/second for the comparative wheel sample.
- wheel 2a samples needed approximately equal normal forces to grind at either a MRR rate of 1 micron/second or a MRR of 2 micron/second.
- the inventive wheels 2a, 2b and 4 of Example 5 also exhibited relative stable normal force demands as the amount of stock ground progressed from 200 to 600 microns. This type of grinding performance is highly desirable in backgrinding AlTiC wafers because these low force, steady state conditions minimize thermal and mechanical damage to the workpiece .
- the control wheel (Ex. 1) could not be tested at higher stock removal levels (e.g., above about 300 microns) because the force needed to grind with these wheels exceeded the normal force capacity of the grinding machine, thereby causing the machine to automatically shut down and preventing accumulation of data at the higher stock removal levels.
- higher stock removal levels e.g., above about 300 microns
- the superior grinding performance of the low diamond concentration, graphite filled inventive wheels is related to the smaller number of individual grains per unit of area of the abrasive segment that come in contact with the surface of the workpiece at any point in time during grinding.
- the wheel 2b sample has a smaller surface area and fewer grinding points in contact with the surface of the workpiece at any point in time during grinding operations than does the wheel 2a sample.
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE29924302U DE29924302U1 (en) | 1998-03-27 | 1999-02-04 | Grinding Tools |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/049,623 US6102789A (en) | 1998-03-27 | 1998-03-27 | Abrasive tools |
US49623 | 1998-03-27 | ||
US09/218,844 US6093092A (en) | 1998-03-27 | 1998-12-22 | Abrasive tools |
US218844 | 1998-12-22 | ||
PCT/US1999/002399 WO1999048646A1 (en) | 1998-03-27 | 1999-02-04 | Abrasive tools |
Publications (3)
Publication Number | Publication Date |
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EP1066134A1 true EP1066134A1 (en) | 2001-01-10 |
EP1066134B1 EP1066134B1 (en) | 2002-05-08 |
EP1066134B9 EP1066134B9 (en) | 2002-11-13 |
Family
ID=26727364
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99906733A Expired - Lifetime EP1066134B9 (en) | 1998-03-27 | 1999-02-04 | Abrasive tools |
Country Status (20)
Country | Link |
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EP (1) | EP1066134B9 (en) |
JP (2) | JP2002507491A (en) |
CN (1) | CN1130274C (en) |
AT (1) | ATE217235T1 (en) |
AU (1) | AU732575B2 (en) |
BR (1) | BR9909194A (en) |
CA (1) | CA2324578C (en) |
CZ (1) | CZ20003542A3 (en) |
DE (2) | DE69901438D1 (en) |
DK (1) | DK1066134T5 (en) |
ES (1) | ES2174590T3 (en) |
HK (1) | HK1034221A1 (en) |
HU (1) | HU222463B1 (en) |
ID (1) | ID25820A (en) |
IL (1) | IL138434A0 (en) |
PL (1) | PL197639B1 (en) |
SE (1) | SE1066134T5 (en) |
SK (1) | SK14402000A3 (en) |
TW (1) | TW393384B (en) |
WO (1) | WO1999048646A1 (en) |
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- 1999-02-04 DE DE69901438A patent/DE69901438D1/en not_active Expired - Lifetime
- 1999-02-04 ID IDW20001926A patent/ID25820A/en unknown
- 1999-02-04 ES ES99906733T patent/ES2174590T3/en not_active Expired - Lifetime
- 1999-02-04 DE DE69901438T patent/DE69901438T4/en not_active Expired - Lifetime
- 1999-02-04 PL PL343171A patent/PL197639B1/en unknown
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- 1999-02-04 CA CA002324578A patent/CA2324578C/en not_active Expired - Fee Related
- 1999-02-04 WO PCT/US1999/002399 patent/WO1999048646A1/en active IP Right Grant
- 1999-02-04 IL IL13843499A patent/IL138434A0/en unknown
- 1999-02-04 BR BR9909194-1A patent/BR9909194A/en not_active IP Right Cessation
- 1999-02-04 AU AU26573/99A patent/AU732575B2/en not_active Ceased
- 1999-02-04 AT AT99906733T patent/ATE217235T1/en active
- 1999-02-04 CZ CZ20003542A patent/CZ20003542A3/en unknown
- 1999-02-04 JP JP2000537677A patent/JP2002507491A/en not_active Withdrawn
- 1999-02-04 HU HU0102438A patent/HU222463B1/en not_active IP Right Cessation
- 1999-02-04 CN CN99804385A patent/CN1130274C/en not_active Expired - Fee Related
- 1999-02-04 DK DK99906733T patent/DK1066134T5/en active
- 1999-02-04 EP EP99906733A patent/EP1066134B9/en not_active Expired - Lifetime
- 1999-02-04 SK SK1440-2000A patent/SK14402000A3/en unknown
- 1999-02-11 TW TW088102167A patent/TW393384B/en not_active IP Right Cessation
-
2001
- 2001-07-09 HK HK01104698A patent/HK1034221A1/en not_active IP Right Cessation
-
2006
- 2006-08-17 JP JP2006222685A patent/JP2006346857A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO9948646A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1066134B1 (en) | 2002-05-08 |
AU732575B2 (en) | 2001-04-26 |
DK1066134T5 (en) | 2003-01-06 |
DE69901438T4 (en) | 2004-07-22 |
CZ20003542A3 (en) | 2001-12-12 |
DE69901438D1 (en) | 2002-06-13 |
DE69901438T2 (en) | 2003-02-27 |
HUP0102438A3 (en) | 2001-12-28 |
SE1066134T5 (en) | 2003-02-04 |
ATE217235T1 (en) | 2002-05-15 |
IL138434A0 (en) | 2001-10-31 |
EP1066134B9 (en) | 2002-11-13 |
HUP0102438A2 (en) | 2001-11-28 |
ID25820A (en) | 2000-11-09 |
JP2002507491A (en) | 2002-03-12 |
CN1130274C (en) | 2003-12-10 |
PL343171A1 (en) | 2001-07-30 |
SK14402000A3 (en) | 2001-10-08 |
JP2006346857A (en) | 2006-12-28 |
AU2657399A (en) | 1999-10-18 |
TW393384B (en) | 2000-06-11 |
HU222463B1 (en) | 2003-07-28 |
CN1294543A (en) | 2001-05-09 |
ES2174590T3 (en) | 2002-11-01 |
CA2324578C (en) | 2004-11-02 |
HK1034221A1 (en) | 2001-10-19 |
PL197639B1 (en) | 2008-04-30 |
WO1999048646A1 (en) | 1999-09-30 |
SE1066134T3 (en) | 2002-09-03 |
CA2324578A1 (en) | 1999-09-30 |
DK1066134T3 (en) | 2002-09-09 |
BR9909194A (en) | 2000-12-05 |
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