EP0827433A1 - Composite and process for the production thereof - Google Patents
Composite and process for the production thereofInfo
- Publication number
- EP0827433A1 EP0827433A1 EP95916564A EP95916564A EP0827433A1 EP 0827433 A1 EP0827433 A1 EP 0827433A1 EP 95916564 A EP95916564 A EP 95916564A EP 95916564 A EP95916564 A EP 95916564A EP 0827433 A1 EP0827433 A1 EP 0827433A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composite material
- phase
- binder metal
- material according
- metal phase
- 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.)
- Withdrawn
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 239000011230 binding agent Substances 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 6
- 239000011195 cermet Substances 0.000 claims abstract description 6
- 239000010959 steel Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 30
- 230000005855 radiation Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 230000035515 penetration Effects 0.000 claims description 7
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 7
- 238000007792 addition Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000001513 hot isostatic pressing Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000997 High-speed steel Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000601 superalloy Inorganic materials 0.000 claims description 2
- 239000012780 transparent material Substances 0.000 claims description 2
- 229910003310 Ni-Al Inorganic materials 0.000 claims 2
- 229910010038 TiAl Inorganic materials 0.000 claims 2
- 229910008484 TiSi Inorganic materials 0.000 claims 2
- 150000001247 metal acetylides Chemical class 0.000 claims 2
- 229910016006 MoSi Inorganic materials 0.000 claims 1
- 229910005883 NiSi Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- COLZOALRRSURNK-UHFFFAOYSA-N cobalt;methane;tungsten Chemical compound C.[Co].[W] COLZOALRRSURNK-UHFFFAOYSA-N 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 229910009043 WC-Co Inorganic materials 0.000 abstract description 4
- 238000005452 bending Methods 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 25
- 150000002739 metals Chemical class 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 210000002381 plasma Anatomy 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000009770 conventional sintering Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009768 microwave sintering Methods 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000013021 overheating 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
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F2003/1042—Sintering only with support for articles to be sintered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the invention relates to composite materials, consisting essentially of a cermet material with a binder metal phase of 5 to 30% by mass, the rest of at least one carbonitride phase or a hard metal with a hard material phase of 70 to 100%, the rest of the binder metal phase, with the exception of a WC-Co hard metal with 25% by mass of cobalt as binder metal or a powder-metallurgically produced steel.
- the invention further relates to a method for producing this composite material.
- Composite materials of the type mentioned are used in particular as cutting inserts for machining or as high-temperature materials.
- materials from the aforementioned class of materials are produced by sintering compacts which are made from the corresponding mixtures of hard materials and metal powders or metal powders.
- the sintering takes place in heatable furnaces which are equipped, for example, with graphite heating elements, the samples being heated indirectly by means of the radiation emitted by the heating elements and by convection or heat conduction.
- the disadvantage of this process technology is that the choice of the furnace atmosphere is limited by the chemical properties of the heating elements.
- the heating of hard metals, cermets or steels takes place from the outside in and is essentially controlled by the thermal conductivity and the emissivity of the samples.
- the composite material according to claim 1 which is characterized according to the invention in that it has been produced by sintering in a microwave field.
- microwave sintering represents direct heating in the volume of the composite materials of any geometry, only the requirement that the size of the sintered bodies be in the order of the wavelength of the used ones Microwave radiation must be observed.
- the composite materials with good electrical conductivity reflect part of the microwave radiation, depending on the binder metal phase content, the special microstructure, in particular porous hard metal and cermet green compacts, enables a high penetration depth of the microwave radiation into the pre-pressed pressed body even at low temperatures.
- Hot isostatic pressing preferably under a pressure of between 5 bar and 3000 bar, at temperatures of 1200 * C to 1750'C.
- Hot isostatic pressing is generally known and is described, for example, in "Powder Metallurgy of Hard Metals” by H. Kolaska, Weinmannuer-to-Stretrachloride, 1992, page 6/11 f. described.
- cermets have proven themselves, which have a carbonitride phase based on titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and / or tungsten and a binder metal phase composed of cobalt and / or nickel.
- hard metals with a hard material phase consisting of oxicarbides, oxynitrides, oxicarbonitrides or borides have proven their worth.
- the aforementioned hard metals can also have a hexagonal mixed carbide phase of the tungsten carbide with molybdenum carbide instead of the pure hexagonal tungsten carbide phase.
- the binder metal phase usually consisting of iron, cobalt and / or nickel can have up to 15% by mass of molybdenum, tungsten, titanium, manganese and / or aluminum.
- a nickel-aluminum alloy with a nickel / aluminum ratio of 90:10 to 70:30 can be used as the binder metal phase. Additions of up to 1% by mass of boron to the binder metal phases mentioned are possible.
- the binder metal phase can also consist of the substances described in claim 10 or mixtures thereof. Additions of 0 to 16% by mass of cobalt, nickel, iron or rare earth metals can be included.
- a heat-resistant binder metal phase can consist of powder-metallurgically produced high-speed steel and / or a superalloy.
- Corrosion-resistant binder metal phases made of nickel and chromium, which may contain additions of molybdenum, manganese, aluminum, silicon and / or copper in manganese of from 0.01 to 5% by mass, have also proven successful.
- the composite material can have one or more surface layers which have been applied by PVD, CVD or PCVD processes, preferably in a microwave field.
- the pre-pressed molded body When the pre-pressed molded body is heated in a microwave field, a controlled increase in the temperature of the product body can be reached even at low temperatures. At low temperatures of the sintered body (up to approx. 1000 ° C.) and at low to medium microwave radiation powers, eddy currents play a major role.
- the special properties of the microwaves also allow the induction of a plasma heating by simple control of the power and suitable choice of materials Depending on the surface temperature of the sintered body, the plasma heating can be dispensed with in order to prevent the danger of the sintered body surface overheating. This prevents the metal parts of the sintered body from evaporating.
- the method according to the invention is based on the use of the so-called "skin effect".
- skin effect In the case of substance mixtures of electrically conductive individual components, depending on the grain size and phase distribution in the mixture, each individual grain is heated by an eddy current, as a result of which the volume heated by microwaves is of the order of the sample volume.
- the microwave radiation can penetrate the sample.
- the microwave radiation can be converted directly into heat in the entire sintered body by relaxation processes, as a result of which any heating rates are possible.
- the microwave sintering allows the properties to be optimized to a far greater extent than that of conventional heat treatments is known.
- the hardness, the corrosion tendency, magnetic, electrical and thermomechanical parameters for known compositions could be considerably improved.
- the pre-pressed shaped bodies can either with a heating rate kontinu ⁇ ous or in pulse mode applied Auf ⁇ heating rate are heated, wherein the heating rate from 0.1 to 10 * C. / min.
- the sintering subsequent to the heating at constant temperature is preferably carried out over a period of 10 to 60 minutes.
- plasticizers such as e.g. Waxes, which are expelled during the heating.
- This process step can be carried out regardless of whether the waxes used themselves absorb the microwave radiation or are transparent to microwaves, as is the case with the waxes normally used.
- the molded article or the molded articles can be made on a base made of microwave-transparent material, such as aluminum oxide, quartz, glass or boron nitride, or on a base microwave-absorbing material, such as carbon, silicon carbide, zirconium dioxide, tungsten carbide or tungsten carbide-cobalt.
- the moldings can be heated indirectly by means of microwave heating of the bases and the furnace space.
- the sintering can be carried out in a vacuum, inert gas or a reducing atmosphere, using as inert gases Argon in particular, and helium in special cases. Helium can possibly be used to suppress plasmas.
- the inert gas atmospheres mentioned can preferably contain up to 5% hydrogen.
- Hydrogen, carbon monoxide, methane or mixtures thereof are suitable as reducing atmospheres.
- the sintering pressure should not exceed 200 bar.
- the first consists in carrying out the PVD, CVD or PCVD coating without intermediate cooling after the sintering, preferably by changing the gas composition.
- the sintering process and / or the HIP process and the coating process can be carried out in separate plants.
- inert organic and / inorganic additives with low dielectric losses can be added to control the penetration depth of the microwave radiation used.
- These can be plasticizers, for example, as in the production of hard metals and cermets, which have been added to the green bodies and which do not absorb the microwave radiation.
- These additives control the penetration depth of the microwave radiation in such a way that, depending on the amount and the spatial distribution of these additives, the degree of percolation of the strongly absorbing constituents of the green body is reduced. The resulting reduction in the electrical conductivity of the green body leads to an increase in the depth of penetration.
- the formation of structures similar to microstrip lines between these binders and additives and the electrically conductive components of the Green bodies are brought about.
- the green body is penetrated by microwave radiation along the structures similar to the microstrip line, as a result of which a further increase in the penetration depth can be achieved.
- the pressed bodies rest on supports made of porous Al 2 O 3 in a container which is also porous Al 2 O 3 and which also serves as a heat insulating jacket.
- inert gas is argon and from 350 "C, an argon-hydrogen mixture, the heating rate used with 5% hydrogen content.
- To 350 * C is from 0.1 to a maximum of 3 * C / min.
- the plasticizer is completely extracted ⁇ burned, so the heating rate is gradually increased, näm ⁇ Lich at 15 * C / min to 1000 * C and at 50 ° C / min between 1000 * C and 1250 °. Thereafter, a holding time of 10 minutes was Patient ⁇ stop before the cutting inserts with a Rate of 20 * C / min have been cooled.
- the sintered indexable inserts have a high hardness, good flexural strength and a Weibull distribution according to the following table. Results of the microwave sintering of WC-Co 25% weight
- hard metals and cermets or steels can be coated with hard materials.
- a chemical sample treatment can take place immediately in the cooling phase of the sintered body, in particular by means of a further microwave plasma atmosphere.
- the relaxation of the microwave radiation in the volume of the hard metals and cermets is no longer an effective heat generation process. Heat is only generated in the edge region of the sintered body by eddy currents. This provides the prerequisites for using the irradiated microwave power to maintain a microwave plasma without causing an undesirable thermal load on the sintered body.
- This procedure is possible with PVD coatings and can be carried out here as an integrated process immediately after sintering.
- the percolation limit of the conductive components of the green body is reached at about 4% paraffin content. With this paraffin content, the penetration depth of the microwave radiation increases abruptly and reaches values that are typical for volume heating.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention concerns composites substantially consisting of: a cermet material having a binder metal phase of between 5 and 30 mass % and the remainder comprising at least one carbon nitride phase; or a hard metal with a hard material phase of between 70 and 100 %, the remainder being a binder metal phase, with the exception of a WC-Co hard metal, with up to 25 mass % cobalt as binder metal; or a powder-metallurgically produced steel. The invention further concerns a process for producing this composite. In order to improve bending strength and hardness, sintering is carried out in a microwave field.
Description
Beschreibung description
Verbundwerkstoff und Verfahren zu seiner HerstellungComposite and process for its manufacture
Die Erfindung betrifft Verbundwerkstoffe, im wesentlichen bestehend aus einem Cermetwerkstoff mit einer Bindemetallphase von 5 bis 30 Massen-%, Rest mindestens eine Carbonitridphase oder einem Hartmetall mit einer Hartstoffphase von 70 bis 100 %, Rest Bindemetallphase, ausgenommen ein WC-Co-Hartmetall mit bis zu 25 Massen-% Cobalt als Binde¬ metall oder einem pulvermetallurgisch hergestelltem Stahl.The invention relates to composite materials, consisting essentially of a cermet material with a binder metal phase of 5 to 30% by mass, the rest of at least one carbonitride phase or a hard metal with a hard material phase of 70 to 100%, the rest of the binder metal phase, with the exception of a WC-Co hard metal with 25% by mass of cobalt as binder metal or a powder-metallurgically produced steel.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung dieses Verbundwerkstoffes.The invention further relates to a method for producing this composite material.
Verbundwerkstoffe der genannten Art werden insbesondere als Schneidplatten zur zerspanenden Bearbeitung oder als Hochtempe¬ ratur-Werkstoffe eingesetzt. Werkstoffe aus der vorgenannten Stoffklasse werden nach dem Stand der Technik durch Sintern von Preßkörpern, die aus den entsprechenden Gemischen von Hartstof¬ fen und Metallpulvern bzw. Metallpulvern hergestellt. Die Sin¬ terung erfolgt in beheizbaren Öfen, die beispielsweise mit Gra¬ phitheizelementen ausgerüstet sind, wobei die Erwärmung der Proben indirekt mittels der von den Heizelementen emittierten Strahlung sowie durch Konvektion bzw. Wärmeleitung erfolgt. Der Nachteil dieser Verfahrenstechnik liegt darin, daß die Wahl der Ofenatmosphäre durch die chemischen Eigenschaften der Heizele¬ mente eingeschränkt ist. Darüber hinaus erfolgt die Erwärmung der Hartmetalle, Cermets oder Stähle von außen nach innen und wird im wesentlichen durch die Wärmeleitfähigkeit und die Emissivität der Proben kontrolliert. Je nach Wärmeleitfähigkeit der Proben ist die Variationsbreite der Aufheiz- und
Abkühlraten stark eingeschränkt, weshalb zum Teil aufwendige Maßnahmen, wie ein hoher apparativer und prozeßtechnischer Auf¬ wand erforderlich sind, um beispielsweise Ultrafein-Hartmetalle zufriedenstellend sintern zu können.Composite materials of the type mentioned are used in particular as cutting inserts for machining or as high-temperature materials. According to the prior art, materials from the aforementioned class of materials are produced by sintering compacts which are made from the corresponding mixtures of hard materials and metal powders or metal powders. The sintering takes place in heatable furnaces which are equipped, for example, with graphite heating elements, the samples being heated indirectly by means of the radiation emitted by the heating elements and by convection or heat conduction. The disadvantage of this process technology is that the choice of the furnace atmosphere is limited by the chemical properties of the heating elements. In addition, the heating of hard metals, cermets or steels takes place from the outside in and is essentially controlled by the thermal conductivity and the emissivity of the samples. Depending on the thermal conductivity of the samples, the range of variation of the heating and Cooling rates are severely restricted, which is why complex measures, such as a high outlay in terms of apparatus and process technology, are sometimes required in order, for example, to be able to sinter ultrafine hard metals satisfactorily.
In der CN 1050908 ist zwar bereits vorgeschlagen worden, ein WC-Co-Hartmetall mit 6 Massen-% und einem kleinen Zusatz von 0,5 Massen-% TaC in einer WasserStoffatmosphäre bei 1250°C 10 bis 20 Minuten in einem Mikrowellenfeld zu sintern, jedoch schien dieses Verfahren auf solche Körper beschränkt, die nur einen geringen Metallanteil aufweisen. Bei massiven, metalli¬ schen Körpern ist nämlich festzustellen, daß sich diese in der Mikrowelle praktisch nicht aufheizen lassen, vielmehr reflek¬ tieren sie aufgrund ihrer hohen elektrischen Leitfähigkeit und der auftretenden Wirbelströme die eingestrahlte Leistung schon im Bereich der Oberfläche.In CN 1050908 it has already been proposed to sinter a WC-Co hard metal with 6 mass% and a small addition of 0.5 mass% TaC in a hydrogen atmosphere at 1250 ° C. for 10 to 20 minutes in a microwave field, however, this process appeared to be limited to those bodies that have a low metal content. In the case of solid, metallic bodies, it should be noted that these can practically not be heated in the microwave; on the contrary, due to their high electrical conductivity and the eddy currents which occur, they reflect the radiated power even in the area of the surface.
Es ist Aufgabe der vorliegenden Erfindung, einen Verbundkörper der eingangs genannten Art hinsichtlich seiner Biegebruchfe¬ stigkeit und seiner Härte zu verbessern und ein Verfahren zur Herstellung solcher Verbundwerkstoffe anzugeben.It is an object of the present invention to improve a composite body of the type mentioned at the outset with regard to its flexural strength and its hardness and to specify a method for producing such composite materials.
Diese Aufgabe wird durch den Verbundwerkstoff nach Anspruch 1 gelöst, der erfindungsgemäß dadurch gekennzeichnet ist, daß er durch Sinterung in einem Mikrowellenfeld hergestellt worden ist. überraschenderweise hat sich nämlich herausgestellt, daß mit größer werdenden Bindemetallgehalten des vorgeformten Pre߬ körpers die Effektivität der Aufheizung durch Mikrowellen auch bei Hartmetallen gesteigert werden kann. Mikrowellengesinterte Cermetwerkstoffe sowie mikrowellengesinterte pulvermetallur¬ gisch hergestellte Stähle sind bisher in der Fachliteratur erst gar nicht erwähnt worden. Die Mikrowellensinterung stellt im Gegensatz zur bisherigen konventionellen Sinterung eine direkte Erwärmung im Volumen der Verbundwerkstoffe beliebiger Geometrie dar, einzig die Voraussetzung, daß die Größe der Sinterkörper in der Größenordnung der Wellenlänge der verwendeten
Mikrowellenstrahlung liegt, ist zu beachten. Damit können im Gegensatz zur bisherigen Praxis auch große Bauteile drucklos gesintert werden, da die große Variabilität der Aufheizbedin- gungen eine gezielte Gefügeeinstellung im gesamten Bauteil erlaubt. Obwohl die Verbundwerkstoffe mit guter elektrischer Leitfähigkeit je nach Bindemetallphasengehalt einen Teil der Mikrowellenstrahlung reflektieren, ermöglicht die besondere Mikrostruktur, insbesondere poröser Hartmetall- und Cermet- grünlinge, bereits bei tiefen Temperaturen eine hohe Eindring¬ tiefe der Mikrowellenstrahlung in den vorgepreßten Preßkörper.This object is achieved by the composite material according to claim 1, which is characterized according to the invention in that it has been produced by sintering in a microwave field. Surprisingly, it has been found that with increasing binder metal contents of the preformed compact, the effectiveness of the heating by microwaves can be increased even with hard metals. Microwave-sintered cermet materials and microwave-sintered powder metallurgically produced steels have so far not even been mentioned in the specialist literature. In contrast to conventional sintering to date, microwave sintering represents direct heating in the volume of the composite materials of any geometry, only the requirement that the size of the sintered bodies be in the order of the wavelength of the used ones Microwave radiation must be observed. In contrast to previous practice, this means that even large components can be sintered without pressure, since the great variability of the heating conditions allows a targeted microstructure adjustment in the entire component. Although the composite materials with good electrical conductivity reflect part of the microwave radiation, depending on the binder metal phase content, the special microstructure, in particular porous hard metal and cermet green compacts, enables a high penetration depth of the microwave radiation into the pre-pressed pressed body even at low temperatures.
Weiterbildungen des erfindungsgemäßen Verbundkörpers sind in den Ansprüchen 2 bis 15 beschrieben.Developments of the composite body according to the invention are described in claims 2 to 15.
So hat es sich insbesondere hinsichtlich einer höheren Dichte als vorteilhaft erwiesen, wenn die Verbundwerkstoffe zusätzlich einem abschließenden heißisostatischen Pressen (HIP) unterzogen worden sind, vorzugsweise unter einem Druck zwischen 5 bar und 3000 bar bei Temperaturen von 1200*C bis 1750'C. Das heißisostatische Pressen ist grundsätzlich bekannt und wird beispielsweise in "Pulvermetallurgie der Hartmetalle" H. Kolaska, Fachverband Pulvermetallurgie, 1992, Seite 6/11 f. beschrieben.Thus, it has proven particularly with regard to a higher density to be advantageous if the composites have been additionally subjected to a final hot isostatic pressing (HIP), preferably under a pressure of between 5 bar and 3000 bar, at temperatures of 1200 * C to 1750'C. Hot isostatic pressing is generally known and is described, for example, in "Powder Metallurgy of Hard Metals" by H. Kolaska, Fachverband Pulvermetallurgie, 1992, page 6/11 f. described.
Hinsichtlich der Materialauswahl haben sich Cermets bewährt, die eine auf Titan, Zirkonium, Hafnium, Vanadin, Niob, Tantal, Chrom, Molybdän und/oder Wolfram basierende Carbonitridphase und eine Bindemetallphase aus Cobalt und/oder Nickel aufweisen.With regard to the choice of materials, cermets have proven themselves, which have a carbonitride phase based on titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and / or tungsten and a binder metal phase composed of cobalt and / or nickel.
Gleichermaßen haben sich Hartmetalle mit einer Hartstoffphase, bestehend aus Oxicarbiden, Oxinitriden, Oxicarbonitriden oder Boriden bewährt. Gleiches gilt für Hartmetalle mit einem hexagonalen Wolframcarbid als erster Phase und einem kubischen Mischcarbid des Wolframs, Titans, Tantals und/oder Niobs als zweiter Phase und einer Bindemetallphase aus Cobalt, Nickel, Eisen oder Mischungen hieraus. Die vorgenannten Hartmetalle
können auch anstelle der reinen hexagonalen Wolframcarbid-Phase eine hexagonale Mischcarbid-Phase des Wolframcarbid mit Molyb- däncarbid aufweisen.Likewise, hard metals with a hard material phase consisting of oxicarbides, oxynitrides, oxicarbonitrides or borides have proven their worth. The same applies to hard metals with a hexagonal tungsten carbide as the first phase and a cubic mixed carbide of tungsten, titanium, tantalum and / or niobium as the second phase and a binder metal phase made of cobalt, nickel, iron or mixtures thereof. The aforementioned hard metals can also have a hexagonal mixed carbide phase of the tungsten carbide with molybdenum carbide instead of the pure hexagonal tungsten carbide phase.
Variationen der Bindemetallphase beschreiben die Ansprüche 7 bis 14. So kann die üblicherweise aus Eisen, Cobalt und/oder Nickel bestehende Bindemetallphase bis zu 15 Massen-% Molybdän, Wolfram, Titan, Mangan und/oder Aluminium aufweisen. Insbeson¬ dere kann als Bindemetallphase eine Nickel-Aluminium-Legierung mit einem Nickel/Aluminium-Verhältnis von 90 : 10 bis 70 : 30 verwendet werden. Beimengungen bis zu 1 Massen-% Bor der genannten Bindemetallphasen sind möglich.Variations of the binder metal phase describe claims 7 to 14. Thus, the binder metal phase usually consisting of iron, cobalt and / or nickel can have up to 15% by mass of molybdenum, tungsten, titanium, manganese and / or aluminum. In particular, a nickel-aluminum alloy with a nickel / aluminum ratio of 90:10 to 70:30 can be used as the binder metal phase. Additions of up to 1% by mass of boron to the binder metal phases mentioned are possible.
Alternativ dazu kann die Bindemetallphase auch aus den in Anspruch 10 beschriebenen Stoffen oder Mischungen daraus beste¬ hen. Hierbei können Zusätze von 0 bis 16 Massen-% aus Cobalt, Nickel, Eisen oder Seltenerd-Metalle enthalten sein.Alternatively, the binder metal phase can also consist of the substances described in claim 10 or mixtures thereof. Additions of 0 to 16% by mass of cobalt, nickel, iron or rare earth metals can be included.
Nach einer weiteren Ausgestaltung der Erfindung kann eine warm¬ feste Bindemetallphase aus pulvermetallurgisch hergestelltem Schnellarbeitsstahl und/oder einer Superlegierung bestehen. Auch haben sich korrosionsfeste Bindemetallphase aus Nickel und Chrom bewährt, die ggf. Zusätze von Molybdän, Mangan, Alumi¬ nium, Silicium und/oder Kupfer in Mangan von 0,01 bis zu 5 Massen-% enthalten.According to a further embodiment of the invention, a heat-resistant binder metal phase can consist of powder-metallurgically produced high-speed steel and / or a superalloy. Corrosion-resistant binder metal phases made of nickel and chromium, which may contain additions of molybdenum, manganese, aluminum, silicon and / or copper in manganese of from 0.01 to 5% by mass, have also proven successful.
Nach einer weiteren Ausgestaltung der Erfindung kann der Ver¬ bundwerkstoff eine oder mehrere Oberflächenschichten besitzen, die durch PVD-, CVD- oder PCVD-Verfahren aufgetragen worden sind, vorzugsweise in einem Mikrowellenfeld.According to a further embodiment of the invention, the composite material can have one or more surface layers which have been applied by PVD, CVD or PCVD processes, preferably in a microwave field.
Verfahrenstechnisch wird die eingangs gestellte Aufgabe durch Maßnahmen nach den Ansprüchen 16 bis 28 gelöst.In terms of process technology, the task set out above is achieved by measures according to claims 16 to 28.
Bei einer Erwärmung des vorgepreßten Formkörpers in einem Mikrowellenfeld kann eine geregelte Temperaturerhöhung des Pro-
benkörpers selbst bei tiefen Temperaturen erreicht werden. Bei tiefen Temperaturen der Sinterkörper (bis ca. 1000"C) und bei niedrigen bis mittleren Mikrowellenstrahlungsleistungen spielen Wirbelströme eine große Rolle. Die besonderen Eigenschaften der Mikrowellen erlauben ferner durch einfache Regelung der Lei¬ stung und geeignete Materialauswahl zusätzlich die Induktion einer Plasmaheizung, die je nach Bedarf verstärkt oder unter¬ drückt werden kann. Je nach Oberflächentemperatur der Sinter¬ körper kann auf die Plasmaheizung verzichtet werden, um die Gefahr einer überhitzung der Sinterkörperoberfläche zu verhin¬ dern. Hierdurch kann ein Ausdampfen der Metallanteile des Sin¬ terkörpers vermieden werden.When the pre-pressed molded body is heated in a microwave field, a controlled increase in the temperature of the product body can be reached even at low temperatures. At low temperatures of the sintered body (up to approx. 1000 ° C.) and at low to medium microwave radiation powers, eddy currents play a major role. The special properties of the microwaves also allow the induction of a plasma heating by simple control of the power and suitable choice of materials Depending on the surface temperature of the sintered body, the plasma heating can be dispensed with in order to prevent the danger of the sintered body surface overheating. This prevents the metal parts of the sintered body from evaporating.
Bei tiefen Temperaturen der Sinterkörper beruht das erfindungs¬ gemäße Verfahren auf der Nutzung des sogenannten "skin-Effek- tes". Bei Stoffgemischen aus elektrisch leitenden Einzelkompo¬ nenten wird, je nach Korngröße und Phaseverteilung im Gemisch, jedes einzelne Korn durch einen Wirbelstrom erwärmt, wodurch das durch Mikrowellen geheizte Volumen in der Größenordnung des Probenvolumens liegt. Damit wird aufgrund der MikroStruktur der Sinterkörper nicht nur eine dünne Randschicht des Sinterkörpers beheizt, sondern die Mikrowellenstrahlung kann die Probe durch¬ dringen. Bei höheren Temperaturen und insbesondere bei Ausbil¬ dung kleinster Mengen einer Schmelzphase kann die Mikrowellen¬ strahlung direkt im gesamten Sinterkörper durch Relaxationspro¬ zesse in Wärme umgewandelt werden, wodurch beliebige Aufheizra¬ ten möglich sind. Hierdurch ist es möglich, physikalische Pro¬ zesse, wie die Auflösung und Ausscheidung von Phasen in einem weit größeren Maße zu variieren als bei einer konventionellen Sinterung. Darüber hinaus ist eine vollständige Verdichtung der Sinterkörper bei geringeren Haltezeiten möglich. Desgleichen wird die Geschwindigkeit von chemischen Reaktionen durch die Mikrowelle positiv beeinflußt. Insgesamt erlaubt die Mikrowel¬ lensinterung eine Optimierung der Eigenschaften in einem weit größeren Ausmaß als dies von konventionellen Wärmebehandlungen
bekannt ist. Insbesondere konnten die Härte, die Korrosionsnei¬ gung, magnetische, elektrische und thermomechanische Kenngrößen für bekannte Zusammensetzungen erheblich verbessert werden.At low temperatures of the sintered body, the method according to the invention is based on the use of the so-called "skin effect". In the case of substance mixtures of electrically conductive individual components, depending on the grain size and phase distribution in the mixture, each individual grain is heated by an eddy current, as a result of which the volume heated by microwaves is of the order of the sample volume. Because of the microstructure of the sintered body, not only is a thin edge layer of the sintered body heated, but the microwave radiation can penetrate the sample. At higher temperatures and in particular when small amounts of a melting phase are formed, the microwave radiation can be converted directly into heat in the entire sintered body by relaxation processes, as a result of which any heating rates are possible. This makes it possible to vary physical processes, such as the dissolution and separation of phases, to a far greater extent than with conventional sintering. In addition, complete compaction of the sintered body is possible with shorter holding times. Likewise, the speed of chemical reactions is positively influenced by the microwave. Overall, the microwave sintering allows the properties to be optimized to a far greater extent than that of conventional heat treatments is known. In particular, the hardness, the corrosion tendency, magnetic, electrical and thermomechanical parameters for known compositions could be considerably improved.
Die vorgepreßten Formkörper können entweder mit einer kontinu¬ ierlichen Aufheizrate oder im Pulsbetrieb aufgebrachten Auf¬ heizrate erhitzt werden, wobei die Aufheizrate 0,1 bis 10 *C/min beträgt.The pre-pressed shaped bodies can either with a heating rate kontinu¬ ous or in pulse mode applied Auf¬ heating rate are heated, wherein the heating rate from 0.1 to 10 * C. / min.
Die sich an das Aufheizen anschließende Sinterung bei konstan¬ ter Temperatur wird vorzugsweise über eine Dauer von 10 bis 60 Minuten durchgeführt.The sintering subsequent to the heating at constant temperature is preferably carried out over a period of 10 to 60 minutes.
Zur Herstellung von Hartmetallen und Cermets werden bei den Grünkörpern Plastifizierer, wie z.B. Wachse, verwendet, die während der Aufheizung ausgetrieben werden. Dieser Proze߬ schritt kann durchgeführt werden unabhängig davon, ob die ver¬ wendeten Wachse selbst die Mikrowellenstrahlung absorbieren oder für Mikrowellen transparent sind, wie es bei den üblicher¬ weise verwendeten Wachsen der Fall ist. Je nach dem, ob gewünscht ist, daß die Mikrowellen den vorgepreßten Formkörper auf allen Oberflächenseiten erreichen, kann der Formkörper bzw. können die Formkörper auf einer Unterlage aus mikrowellen¬ transparentem Material, wie Aluminiumoxid, Quarz, Glas oder Bornitrid, oder auf einer Unterlagen aus mikrowellenabsorbie¬ rendem Material, wie Kohlenstoff, Siliciumcarbid, Zirkondioxid, Wolframcarbid oder Wolframcarbid-Cobalt gelagert sein. Ferner kann durch Auswahl des Materials für die Unterlage und den Ofenraum zusätzlich zur direkten Mikrowellenheizung eine indi¬ rekte Heizung der Formkörper durch Mikrowellenheizung der Unterlagen und des Ofenraumes erfolgen.For the production of hard metals and cermets, plasticizers such as e.g. Waxes, which are expelled during the heating. This process step can be carried out regardless of whether the waxes used themselves absorb the microwave radiation or are transparent to microwaves, as is the case with the waxes normally used. Depending on whether it is desired that the microwaves reach the pre-pressed molded article on all surface sides, the molded article or the molded articles can be made on a base made of microwave-transparent material, such as aluminum oxide, quartz, glass or boron nitride, or on a base microwave-absorbing material, such as carbon, silicon carbide, zirconium dioxide, tungsten carbide or tungsten carbide-cobalt. Furthermore, by selecting the material for the base and the furnace space, in addition to direct microwave heating, the moldings can be heated indirectly by means of microwave heating of the bases and the furnace space.
Die Sinterung kann in einer Vakuum-, Inertgas- oder einer redu¬ zierenden Atmosphäre durchgeführt werden, wobei als Inertgase
insbesondere Argon, in Sonderfällen auch Helium, infrage kom¬ men. Helium kann ggf. als Unterdrückung von Plasmen eingesetzt werden. Die genannten Inertgasatmosphären können vorzugsweise bis zu 5 % Wasserstoff enthalten.The sintering can be carried out in a vacuum, inert gas or a reducing atmosphere, using as inert gases Argon in particular, and helium in special cases. Helium can possibly be used to suppress plasmas. The inert gas atmospheres mentioned can preferably contain up to 5% hydrogen.
Als reduzierende Atmosphären bieten sich Wasserstoff, Kohlen- monoxid, Methan oder Mischungen hieraus an. Der Sinterdruck soll 200 bar nicht übersteigen.Hydrogen, carbon monoxide, methane or mixtures thereof are suitable as reducing atmospheres. The sintering pressure should not exceed 200 bar.
Zur Aufbringung von Oberflächenbeschichtungen bieten sich zwei Möglichkeiten an: Die erste besteht darin, die PVD-, CVD- oder PCVD-Beschichtung ohne zwischenzeitige Abkühlung im Anschluß an das Sintern durchzuführen, vorzugsweise durch Wechsel der Gas¬ zusammensetzung. Alternativ hierzu können jedoch der Sinterpro¬ zeß und/oder der HIP-Prozeß und der Beschichtungsprozeß in getrennten Anlagen durchgeführt werden.There are two possibilities for applying surface coatings: The first consists in carrying out the PVD, CVD or PCVD coating without intermediate cooling after the sintering, preferably by changing the gas composition. Alternatively, however, the sintering process and / or the HIP process and the coating process can be carried out in separate plants.
Dem Formkörper können nach einer weiteren Ausgestaltung der Erfindung zur Steuerung der Eindringtiefe der verwendeten Mikrowellenstrahlung inerte organische und/ anorganische Zusätze mit geringen dielektrischen Verlusten zugegeben werden. Dies können beispielsweise wie bei der Herstellung von Hartmetallen und Cermets Plastifizierer sein, die den Grünkör¬ pern beigegeben worden sind und die die Mikrowellenstrahlung nicht absorbieren. Diese Zusätze steuern die Eindringtiefe der Mikrowellenstrahlung derart, daß abhängig von der Menge und der räumlichen Verteilung dieser Zusätze der Perkolationsgrad der stark absorbierenden Bestandteile des Grünkörpers vermindert wird. Die sich daraus ergebende Verminderung der elektrischen Leitfähigkeit des Grünkörpers führt zur Erhöhung der Eindring¬ tiefe. Ferner kann durch eine besondere Verteilung der nicht absorbierenden Binder und Zusätze die Bildung von ikrostrei- fenleiterähnlichen Strukturen zwischen diesen Bindern und Zusätzen und den elektrisch leitenden Bestandteilen der
Grünkörper herbeigeführt werden. Dadurch wird eine Penetration des Grünkörpers durch Mikrowellenstrahlung entlang der mikrostreifenleiterähnlichen Strukturen erreicht, wodurch eine weitere Erhöhung der Eindringtiefe erzielbar ist.According to a further embodiment of the invention, inert organic and / inorganic additives with low dielectric losses can be added to control the penetration depth of the microwave radiation used. These can be plasticizers, for example, as in the production of hard metals and cermets, which have been added to the green bodies and which do not absorb the microwave radiation. These additives control the penetration depth of the microwave radiation in such a way that, depending on the amount and the spatial distribution of these additives, the degree of percolation of the strongly absorbing constituents of the green body is reduced. The resulting reduction in the electrical conductivity of the green body leads to an increase in the depth of penetration. Furthermore, through a special distribution of the non-absorbent binders and additives, the formation of structures similar to microstrip lines between these binders and additives and the electrically conductive components of the Green bodies are brought about. As a result, the green body is penetrated by microwave radiation along the structures similar to the microstrip line, as a result of which a further increase in the penetration depth can be achieved.
Im folgenden wird die Erfindung anhand von Ausführungsbeispie¬ len näher erläutert.The invention is explained in more detail below on the basis of exemplary embodiments.
Aus einer 25 Gew.-% Cobalt mit einem Gehalt von 1,5 Gew.-% Wachse als Plastifizierer, Rest WC bestehende Wendeschneidplat¬ ten-Preßkörper werden gemäß der Ofengeometrie gleichmäßig ver¬ teilt angeordnet und bei einer Leistungsdichte von 0,3 W/cm3 mittels Mikrowellen aufgeheizt. Die Temperaturregelung erfolgt über die Einstellung der Mikrowellenleistung. Die Preßkörper ruhen auf Auflagen aus porösem AI2O3 in einem Behälter als ebenfalls porösem AI2O3, der gleichzeitig als Wärmeisolierman¬ tel dient. Als Inertgasatmosphäre wird Argon und ab 350"C ein Argon-Wasserstoffgemisch mit 5 % Wasserstoffgehalt verwendet. Die Aufheizrate bis 350*C beträgt 0,1 bis maximal 3*C/min. Bis zu dieser Aufheizung ist der Plastifizierer vollständig ausge¬ brannt, weshalb die Aufheizrate stufenweise erhöht wird, näm¬ lich auf 15*C/min bis 1000*C und auf 50°C/min zwischen 1000*C und 1250° . Hiernach wurde eine Haltezeit von 10 Minuten einge¬ halten, bevor die Wendeschneidplatten mit einer Rate von 20*C/min abgekühlt worden sind.Inserts made of a 25% by weight cobalt with a content of 1.5% by weight waxes as plasticizers, the rest of the WC are evenly distributed according to the furnace geometry and at a power density of 0.3 W / cm 3 heated by microwaves. The temperature is controlled by setting the microwave power. The pressed bodies rest on supports made of porous Al 2 O 3 in a container which is also porous Al 2 O 3 and which also serves as a heat insulating jacket. As inert gas is argon and from 350 "C, an argon-hydrogen mixture, the heating rate used with 5% hydrogen content. To 350 * C is from 0.1 to a maximum of 3 * C / min. Up to this heating, the plasticizer is completely ausge¬ burned, so the heating rate is gradually increased, näm¬ Lich at 15 * C / min to 1000 * C and at 50 ° C / min between 1000 * C and 1250 °. Thereafter, a holding time of 10 minutes was einge¬ stop before the cutting inserts with a Rate of 20 * C / min have been cooled.
Die gesinterten Wendeschneidplatten weisen eine hohe Härte, eine gute Biegebruchfestigkeit und eine Weibull-Verteilung nach folgender Tabelle auf.
Ergebnisse der Mikrowellensinterung von WC-Co 25 % GewichtThe sintered indexable inserts have a high hardness, good flexural strength and a Weibull distribution according to the following table. Results of the microwave sintering of WC-Co 25% weight
Kennwerte Mikrowellen Konventionelle Sinterung SinterungCharacteristic microwaves Conventional sintering Sintering
Biegebruchfestigkeit σg 3017 2620Flexural strength σg 3017 2620
Weibull-Modulus 24,8 16Weibull modulus 24.8 16
Härte HV3o 836 798Hardness H V 3o 836 798
Zur Verbesserung der Verschleißfestigkeit können Hartmetalle und Cermets oder auch Stähle mit Hartstoffen beschichtet wer¬ den. So kann unmittelbar in der Abkühlphase der Sinterkörper eine chemische Probenbehandlung erfolgen, insbesondere durch weitere Mikrowellenplasma-Atmosphäre. Sobald die flüssige Phase erstarrt ist, ist die Relaxation der Mikrowellenstrahlung im Volumen der Hartmetalle und Cermets kein effektiver Wärmeerzeu¬ gungsprozeß mehr. Eine Wärmeerzeugung findet nur noch im Rand¬ bereich der gesinterten Körper durch Wirbelströme statt. Damit sind die Voraussetzungen gegeben, die eingestrahlte Mikrowel¬ lenleistung zur Aufrechterhaltung eines Mikrowellenplasmas zu nutzen, ohne eine unerwünschte Wärmebelastung der Sinterkörper zu verursachen. Diese Verfahrensweise ist bei PVD-Beschichtun- gen möglich und hier als integrierter Prozeß unmittelbar im Anschluß an die Sinterung durchführbar. Besondere Vorteile ergeben sich auch beim Einsatz von Mikrowellen zur Sinterung von Hartmetallen und Cermets bei einer abschließenden CVD- Beschichtung. Da die Sinterkörper nach einer Abkühlphase heißer sind als die Umgebung, findet die CVD-Reaktion bevorzugt an den Sinterkörpern statt. Ferner muß im Gegensatz zu konventionellen Sinterverfahren bei der Wahl der Ofenatmosphäre keine Rücksicht auf die chemischen Eigenschaften von Heizelementen genommen werden.
Die Herstellung von Hartmetallen und Cermets durch Erwärmung mittels Mikrowellen führt zu einer erheblichen Vereinfachung des Herstellungsprozesses und damit zu einer erheblichen Ver¬ kürzung der gesamten Prozeßdauer. Die Aufheizraten können im Bereich von lO-1"C/min für die Entwachsung bis hin zu 5 • 103°C/min bei Temperaturen oberhalb 1000"C variiert werden, Die Abkühlung ist nicht primär von der thermischen Masse des Ofens abhängig, sondern von der thermischen Masse der Sintercharge. Vorteilhafterweise steht der Ofen nach einer Sinterung sofort für eine Neubelegung zur Verfügung.To improve wear resistance, hard metals and cermets or steels can be coated with hard materials. A chemical sample treatment can take place immediately in the cooling phase of the sintered body, in particular by means of a further microwave plasma atmosphere. As soon as the liquid phase has solidified, the relaxation of the microwave radiation in the volume of the hard metals and cermets is no longer an effective heat generation process. Heat is only generated in the edge region of the sintered body by eddy currents. This provides the prerequisites for using the irradiated microwave power to maintain a microwave plasma without causing an undesirable thermal load on the sintered body. This procedure is possible with PVD coatings and can be carried out here as an integrated process immediately after sintering. Special advantages also result from the use of microwaves for sintering hard metals and cermets with a final CVD coating. Since the sintered bodies are hotter than the environment after a cooling phase, the CVD reaction preferably takes place on the sintered bodies. Furthermore, in contrast to conventional sintering processes, the chemical properties of heating elements do not have to be taken into account when choosing the furnace atmosphere. The production of hard metals and cermets by heating by means of microwaves leads to a considerable simplification of the production process and thus to a considerable reduction in the total process time. The heating rates can be varied in the range of 10 -1 "C / min for dewaxing up to 5 • 10 3 ° C / min at temperatures above 1000" C. The cooling is not primarily dependent on the thermal mass of the furnace, but on the thermal mass of the sinter batch. After sintering, the furnace is advantageously immediately available for a new assignment.
Wie aus der in der einzigen Figur gezeigten Abhängigkeit der elektrischen Leitfähigkeit eines Hartmetall-Grünkörpers vom Gewichtsanteil des Binders ersichtlich, wird bei ca. 4% Paraffinanteil die Perkolationsgrenze der leitfähigen Bestand¬ teile des Grünkörpers erreicht. Bei diesem Paraffinanteil er¬ höht sich auch die Eindringtiefe der Mikrowellenstrahlung sprunghaft und erreicht Werte, die typisch für Volumenheizung sind.
As can be seen from the dependence of the electrical conductivity of a hard metal green body on the weight fraction of the binder shown in the single figure, the percolation limit of the conductive components of the green body is reached at about 4% paraffin content. With this paraffin content, the penetration depth of the microwave radiation increases abruptly and reaches values that are typical for volume heating.
Claims
1. Verbundwerkstoffe, im wesentlichen bestehend aus einem Cermetwerkstoff mit einer Bindemetallphase von 5 bis 30 Massen-%, Rest mindestens eine Carbonitrid¬ phase oder einem Hartmetall mit einer Hartstoffphase von 70 bis 100 %, Rest Bindemetallphase, ausgenommen ein Wolf- ramcarbid-Cobalt-Hartmetall mit bis zu 25 Massen-% Cobalt als Bindemetall oder einem pulvermetallurgisch hergestelltem Stahl, d a d u r c h g e k e n n z e i c h n e t, daß der Verbundwerkstoff durch Sinterung in einem Mikro¬ wellenfeld hergestellt worden ist.1. Composite materials, essentially consisting of a cermet material with a binder metal phase of 5 to 30% by mass, the remainder at least one carbonitride phase or a hard metal with a hard material phase of 70 to 100%, the remainder of the binder metal phase, with the exception of a tungsten carbide cobalt Tungsten carbide with up to 25% by mass of cobalt as binding metal or a powder-metallurgically produced steel, characterized in that the composite material has been produced by sintering in a microwave field.
2. Verbundwerkstoff nach Anspruch l, dadurch gekennzeichnet, daß der Verbundwerkstoff zusätzlich einem abschließenden heißisostatischen Pressen (HIP) zur Nachverdichtung unter¬ zogen worden ist, vorzugsweise unter einem Druck zwischen 5 bar und 3000 bar bei Temperaturen von 1200*C bis 1750"C.2. Composite material according to claim l, characterized in that the composite material has additionally undergone a final hot isostatic pressing (HIP) for post-compression, preferably under a pressure between 5 bar and 3000 bar at temperatures from 1200 * C to 1750 "C.
3. Verbundwerkstoff nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß das Cermet eine auf Ti, Zr, Hf, V, Nb, Ta, Cr, Mo und/oder W basierende Carbonitrid¬ phase und eine Bindemetallphase aus Co und/oder Ni auf¬ weist.3. Composite material according to one of claims 1 or 2, characterized in that the cermet is based on Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and / or W based Carbonitrid¬ phase and a binder metal phase made of Co and / or Ni has.
4. Verbundwerkstoff nach Anspruch 1 oder 2, dadurch gekenn¬ zeichnet, daß die Hartstoffphase Oxicarbide, Oxinitride, Oxicarbonitride oder Boride aufweist.4. Composite material according to claim 1 or 2, characterized gekenn¬ characterized in that the hard material phase has oxicarbide, oxynitride, oxicarbonitride or boride.
5. Verbundwerkstoff nach Anspruch 1, 2 oder 4, dadurch gekennzeichnet, daß das Hartmetall hexagonales WC als 1. Phase und kubisches Carbid des Mischkristalles aus W, Ti, Ta und/oder Nb als 2. Phase und eine Bindemetallphase aus Co, Ni. Fe oder Mischungen hiervon aufweist. 5. Composite material according to claim 1, 2 or 4, characterized in that the hard metal hexagonal toilet as the 1st phase and cubic carbide of the mixed crystal of W, Ti, Ta and / or Nb as the 2nd phase and a binder metal phase made of Co, Ni. Fe or mixtures thereof.
6. Verbundwerkstoff nach einem der Ansprüche 1, 2, 4 oder 5, dadurch gekennzeichnet, daß das Hartmetall aus hexagona¬ len Mischcarbiden WC mit MoC und/oder kubischen Mischcar- biden der Elemente Ti, Zr, Hf, V, Nb, Ta, Cr, Mo und/oder W mit einer Bindemetallphase aus Co, Fe und/oder Ni besteht.6. Composite material according to one of claims 1, 2, 4 or 5, characterized in that the hard metal made of hexagona¬ len mixed carbides WC with MoC and / or cubic mixed carbides of the elements Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and / or W with a binder metal phase consists of Co, Fe and / or Ni.
7. Verbundwerkstoff nach einem der Ansprüche l bis 6, dadurch gekennzeichnet, daß die Bindemetallphase bis zu 15 Massen-% Mo, W, Ti, Mn und/oder AI - bezogen auf die Gesamtmasse der Bindemetallphase - aufweist.7. Composite material according to one of claims 1 to 6, characterized in that the binder metal phase has up to 15% by mass of Mo, W, Ti, Mn and / or Al - based on the total mass of the binder metal phase.
8. Verbundwerkstoff nach Anspruch 7, dadurch gekennzeichnet, daß die Bindemetallphase aus einer Ni-AI-Legierung mit einem Ni-Al-Verhältnis von 90 : 10 bis 70 : 30 besteht.8. Composite material according to claim 7, characterized in that the binder metal phase consists of a Ni-Al alloy with a Ni-Al ratio of 90: 10 to 70: 30.
9. Verbundwerkstoff nach Anspruch 8, dadurch gekennzeichnet, daß die Bindemetallphase bis zu 1 Massen-% Bor (bezogen auf die Gesamtmasse der Bindemetallphase) enthält.9. A composite material according to claim 8, characterized in that the binder metal phase contains up to 1% by mass of boron (based on the total mass of the binder metal phase).
10. Verbundwerkstoff nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Bindemetallphase aus Ni3Äl, TiSi3, Ti2Si3, Ti3Al, Ti5Si3, TiAl, Ni2TiAl, TiSi2, NiSi, MoSi2, MoSi02 oder Mischungen hieraus besteht.10. Composite material according to one of claims 1 to 6, characterized in that the binder metal phase made of Ni3Äl, TiSi 3 , Ti 2 Si 3 , Ti 3 Al, Ti 5 Si 3 , TiAl, Ni 2 TiAl, TiSi 2 , NiSi, MoSi 2 , MoSi0 2 or mixtures thereof.
11. Verbundwerkstoff nach Anspruch 10, gekennzeichnet durch Zusätze von 0 bis 16 Massen-% aus Co, Ni, Fe und/oder Sel- tenerd-Metallen.11. Composite material according to claim 10, characterized by additions of 0 to 16% by mass of Co, Ni, Fe and / or rare earth metals.
12. Verbundwerkstoff nach einem der Ansprüche l, 2 oder 4, gekennzeichnet durch eine warmfeste Bindemetallphase, bestehend aus pulvermetallurgisch hergestelltem Schnell- arbeitsstahl und/oder einer Superlegierung.12. Composite material according to one of claims 1, 2 or 4, characterized by a heat-resistant binder metal phase, consisting of powder metallurgically produced high-speed steel and / or a superalloy.
13. Verbundwerkstoff nach einem der Ansprüche 1, 2 oder 4, gekennzeichnet durch eine Bindemetallphase aus Ni und Cr. 13. Composite material according to one of claims 1, 2 or 4, characterized by a binder metal phase made of Ni and Cr.
14. Verbundwerkstoff nach Anspruch 13, gekennzeichnet durch Zusätze von Mo, Mn, AI, Si und Cu in Mangan von 0,01 bis zu 5 Massen-%.14. Composite material according to claim 13, characterized by additions of Mo, Mn, Al, Si and Cu in manganese from 0.01 to 5% by mass.
15. Verbundwerkstoff nach einem der Ansprüche 1 bis 14, gekennzeichnet durch eine oder mehrere mittels PVD, CVD und/oder PCVD, vorzugsweise in einem Mikrowellenfeld auf¬ getragene Schichten.15. Composite material according to one of claims 1 to 14, characterized by one or more layers applied by means of PVD, CVD and / or PCVD, preferably in a microwave field.
16. Verfahren zur Herstellung der Verbundwerkstoffe nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß der vorgepreßte Formkörper in einem Mikrowellenfeld von 0,01 bis 10 W/cm3 Energiedichte erwärmt und gesintert wird.16. A method for producing the composite materials according to one of claims 1 to 15, characterized in that the pre-pressed molded body is heated and sintered in a microwave field of 0.01 to 10 W / cm 3 energy density.
17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß der Formkörper kontinuierlich oder gepulst mit Mikrowellen bestrahlt und mit Aufheizraten von 0.1 bis 104°C/min erhitzt wird.17. The method according to claim 16, characterized in that the shaped body is irradiated continuously or in a pulsed manner with microwaves and is heated at heating rates of 0.1 to 10 4 ° C / min.
18. Verfahren nach Anspruch 16 oder 17, dadurch gekennzeich¬ net, daß der Formkörper nach dem Aufheizen mindestens 10 bis 60 Minuten bei konstanter Temperatur gesintert wird.18. The method according to claim 16 or 17, characterized gekennzeich¬ net that the shaped body is sintered after heating at least 10 to 60 minutes at a constant temperature.
19. Verfahren nach einem der Ansprüche 16 bis 18, dadurch gekennzeichnet, daß der vorgepreßte Formkörper Plastifi¬ zierer, wie Wachs, enthält, die vorzugsweise während der Aufheizung ausgetrieben werden.19. The method according to any one of claims 16 to 18, characterized in that the pre-pressed molded plasticizer, such as wax, contains, which are preferably expelled during the heating.
20. Verfahren nach einem der Ansprüche 16 bis 19, dadurch gekennzeichnet, daß der vorgepreßte Formkörper während des Aufheizens und Sinterns auf einer Unterlage aus mikrowel¬ lentransparentem Material, wie AI2O3, Quarz, Glas oder Bornitrid gelagert ist. 20. The method according to any one of claims 16 to 19, characterized in that the pre-pressed molded body is mounted during heating and sintering on a base made of microwell-transparent material such as Al2O3, quartz, glass or boron nitride.
21. Verfahren nach einem der Ansprüche 16 bis 19, dadurch gekennzeichnet, daß der vorgepreßte Formkörper auf einer Unterlage aus mikrowellenabsorbierendem Material wie Koh¬ lenstoff, Siliciumcarbid, Zirkoniumdioxid, Wolframcarbid, Wolframcarbid-Cobalt gelagert ist.21. The method according to any one of claims 16 to 19, characterized in that the pre-pressed molded body is mounted on a base made of microwave-absorbing material such as carbon, silicon carbide, zirconium dioxide, tungsten carbide, tungsten carbide cobalt.
22. Verfahren nach einem der Ansprüche 16 bis 21, dadurch gekennzeichnet, daß die Sinterung in einer Vakuum-, einer Inertgas- oder einer reduzierenden Atmosphäre durchgeführt wird.22. The method according to any one of claims 16 to 21, characterized in that the sintering is carried out in a vacuum, an inert gas or a reducing atmosphere.
23. Verfahren nach Anspruch 22, dadurch gekennzeichnet, daß die Inertgas-Atmosphäre bis zu 5 Volumen-% H2 enthält.23. The method according to claim 22, characterized in that the inert gas atmosphere contains up to 5% by volume of H 2 .
24. Verfahren nach Anspruch 22, dadurch gekennzeichnet, daß die reduzierende Atmosphäre aus Wasserstoff, Kohlenmon- oxid, Methan oder Mischungen hieraus besteht.24. The method according to claim 22, characterized in that the reducing atmosphere consists of hydrogen, carbon monoxide, methane or mixtures thereof.
25. Verfahren nach einem der Ansprüche 22 bis 24, dadurch gekennzeichnet, daß die Sinterung unter einem Druck von maximal 200 bar durchgeführt wird.25. The method according to any one of claims 22 to 24, characterized in that the sintering is carried out under a pressure of at most 200 bar.
26. Verfahren nach einem der Ansprüche 16 bis 25, dadurch gekennzeichnet, daß die PVD-, CVD- oder PCVD-Beschichtung ohne zwischenzeitige Abkühlung im Anschluß an das Sintern aufgetragen wird.26. The method according to any one of claims 16 to 25, characterized in that the PVD, CVD or PCVD coating is applied without intermediate cooling after sintering.
27. Verfahren nach Anspruch 26, dadurch gekennzeichnet, daß die PVD-, CVD- oder PCVD-Beschichtung durch Wechsel der Gaszusammensetzung aufgetragen wird.27. The method according to claim 26, characterized in that the PVD, CVD or PCVD coating is applied by changing the gas composition.
28. Verfahren nach einem der Ansprüche 16 bis 27, dadurch gekennzeichnet, daß dem Formkörper zur Steuerung der Eindringtiefe der verwendeten Mikrowellenstrahlung inerte organische und/oder anorganische Zusätze mit geringen dielektrischen Verlusten zugegeben werden. 28. The method according to any one of claims 16 to 27, characterized in that inert organic and / or inorganic additives with low dielectric losses are added to the shaped body for controlling the penetration depth of the microwave radiation used.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE4340652A DE4340652C2 (en) | 1993-11-30 | 1993-11-30 | Composite and process for its manufacture |
PCT/DE1995/000548 WO1996033830A1 (en) | 1993-11-30 | 1995-04-26 | Composite and process for the production thereof |
Publications (1)
Publication Number | Publication Date |
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EP0827433A1 true EP0827433A1 (en) | 1998-03-11 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP95916564A Withdrawn EP0827433A1 (en) | 1993-11-30 | 1995-04-26 | Composite and process for the production thereof |
Country Status (5)
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US (1) | US6124040A (en) |
EP (1) | EP0827433A1 (en) |
JP (1) | JPH11504074A (en) |
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DE4004576C1 (en) * | 1990-02-14 | 1991-02-21 | Deutsche Thomson-Brandt Gmbh, 7730 Villingen-Schwenningen, De | |
JPH03267304A (en) * | 1990-03-19 | 1991-11-28 | Hitachi Ltd | Microwave sintering process |
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JPH04144992A (en) * | 1990-10-01 | 1992-05-19 | Idemitsu Petrochem Co Ltd | Microwave plasma-generating device and method for producing diamond film with the same |
CN1015646B (en) * | 1990-11-16 | 1992-02-26 | 武汉工业大学 | Microwave sintering process of w-co carbide hard metals |
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-
1993
- 1993-11-30 DE DE4340652A patent/DE4340652C2/en not_active Expired - Lifetime
-
1995
- 1995-04-26 WO PCT/DE1995/000548 patent/WO1996033830A1/en not_active Application Discontinuation
- 1995-04-26 US US08/945,561 patent/US6124040A/en not_active Expired - Lifetime
- 1995-04-26 JP JP8532068A patent/JPH11504074A/en not_active Ceased
- 1995-04-26 EP EP95916564A patent/EP0827433A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO9633830A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE4340652A1 (en) | 1995-06-01 |
US6124040A (en) | 2000-09-26 |
JPH11504074A (en) | 1999-04-06 |
DE4340652C2 (en) | 2003-10-16 |
WO1996033830A1 (en) | 1996-10-31 |
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