US3352694A - Low temperature metallizing paint and method of making same - Google Patents
Low temperature metallizing paint and method of making same Download PDFInfo
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- US3352694A US3352694A US288454A US28845463A US3352694A US 3352694 A US3352694 A US 3352694A US 288454 A US288454 A US 288454A US 28845463 A US28845463 A US 28845463A US 3352694 A US3352694 A US 3352694A
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- metallizing
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- Expired - Lifetime
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- 239000003973 paint Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000843 powder Substances 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 239000003870 refractory metal Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 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 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- -1 Dowenol EE Chemical compound 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5133—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the refractory metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5183—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal inorganic
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
Definitions
- This invention relates to a metallizing paint composition. More particularly, this invention relates to a low temperature metallizing paint composition for obtaining a vacuum tight metallized surface on ceramic bodies and the method of obtaining the metallizing paint.
- a ceramic body is metallized by painting the portion of the ceramic body to be metallized with a metallizing paint and then heating the coated ceramic to sinter a refractory metal, present in the paint, onto the ceramic.
- the resulting metallized layer generally comprises a refractory metal phase which is extensively penetrated by a non-metallic glassy phase that wets and adheres to both the refractory metal and the ceramic body.
- the metallizing paint may comprise a vehicle which includes a binder and a solvent with the refractory metal and the glassy phase material suspended therein. The metallizing paint is applied to the ceramic body by hand painting, spraying, dipping, silk screening or by any other suitable means.
- an object of this invention is to provide a low temperature metallizing paint.
- Still another object of this invention is to provide a metallizing paint having a sintering temperature of about 1000 C. for producing a vacuum tight metallized layer on ceramic bodies.
- a further object of this invention is to provide a method for obtaining a low temperature metallizing paint.
- a metallizing paint composition which includes at least one material therein which acts to reduce the sintering temperature of the refractory metal and the melting temperature of the glassy phase material contained in the metallizing paint.
- a low temperature metallizing paint composition comprises a vehicle including a binder in a solvent.
- a plurality of metal powders are dispersed in the vehicle and include a refractory metal and a quantity of at least one metal which reduces the sintering temperature of the refractory metal and the melting temperature of glassy phase material.
- a plurality of glassy phase producing powders are also dispersed in the vehicle.
- a low temperature metallizing paint is obtained by preparing a vehicle which includes a solvent and a binder.
- a preferred binder material is nitrocellulose.
- the binder material may be any organic film- Patented Nov. 14, 1967 forming substance, such as ethyl cellulose or methacrylate resin, commonly used and well known in the art, which decompose upon heating leaving little or no residue.
- a plurality of metal powders are placed in the vehicle and include a refractory metal selected from the group consisting of tungsten, molybdenum and rhenium and a quantity of at least one metal, selected from the group consisting of copper, nickel, cobalt and iron, for reducing the sintering temperature of the refractory metal and the melting temperature of glassy phase producing material.
- metal powders are defined as any one or more of the various powder forms of metal, such as pure metal powder, metal oxide powder, metal hydride powder, etc.
- a plurality of non-metallic glassy phase producing powders are also placed in the vehicle and include by weight a majority of manganese dioxide and a minority by weight of silica, and titanium dioxide.
- a non-metallic powder, preferably boric acid may be added to the vehicle to further aid in reducing the melting temperature of the glassy phase material.
- a uniform distribution or suspension of the powders in the vehicle is obtained by ball milling the metallizing paint mix.
- a low temperature metallizing paint composition having a sintering temperature of about 1000 C. is formed by preparing a vehicle which includes a binder and a solvent.
- a preferred solvent comprises about 50 cc. of ethylene glycol monoethyl ether, such as Dowenol EE, and 50 cc. of methylethyl ketone.
- the vehicle is formed by adding by weight about 1.5 grams of nitrocellulose to cc. of the solvent.
- a plurality of at least 325 mesh metal oxide powders are added to the 100 cc.
- a refractory metal selected from the group consisting of tungsten oxide, molybdenum oxide or rhenium oxide and about 10 grams nickel oxide, about 5 grams of copper oxide and about 2 grams of iron oxide.
- the nickel, copper and iron oxides act to reduce the sintering temperature of the refractory metal, which is preferably tungsten oxide, and also reduce the melting temperature of the glassy phase materials described hereinbelow.
- a plurality of at least -325 mesh glassy phase producing powders are also added to the 100 cc. of vehicle and include about 10.4 grams of manganese dioxide, about 4.4 grams of silica, and about 2.2 grams of titanium dioxide. Also, about 4.2 grams of boric acid is added to the vehicle to aid in reducing the melting temperature of the glassy phase material.
- a uniform distribution or dispersion of the powders in the vehicle is obtained by ball milling the metallizing paint mix for approximately 48 hours.
- the ball milling is performed in an iron ball mill with /2 inch diameter iron balls which intimately coats at least a portion of the powder particles dispersed in the vehicle with iron from the iron balls by a disintegration commutation process.
- the metallizing paint may be applied to any suitable ceramic, such as a beryllium oxide ceramic or a high alumina ceramic, that is, one containing at least 85% alumina.
- the sintering temperature of the metallizing paint is about 1000 C.
- the sintering preferably takes place for /2 hour in an atmosphere of four parts nitrogen to one part hydrogen having a dew point of plus 1000 F. This low sintering temperature is due to the materials used, such as the copper, nickel and iron. In the absence of these materials, the sintering temperature of the metallizing paint would be in the vicinity of 1500 to 1600" C.
- the presence of the copper, nickel and iron powders intermingled with the refractory metal powder causes-this reduction in the sintering temperature of the refractory metal.
- a portion of the copper, nickel and iron exist in ionic form in the glassy phase melt during sintering and reduce the melting temperature of the glassy phase material, that it, the manganese, silica and titanium oxides.
- the boric acid further aids in reducing the melting temperature of the glassy phase material.
- the metallizing paint composition described hereinabove in detail is such that at about 1000" C.
- the glassy phase materials produce a manganese-titaniumalumino-borosilicate melt that extensively penetrates the refractory metal and wets and adheres to both the refractory metal and the ceramic to form a vacuum tight metallized surface on the ceramic body.
- Tensile strengths up to 12,000 p.s.i. have been obtained by utilizing this metallizing paint in conjunction with an overplate of nickel followed by a copper-silver braze to a copper metal member.
- the materials comprising a novel low temperature metallizing paint are given hereinabove, it is to be understood that these quantities may be varied according to the paint characteristics de sired without departing from the spirit and scope of the present invention.
- the metal oxide powders may be replaced by pure metal powders.
- the boric acid need not be used in which case the metallizing paint will have a sintering temperature of about 1000 to 1100 C.
- the consistency of the paint desired may be controlled by varying the amounts of the solvent and binder used.
- cobalt oxide may be used in place of the nickel and/ or copper oxide; and other glassy phase producing materials may be used rather than the manganese, silica and titanium described hereinabove.
- a metalizing paint for producing a vacuum-tight metalized surface on ceramic said metalizing paint having a sintering temperature of about 1000 C. comprising:
- a vehicle including a binder and a solvent
- metal powders dispersed in said vehicle, said metal powders consisting essentially of approximately 85% to 90% by weight of a refractory metal selected from the group consisting of tungsten molybdenum and rhenium, and approximately to by weight of at least one other metal selected from the group consisting of nickel, copper, cobalt and iron; and
- Claim 1 wherein said other metal consists of approximately 60% nickel, approximately 30% copper and approximately 10% iron by weight.
- Claim 1 wherein said glassy phase producing pow- 4 ders consist essentially of a majority by weight of manganese dioxide and a minority by weight of silica and titanium dioxide.
- Claim 1 wherein said glassy phase producing powders consist essentially of approximately of manganese dioxide, 26% silica and 14% titanium dioxide by weight.
- Claim 1 further including boric acid to reduce the melting temperature of the glassy phase producing powders.
- Claim 1 wherein the metal powders and the glassy phase producing powders are at least partially coated with iron.
- metal powders consisting essentially of a refractory metal selected from the group consisting of tungsten, molybdenum and rhenium and a quantity of at least one metal selected from the group consisting of cobalt, nickel, copper and iron;
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Description
United States Patent 3,352,694 LOW TEMPERATURE METALLIZING PAINT AND METHOD OF MAKING $AME Leonard Reed, San Jose, and Donald C. Figone, San Francisco, Calif., assignors, by mesne assignments, to Varian Associates, a corporation of Caiifornia N0 Drawing. Filed June 17, 1963, Ser. No. 288,454 Claims, (Cl. 1061) This invention relates to a metallizing paint composition. More particularly, this invention relates to a low temperature metallizing paint composition for obtaining a vacuum tight metallized surface on ceramic bodies and the method of obtaining the metallizing paint.
Generally, a ceramic body is metallized by painting the portion of the ceramic body to be metallized with a metallizing paint and then heating the coated ceramic to sinter a refractory metal, present in the paint, onto the ceramic. The resulting metallized layer generally comprises a refractory metal phase which is extensively penetrated by a non-metallic glassy phase that wets and adheres to both the refractory metal and the ceramic body. The metallizing paint may comprise a vehicle which includes a binder and a solvent with the refractory metal and the glassy phase material suspended therein. The metallizing paint is applied to the ceramic body by hand painting, spraying, dipping, silk screening or by any other suitable means. Heretofore in the prior art, the high sintering temperature (1300 to 1600 C.) of many metallizing paints has tended to warp various ceramic bodies. Also, expensive apparatus, such as high temperature furnaces, etc. are required to produce these high sintering temperatures- Therefore, an object of this invention is to provide a low temperature metallizing paint.
Another object of this invention is to provide a metallizing paint having a sintering temperature of about 1000" C.
Still another object of this invention is to provide a metallizing paint having a sintering temperature of about 1000 C. for producing a vacuum tight metallized layer on ceramic bodies.
A further object of this invention is to provide a method for obtaining a low temperature metallizing paint.
These and other objects of this invention are obtained by a metallizing paint composition which includes at least one material therein which acts to reduce the sintering temperature of the refractory metal and the melting temperature of the glassy phase material contained in the metallizing paint. In accordance with this invention, a low temperature metallizing paint composition comprises a vehicle including a binder in a solvent. A plurality of metal powders are dispersed in the vehicle and include a refractory metal and a quantity of at least one metal which reduces the sintering temperature of the refractory metal and the melting temperature of glassy phase material. A plurality of glassy phase producing powders are also dispersed in the vehicle. Also, a nonmetallic powder, such as boric acid, may be added to the vehicle to further aid in reducing the melting temperature of the glassy phase material. Further, the powders in the vehicle may be at least partially coated with iron to improve the density of the sintered refractory metal layer obtained with the metallizing paint.
This invention, as well as other objects, features and advantages thereof, will be readily apparent from the following detailed description. In accordance with this invention, a low temperature metallizing paint is obtained by preparing a vehicle which includes a solvent and a binder. A preferred binder material is nitrocellulose. However, the binder material may be any organic film- Patented Nov. 14, 1967 forming substance, such as ethyl cellulose or methacrylate resin, commonly used and well known in the art, which decompose upon heating leaving little or no residue. A plurality of metal powders are placed in the vehicle and include a refractory metal selected from the group consisting of tungsten, molybdenum and rhenium and a quantity of at least one metal, selected from the group consisting of copper, nickel, cobalt and iron, for reducing the sintering temperature of the refractory metal and the melting temperature of glassy phase producing material. For purposes of describing and claiming the present invention, metal powders are defined as any one or more of the various powder forms of metal, such as pure metal powder, metal oxide powder, metal hydride powder, etc. A plurality of non-metallic glassy phase producing powders are also placed in the vehicle and include by weight a majority of manganese dioxide and a minority by weight of silica, and titanium dioxide. Also, a non-metallic powder, preferably boric acid, may be added to the vehicle to further aid in reducing the melting temperature of the glassy phase material. A uniform distribution or suspension of the powders in the vehicle is obtained by ball milling the metallizing paint mix.
According to a preferred example of the present invention, a low temperature metallizing paint composition having a sintering temperature of about 1000 C. is formed by preparing a vehicle which includes a binder and a solvent. One hundred cc. by weight of a preferred solvent comprises about 50 cc. of ethylene glycol monoethyl ether, such as Dowenol EE, and 50 cc. of methylethyl ketone. The vehicle is formed by adding by weight about 1.5 grams of nitrocellulose to cc. of the solvent. A plurality of at least 325 mesh metal oxide powders are added to the 100 cc. of vehicle and include by weight about 100 to grams of a refractory metal selected from the group consisting of tungsten oxide, molybdenum oxide or rhenium oxide and about 10 grams nickel oxide, about 5 grams of copper oxide and about 2 grams of iron oxide. The nickel, copper and iron oxides act to reduce the sintering temperature of the refractory metal, which is preferably tungsten oxide, and also reduce the melting temperature of the glassy phase materials described hereinbelow. A plurality of at least -325 mesh glassy phase producing powders are also added to the 100 cc. of vehicle and include about 10.4 grams of manganese dioxide, about 4.4 grams of silica, and about 2.2 grams of titanium dioxide. Also, about 4.2 grams of boric acid is added to the vehicle to aid in reducing the melting temperature of the glassy phase material.
A uniform distribution or dispersion of the powders in the vehicle is obtained by ball milling the metallizing paint mix for approximately 48 hours. In order to increase the hardness and density of the metallized layer produced by the metallizing paint, the ball milling is performed in an iron ball mill with /2 inch diameter iron balls which intimately coats at least a portion of the powder particles dispersed in the vehicle with iron from the iron balls by a disintegration commutation process.
The metallizing paint may be applied to any suitable ceramic, such as a beryllium oxide ceramic or a high alumina ceramic, that is, one containing at least 85% alumina. The sintering temperature of the metallizing paint is about 1000 C. The sintering preferably takes place for /2 hour in an atmosphere of four parts nitrogen to one part hydrogen having a dew point of plus 1000 F. This low sintering temperature is due to the materials used, such as the copper, nickel and iron. In the absence of these materials, the sintering temperature of the metallizing paint would be in the vicinity of 1500 to 1600" C. It is believed that the presence of the copper, nickel and iron powders intermingled with the refractory metal powder causes-this reduction in the sintering temperature of the refractory metal. Also, a portion of the copper, nickel and iron exist in ionic form in the glassy phase melt during sintering and reduce the melting temperature of the glassy phase material, that it, the manganese, silica and titanium oxides. The boric acid further aids in reducing the melting temperature of the glassy phase material. The metallizing paint composition described hereinabove in detail is such that at about 1000" C. the glassy phase materials produce a manganese-titaniumalumino-borosilicate melt that extensively penetrates the refractory metal and wets and adheres to both the refractory metal and the ceramic to form a vacuum tight metallized surface on the ceramic body. Tensile strengths up to 12,000 p.s.i. have been obtained by utilizing this metallizing paint in conjunction with an overplate of nickel followed by a copper-silver braze to a copper metal member.
Although specific quantities of the materials comprising a novel low temperature metallizing paint are given hereinabove, it is to be understood that these quantities may be varied according to the paint characteristics de sired without departing from the spirit and scope of the present invention. For example, the metal oxide powders may be replaced by pure metal powders. Also, the boric acid need not be used in which case the metallizing paint will have a sintering temperature of about 1000 to 1100 C. Further, the consistency of the paint desired may be controlled by varying the amounts of the solvent and binder used. Also, cobalt oxide may be used in place of the nickel and/ or copper oxide; and other glassy phase producing materials may be used rather than the manganese, silica and titanium described hereinabove.
What is claimed is:
1. A metalizing paint for producing a vacuum-tight metalized surface on ceramic, said metalizing paint having a sintering temperature of about 1000 C. comprising:
a vehicle including a binder and a solvent;
a plurality of metal powders dispersed in said vehicle, said metal powders consisting essentially of approximately 85% to 90% by weight of a refractory metal selected from the group consisting of tungsten molybdenum and rhenium, and approximately to by weight of at least one other metal selected from the group consisting of nickel, copper, cobalt and iron; and
a plurality of glassy phase producing powders dispersed in said vehicle.
2. Claim 1 wherein said refractory metal is in oxide form.
3. Claim 1 wherein said other metal is in oxide form.
4. Claim 1 wherein said other metal consists of approximately 60% nickel, approximately 30% copper and approximately 10% iron by weight.
5. Claim 1 wherein said glassy phase producing pow- 4 ders consist essentially of a majority by weight of manganese dioxide and a minority by weight of silica and titanium dioxide.
6. Claim 1 wherein said glassy phase producing powders consist essentially of approximately of manganese dioxide, 26% silica and 14% titanium dioxide by weight.
7. Claim 1 further including boric acid to reduce the melting temperature of the glassy phase producing powders.
8. Claim 7 wherein the proportion of glassy phase producing powders to boric acid is approximately 4:1 by weight.
9. Claim 1 wherein the metal powders and the glassy phase producing powders are at least partially coated with iron.
10. The method of making a metalizing paint having a sinteringtemperature of about 1000 C. comprising the steps of:
preparing a vehicle by combining a binder with a solvent;
placing in the vehicle a plurality of metal powders consisting essentially of a refractory metal selected from the group consisting of tungsten, molybdenum and rhenium and a quantity of at least one metal selected from the group consisting of cobalt, nickel, copper and iron;
placing in the vehicle a plurality of glassy phase producing powders; and
coating the powder particles in the vehicle with iron such as by ball-milling the vehicle containing the powders with iron balls.
References Cited UNITED STATES PATENTS 869,013 10/1907 McOuat. 1,947,112 2/1934 Ruben. 2,100,425 11/1937 Bent et al 106187 2,160,133 5/1939 Ellis 106187 XR 2,461,878 2/ 1949 Christensen et al. 2,488,731 11/1949 Lambert et al. 2,530,217 11/1950 Bain. 2,750,657 6/1956 Herbert et al. 2,759,446 8/ 1956 Ewing.
2,985,547 5/1961 Luks 117-160 3,093,490- 6/1963 MacKay 1061 3,110,571 11/1963 Alexander 117160 X 3,189,504 6/1965 Whittle et a1. 156--234 3,227,591 1/1966 Lambert et al 15680 3,290,171 12/1966 Zollman et al. 1061 3,293,072 12/1966 Doolittle et al l17138.8
ALEXANDER H. BR'ODMERKEL, Primary Examiner.
J. H. WOO, Assistant Examiner.
Claims (1)
1. A METALIZING PAINT FOR PRODUCING A VACUUM-TIGHT METALIZED SURFACE ON CERAMIC, SAID METALLIZING PAINT HAVING A SINTERING TEMPERATURE OF ABOUT 1000*C. COMPRISING: A VEHICLE INCLUDING A BINDER AND A SOLVENT; A PLURALITY OF METAL POWDERS DISPERSED IN SAID VEHICLE, SAID METAL POWDERS CONSISTING ESSENTIALLY OF APPROXIMATELY 85% TO 90% BY WEIGHT OF A REFRACTORY METAL SELECTED FROM THE GROUP CONSISTING OF TUNGSTEN MOLYBDENUM AND RHENIUM, AND APPROXIMATELY 10% TO 15% BY WEIGHT OF AT LEAST ONE OTHER METAL SELECTED FROM THE GROUP CONSISTING OF NICKEL, COPPER, COBALT AND IRON; AND A PLURALITY OF "GLASSY" PHASE PRODUCING POWDERS DISPERSED IN SAID VEHICLE.
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US288454A US3352694A (en) | 1963-06-17 | 1963-06-17 | Low temperature metallizing paint and method of making same |
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US288454A US3352694A (en) | 1963-06-17 | 1963-06-17 | Low temperature metallizing paint and method of making same |
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US3537888A (en) * | 1968-06-10 | 1970-11-03 | Gen Motors Corp | Process and composition for metallizing ceramics |
US3620799A (en) * | 1968-12-26 | 1971-11-16 | Rca Corp | Method for metallizing a ceramic body |
US3647519A (en) * | 1969-09-26 | 1972-03-07 | Sperry Rand Corp | Method for metallizing beryllium oxide at low temperatures |
US4957561A (en) * | 1986-01-25 | 1990-09-18 | Nippon Hybrid Technologies Co., Ltd. | Composition for metallizing a surface of ceramics, a method for metallizing, and metallized ceramics |
EP0467462A1 (en) * | 1990-07-20 | 1992-01-22 | F.M. Velterop B.V. | Method of connecting ceramic material to another material |
EP1970357A1 (en) * | 2007-03-14 | 2008-09-17 | Colorobbia Italia S.p.a. | Materials for coating ceramic bodies, preparation and use thereof and ceramic bodies comprising them |
EP2014629A3 (en) * | 2007-06-22 | 2009-09-30 | Colorobbia Italia S.p.a. | Materials for coating ceramic bodies, preparation and use thereof and ceramic bodies including the same |
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