Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS2461878 A
Publication typeGrant
Publication dateFeb 15, 1949
Filing dateNov 1, 1944
Priority dateNov 1, 1944
Publication numberUS 2461878 A, US 2461878A, US-A-2461878, US2461878 A, US2461878A
InventorsCarl J Christensen, Merle D Rigterink, Arnold W Treptow
Original AssigneeBell Telephone Labor Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Metallizing composition
US 2461878 A
Images(1)
Previous page
Next page
Description  (OCR text may contain errors)

Feb. 15, 1949. c. J. CHRISTENSEN ET AL METALLIZING COMPOSITION Filed Nov. 1, 1944 C. J- CHRISTENSEN INVENTORS M D. R/GTER/NK AW TREPTOW AT7DRNEY Patented Feb. 15, 1949 METALLIZING COMPOSITION New York Application November 1, 1944, Serial No. 561,392

11 Claims. (01. 111-327) This invention relates to metallizing compositions and more particularly to metallizing compositions comprisin a finely divided metal-containin substance, an inorganic flux, and an organic vehicle, which metallizing compositions are useful for forming on quartz, ceramic material, glass or other materials metallic layers which are highly adherent and which if soldered to provide strong soldered joints.

Metallizing compounds comprising a finely divided easily reducible metal such as silver, a finely divided inorganic flux, and an organic vehicle have been used heretofore for forming on glass, ceramics and other base materials metallic layers, usually for decorative purposes. In general, such prior metallizing compounds are employed by spreading the metallizing composition in a layer on the base material which is to be metallized, and then heatin the layer to a suitable temperature usually between about 500 C. and about 800 C. The heating is intended to volatilize the organic vehicle and to melt the flux and cause it to bind thefinely divided metal particles together and to the underlying base material to form an adherent metallic layer.

It has been found, however, that the metallizing compositions of this type heretofore available do not produce layers having properties as good as are desired for many purposes. Often the metallic layers are characterized by roughness, cracking or :razing, blistering, non-uniformity of composition or poor adherence to the base material. Even more serious disadvantages often arise when the metallic layers are employed in soldered joints.

Thus, when it is attempted to fix a metal element to a base material such as a quartz piezoelectric crystal, ceramic material or glass by first applying and baking a layer of such metallizing composition to form a metallic layer and then solderin the metal element to such metallic layer, the connection between the metal element and the base material often is weak because the metallic layer does not adhere sufficiently well to the base material, or because the solder does not adhere well to ,the metallic layer, or for both reasons. Such disadvantages are particularly troublesome in connection withthe soldering of metallic elements to quartz crystals, since it is important that a strong joint be provided between the quartz crystal and the metal element which may act as an electrical lead or as asupporting lead or both.

It has been found that poor adherence of the metallic layer to the base material or to solder 2 or to both may be caused by one or more ofseveral factors.

The character of the metallic layer which is formed is greatly influenced by the nature of the organic vehicle employed. The vehicle should keep the particles of metal and flux suspended in uniform distribution; it should be of sumcient viscosity to make a metallizing composition of such consistency as to facilitate the formation of a layer by spreading, brushing or spraying; the vehicle moreover should be removed in the heating operationand after removal should leave an adherent metallic layer which for some uses should adhere well to solder. However, many metallizlng compounds heretofore available include a vehicle which does not keep the metal and flux particles dispersed but permits the par ticles to agglomerate so that the resulting metallic layer is not homogeneous or smooth. This impairs adhesion to the underlying base material or to solder. It also appears that in the formation of a metallic layer from such a prior metallizing composition the organic vehicle decomposes during the heating operation and leaves behind in the metallic layer a residue of carbon which impairs adhesion to the underlying base material or to solder, or which, if it is burned out in the heating operation, leaves the metallic layer in a -metallic layer is cracked or crazed during the heatin operation because the portion of the organic vehicle temporarily remaining after its more volatile portions have evaporated, has such a stron cohesive action that the metallic layer shrinks excessively relative to the base and cracks.

The inorganic flux should have a relatively low melting point so that when the layer of metallic composition is heated, the flux melts and binds the metal powder particles together and to the surface of the base material. The flux should be of such a character that it wets the metal particles and base material, and preferably fuses to the base material. The metallizing compositions heretofore available often do not embody fluxes having these properties, so that the adherence of the metallic layer to 'the base material and the strength of the layer are not as good as could be desired.

It appears that if the metallizing composition films which adhere well to quartz, ceramic material, glass and other materials, and which adhere well to solder. The metallizin composition of the present invention may be employed for various purposes including the formation on quartz, ceramic material, glass or other materials of adherent metallic layers which when soldered to provide strong soldered joints, or which are useful for decorative purposes. lletalllzing compositions embodying the invention may be employed to particular advantage in the formation of soldered joints between quartz pieaoelectrlc crystals and metal elements, and for the purpose of illustration will be primarily discuaed hereinafter in' that connection.

The drawing illustrates a quartz piezoelectric crystal having connected thereto metallic members which serve as electrical connections and supporting members, which are soldered to metallic layers adhering to the quartz and resulting from heating of a metallizing composition embodying the invention.

The present invention provides a metallizing composition comprising a finely divided noble metal-containing substance, a finely divided low melting glass, and an organic vehicle comprising a high molecular weight heat-depolymerizable organic polymer which preferably is a normally solid polymer, and an organic solvent for said polymer. Upon baking of a layer of the metallizlng composition the solvent evaporates and the organic polymer depolymerizes sufllciently so that it evaporates without decomposing, and the low melting glass melts and wets and cements the metal particles together and to the base material which may be quartz.

The finely divided noble metal-containing substance employed in the metallizing composition may consist of particles of one or more noble metals as such or alloys thereof, or of one or more noble metal compounds which are easily reducible to the noble metal upon heating in air at temperatures of about 550 C. or less and which are insoluble in organic solvents, or of mixtures of particles of noble metals and particles of such compounds of noble metals. Examples of noble metals which may be employed as such or in the form of such compoimds are silver, gold and platinum; of these silver is the most commonly used because of its greater availability and lower cost; the term noble metal" as used herein and in the claims is intended to include alloys of noble metals. The oxides and carbonates are examples of compounds of noble metals which are easily reducible by heating in air at the indicated temperatures and which are insoluble in organic solvents; silver oxide and silver carbonate may be employed to particular advantage. Such a noble metal compound will be reduced to the metal during baking of the metallizin composition. Particular advantages in making possible the formation of strong metallic layers which adhere well to quartz and to solder are provided if the particles of noble metal or compound thereof employed in the metallizing composition are of a particle size of 300 mesh or smaller.

The inorganic flux employed in the metallizing composition of this invention is a low melting flux in the sense that it melts at a temperature below about 500 C. While any one of various finely divided low melting glasses may be employed as a flux in a metallizing composition embodying the present invention, exceptional advantages are provided if the finely divided glass employed in the metallizing composition of the invention comprises by weight about to 90 per cent PbO, from about 5 to 25 per cent of B203, and a minor proportion of at least one of the glass-forming constituents or modifications SiOz, BizOs, PbF'z and TiQz. Advantageous proportions of these constituents are from about 1 to about 20 per cent of 810:, from about 5 to about 25 per cent B1203, from about 1 to about 10 per cent of PbFz, and from about 1 to about, 5 per cent 01' T192. The glass may be made by mixing together and firing the finely divided constituents in known manners and then grinding to a suitable particle size The smaller the average particle size oi the glass, the more eflective will be the bond between the metal particles themselves and between the metal particles and the base material which is coated with the metallic layer, The particles of glass, like the particles of noble metal or compound thereof, should be as small as possible for best results. When a layer of metallizing composition embodying the invention and comprising such a glass is baked at a suitable temperature, the glass melts at a relatively low temperature and readily wets the glass and the base material and firmly cements the metal particles together and to the base material. As a result there is formed a strong metallic layer havin excellent adherence for the base material and for solder applied thereto. Such a glass has a melting point well below 573 C., the temperature-at which a change in structure of quartz occurs, and therefore a 'metallizing compound embodying it may be advantageously used to form a metal layer on quartz crystals.

Examples of particularly useful glasses of the above type are the following, in which the proportions are by weight:

layer-is soft and does not adhere well to the quartz. If too much glass is present the electrical conductivity of the resulting metallic layer is decreased and the solderability is diminished.

The amount of flux which it is necessary to em-' ploy is somewhat dependent upon the noble metal employed and the size and shape of the particles metal present in the metallizing composition as such or in a noble metal compound.

The organic vehicle may comprise one or more heat depolymerizable binders and one or more solvents therefor; various heat depolymerizable organic polymers and various solvents therefor are suitable. The heat-depolymerizable organic polymers which may be employed in the metallizing compounds of the present invention are normally solid at room temperatures and are capable of being depolymerized upon moderate heating, 1. e., at temperatures below about 500 0., into monomeric or low molecular weight compounds which at such temperatures are vapors. Examples of highly satisfactory heat depolymerizable organic polymers which may be employed are such vinyl or substituted vinyl polymers as polymethylmethacrylate, polybutylmethacrylate, polyisobutylmethacrylate, polyethylmethacrylate, which are polymers of alkyl esters of methacrylic acid, polyisobutylene, and other polymers such as the recently developed itaconic acid polymers may also be employed. Examples of suitable organic solvents for such a polymer which may be employed in a metallizing composition of the invention are Cellosolve acetate (ethylene glycol monoethyl ether acetate), "Carbitol acetate" (diethylene glycol monoethyl ether acetate), benzene and certain higher alcohols. Other solvents for such polymers which may be employed will be apparent to those skilled in the art.

The organic vehicle comprising such an organic polymer and solvent therefor provides numerous advantages in the metallizing composition of the invention. When the metallizing composition after application to the material to be metallized is properly heated, the solvent evaporates and the organic polymer depolymerizes to a monomeric or low molecular state in which it vaporizes readily; therefore, no part of the organic vehicle decomposes and leaves a carbonaceous solid residue in the resulting metallic layer. Moreover, when proper proportions of polymer and solvent are present in the metallizing composition, the composition produces upon baking an uncracked metallic layer. the heating operation the organic vehicle on removal leaves, or assists the deposition of, the particles of metal and glass in a compact layer which, on further heating, produces a metallic layer which is well bonded and substantially nonporous.

The proportion of the organic polymer employed in the metallizing composition is also relatively important. If too little of the organic polymer is employed the'metallizing composition does not have suflicient consistency to permit good spreading. does not maintain the metalcontaining substance and the glass .well dispersed in the metallizing composition, and does not permit or assist the metal and glass particles to form a compact metallic layer. If too much of the polymer is employed the resulting metal layer Under such circumstances during.

fin may be spongy or cracked. In generaiJ-it is advantageous to employ the organic polymer in an amount constituting from about 2 to 25 per centv of the weight of the finely divided glass and the finely divided metal-containing substance in the metallizing composition.

Varying amounts of organic solvent may be employed. Enough solvent should be employed to disperse completely the organic polymer, but apart from this the amount employed will be largely dependent upon the consistency desired in the metallizing composition. The .metallizin composition may-range in consistency from a still paste to a paint-like liquid.

Informing a metallic layer on quartz, ceramic material, glass. or other base material by using a metallizing composition embodying the present invention, the metallizing compound is first formed into a layer on' the surface or portion thereof to be metallized, as by spreading, painting or spraying. After drying or while still wet, said layer is then baked at a temperature and for a time suflicient completely to remove any solvent which may be present, depolymerize and completely remove the polymer by evaporation, reduce to metal any metal compound which may be in the metallizing composition, and melt the glass and cause it to wet the metal particles and base material and cement the metal particles together and to the base material. The temperature and time of heating may vary widely. Optimum conditions may be determined by a few experiments. In general, however, a heating temperature of between about 500 C. and about 850 C. may be'employed, and a heating time of from about 5 to about 30 minutes at such temperature. The rate of heating should not be so great that the organic polymer decomposes before it can be completely removed by depolymerization or evaporation, or that blistering or porosity of the metallic layer resultv because of too rapid discharge of gases from the organic vehicle. However, in general the layer of the metallizing composition can be heated quite rapidly without causing these difficulties; indeed in most cases the layer can be placed directly in an oven heated to the maximum temperature with satisfactory results. While the heating may be caused to take place in an inert atmosphere, it appears that particularly advantageous results are provided if the heating occurs in an oxidizing atmosphere such as air. Apparently the presence of oxygen promotes the adhesion of the metallic layer to a base material such as quartz, ceramic material, or glass. In general, a strongly reducing atmosphere should be avoided in the heating since such an atmosphere may reduce compounds in the glass flux, such as lead compounds, and cause poor adherence.

The following are examples of advantageous metallizing compositions embodying the. present invention:

Example 1.The metallizing composition of this example contained the following ingredients:

46.0 grams of polished silver powder, all particles less than 325 mesh 1 4.0 grams of above Glass A, finely divided 12.5 cc. Acryloid A-10" 22.0 cc. Cellosolve acetate "Acryloid A-lO was the trade-mark of a solution of polymethyl-methacrylate in Cellosolve acetate in which the polymer was 30 per cent by weight of the solution; therefore the above v 7 metallizing composition contained about 3.85 grams ofthe polymer. In preparing the composition the above ingredients were thoroughly mixed in a ball mill for between about 30 and about 40 hours. This was done to reduce further the particle size of the glass and noble metal and to mix thoroughly the ingredients and particularly the noble metal and glass particles. Numerous tests of the metallizing composition were made by forming'a spot of the composition on a piece of quartz, firing in air at about 520 C. for about 30 minutes, then soldering a headed wire of phosphor bronze to the resulting metallic spot, and then pulling until rupturing occurred.

It was found in most cases rupturing occurred when a chip broke out of the quartz rather than by breakage of the soldered joint or by separation of the silver layer and the quartz. This indicated that the resulting silver layer had exceptionally good adherence to the quartz and to the solder.

Example 2.The metallizing composition of this example contained the following ingredients:

46.0 grams polished silver powder, all particles less than 325 mesh 4.0 grams of above Glass B, finely divided 12.5 cc. Acryloid A- 23.0 "Cellosolve acetate" This metallizing composition was prepared as described in Example 1, and also displaced excellent adherence to quartz and solder when tested as described in Example 1.

Example 3.--The metallizing composition in this example had the following formulation:

46.0 grams polished silver powder, all particles less than 325 mesh 4.0 grams of above Glass C, finely divided 12.5 cc. Acryloid A-10 23.0 cc. Cellosolve acetate This silver metallizing composition was prepared in the same manner as that described in Example 1 and displayed excellent adherence to quartz and solubility when tested as described in Example 1.

Example 4.The metallizing composition of this example had the following formulation:

46.0 grams polished silver powder, all particles less than 325 mesh 4.0 grams of above Glass D, finely divided 12.5 cc Acryloid A-10 23.0 cc. "Cellosolve acetate The metallizing composition was prepared as described in Example 1 and displayed excellent adherence to quartz and solderability when tested as described in Example 1.

The drawing shows an illustrated piezoelectric crystal structure embodying a metallic coating deposited from a metallizing composition embodying the present invention. The illustrated apparatus comprises a glass press I forming part of a container for the piezoelectric crystal, having extending therethrough rigid wires 2 and 3 connected to an electrical circuit not shown. Piezoelectric quartz crystal 4 is supported from and electrically connected to said wires 2 and 3 by means of non-linear wires 5 and 6 each of which is fixed at one end to the rigid wires 2 and 3 and at the other end to a surface of a crystal at its nodal point. Each of wires 5 and 6 is soldered at its crystal-connecting end to a silver spot 1 formed on the surface of a crystal by heating a spot of metallizing composition embodying the invention. While any one of many metallizing compositions embodying the invention may be employed, that described in Example 1 is particularly advantageous. The illustrated crystal 4 also has each of its faces coated with a layer of silver 8 in contact with the silver spot I and formed by deposition of silver from silver vapor; layers 8 constitute electrodes.

While the metallizing compositions of the present invention have been described previously in connection with the formation of solderable metal layers on quartz crystals, they may be employed to advantage for forming metal coatings on other materials for soldering or decorative or other purposes. Various modifications may be made in the metallizing compositions described above as embodying the invention without departing from the spirit of the invention. For example, small additions of other substances may be included in the glass flux or in the metallizing composition as a whole.

It is intended that the patent shall cover, by suitable expression in the appended claims, whatever features of patentable novelty reside in the invention.

What is claimed is:

1. A metallizing composition essentially comprising by weight: 46 parts of finely divided silver; 4 parts of a glass flux consisting essentially. of constituents which, expressed as PbO, BzQs, S102 and PbFz, are present in the proportions by weight of 82.5 per cent of PbO, 11.4 per cent of B203, 1.1 per cent of SiOz, and 5.0 per cent of PbFz; 3.85 parts of polymethylmethacrylate; and an organic solvent in which said polymethylmethacrylate is dissolved.

2. A metallizin composition essentially comprising by weight: 46 parts of finely divided silver; 4 parts of a glass fiux consisting essentially of constituents which, expressed as PbO, B203, S102 and PbF2, are present in the proportions by weight of 72.6 per cent of PbO, 6.1 per cent of B203, 16.3 per cent of SiOz, and 5.0 parts of PbFz; 3.85 parts of polymethylmethacrylate; and an organic solvent in which said polymethylmethacrylate is dissolved.

3. A metallizing composition essentially com-- prising by weight: 46 parts of finely divided silver; 4 parts of a glass flux the constitution of which, in terms of oxides, is by weight 87.5 per cent of PbO, 11.4 per cent of B203, and 1.1 per cent of S102; 3.85 parts of polymethylmethacrylate; and an organic solvent in which said polymethylmethacrylate is dissolved.

4. In combination, a quartz piezoelectric crystal; a metallic silver layer firmly adhering thereto and comprising finely divided silver and a fused glass fiux essentially comprising by weight 82.5 per cent of PbO, 11.4 per cent of B203, 1.1 per cent of S102, and 5.0 per cent of PbFa; and a metal element fixed by solder to said metallic silver layer.

5. In combination, a quartz piezoelectric crystal; a metallic silver layer firmly adhering thereto and comprising finely divided silver and a fused glass fiux essentially comprising by weight 72.6 per cent of PbO, 6.1 per cent of B203, 16.3 per cent of SiOz, and 5.0 per cent of PbFz; and a metal element fixed by solder to said metallic silver layer.

6. In combination, a quartz piezoelectric crystal, a metallic silver layer firmly adhering thereto and comprising finely divided silver and a fused glass fiux essentially comprising by weight 87.5

per cent of PbO, 11.4 per cent of B203, and 1.1

aeencvs 7. The method of fastening electric leads to a quartz crystal comprising forming on the surface of said crystal 8. layer containing a finely divided metal and a finely divided glass flux and heating said layer to a temperature above the melting point of said glass flux for a time willcient to fuse said flux and cause it to bind the metal particles together and to the surface of said body and soldering said electric leads to the resulting metallized surface. said glass flux comprising by weight about 50 to 90 per cent of PhD, about to about 25 per cent of B203, and the indicated-proportion of a substance chosen from the group consisting of about 1 to about 20 per cent of. SiOz, from about 5 to about 25 per cent of 31205, from about 1 to about per cent of PbF2, and from about 1 to about 5 per cent of TiOz.

8. The method of fastening electric leads to a quartz crystal comprising forming on the surface of said crystal an adherent metal-containing layer by applying to said surface a layer of a metallizing composition comprising an organic solvent solution of an organic polymer which is heatdepolymerizable without decomposition mixed with a finely divided metal and a finely divided 7 glass flux, and heating said applied layer of metallizing composition to a temperature and for a time sufficient to depolymerize and volatilize said organic polymer and to melt said glass flux and cause it to bind the particles of said finely divided metal together and to said surface, and soldering said electric leads to the resulting metallized surface, said glass flux comprising by weight about 50 per cent to about 90 per cent PbO, about 5 per cent to about 25 per cent of B203, and the indicated proportion of a substance chosen from the group consisting of about 1 to about per cent of S102, from about 5 to about 25 per cent of 131203, from about 1 to about 10 per cent of PbFz, and from about 1 to about 5 per cent of T102.

9. A metallizing composition comprising a fine- 'ly divided noble metal-containing substance, a

finely divided glass which melts below about 500 C. present in an amount constituting about 3 to about 10 per cent of the weight of the metal in said metal-containing substance, an organic polymer which isheat-depolymerizable without decomposition present in an amount constituting about 2 to about 25 per cent of the weight of said noble metal-containing substance and said glass, said organic polymer being an alkyl ester of methacrylic acid, and an organic solvent for said polymer in which said polymer is dissolved.

10. A metallizing composition as described in claim 9 wherein the organic polymer is polymethylmethacrylate.

11. A metallizing composition as described in claim 9 wherein the finely divided noble metalcontaining substance is finely divided silver, and wherein the organic polymer is polymethylmethacrylate.

CARL J. CHRISTENSEN. MERLE D. RIGTERINK. ARNOLD W. TREPTOW.

REFERENCES CITED The following references are of record inv the file of this patent:

UNITED STATES PATENTS Kertesz Apr. 2,1946

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2046629 *Jun 25, 1934Jul 7, 1936Globe Steel Tubes CoProcess of cementation
US2103598 *Nov 21, 1935Dec 28, 1937Corning Glass WorksMetallizing composition for glass
US2139469 *Jan 27, 1937Dec 6, 1938Siemens AgPiezoelectric crystal electrode and method of forming the same
US2385580 *Jul 1, 1944Sep 25, 1945Du PontVitrifiable flux and bonding composition containing same
US2397744 *Jul 1, 1944Apr 2, 1946Du PontMetallic coating composition and structure produced therefrom
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2530217 *Apr 4, 1946Nov 14, 1950Western Electric CoConductive coating compositions
US2554373 *Jun 1, 1948May 22, 1951Usines Chimiques Rhone PouleneProcess for producing glossy coatings on earthenware and metal
US2608539 *Mar 22, 1950Aug 26, 1952Western Electric CoMetallized ceramic coating composition
US2692218 *Jun 29, 1949Oct 19, 1954Rca CorpMethod of making insulated wire
US2697047 *Sep 14, 1950Dec 14, 1954Bell Telephone Labor IncMethod of providing a spot of silver on a piezoelectric crystal
US2731533 *May 5, 1953Jan 17, 1956Magrath Richard AMounting base for bolometer
US2734840 *Oct 1, 1952Feb 14, 1956 Ceramic decalcomania and method of making same
US2751477 *Jul 15, 1952Jun 19, 1956Pittsburgh Plate Glass CoElectrical resistive device
US2776472 *Jul 24, 1952Jan 8, 1957Gen ElectricMethod of making a ceramic-to-metal bond
US2805944 *Sep 16, 1953Sep 10, 1957Sylvania Electric ProdLead alloy for bonding metals to ceramics
US2808351 *Oct 31, 1952Oct 1, 1957Libbey Owens Ford Glass CoElectrically conducting coated glass or ceramic articles suitable for use as a lens, a window or a windshield, or the like
US2814165 *Jun 12, 1952Nov 26, 1957Cinema Television LtdVacuum-tight electrical connections for electron-discharge devices
US2816996 *Dec 14, 1953Dec 17, 1957Wilbur M KohringResistance production
US2835601 *Jun 24, 1953May 20, 1958Pemco CorpProduction of ceramic ware
US2878560 *Jan 10, 1955Mar 24, 1959Jr John R GierMethod of making composite light weight structural elements
US2882187 *Sep 6, 1955Apr 14, 1959Therm O Lab CorpElectrical heating element
US2950995 *Mar 18, 1957Aug 30, 1960Beckman Instruments IncElectrical resistance element
US2950996 *Dec 5, 1957Aug 30, 1960Beckman Instruments IncElectrical resistance material and method of making same
US3006069 *May 23, 1957Oct 31, 1961Rca CorpMethod of sealing a metal member to a ceramic member
US3012924 *Dec 17, 1956Dec 12, 1961Libbey Owens Ford Glass CoElectrically conducting unit
US3031344 *Aug 8, 1957Apr 24, 1962Radio Ind IncProduction of electrical printed circuits
US3037180 *Aug 11, 1958May 29, 1962Nat Lead CoN-type semiconductors
US3052573 *Mar 2, 1960Sep 4, 1962Du PontResistor and resistor composition
US3091027 *Nov 19, 1959May 28, 1963Pechiney Prod Chimiques SaMethod and composition for assembling together refractory bodies
US3123470 *Jan 28, 1955Mar 3, 1964 Bonding means and method
US3149002 *Mar 4, 1960Sep 15, 1964Beckman Instruments IncMethod of making electrical resistance element
US3206658 *Dec 7, 1959Sep 14, 1965Sprague Electric CoSolid electrolyte capacitor with surface-contacting cathode lead
US3227591 *Apr 26, 1963Jan 4, 1966Sylvania Electric ProdFilm techniques
US3252831 *May 6, 1964May 24, 1966Electra Mfg CompanyElectrical resistor and method of producing the same
US3296693 *Sep 21, 1962Jan 10, 1967Carter Shirley JTungsten carbide brazing
US3323924 *Mar 27, 1964Jun 6, 1967Varian AssociatesLow dielectric loss metallizing paint composition having a reduced sintering temperature
US3352694 *Jun 17, 1963Nov 14, 1967Varian AssociatesLow temperature metallizing paint and method of making same
US3455708 *Mar 18, 1964Jul 15, 1969Physical Sciences CorpCeramic material
US3507646 *Dec 27, 1965Apr 21, 1970Xerox CorpElectrophotographic process using a single phase photoconductive glass imaging layer
US3661615 *Mar 11, 1969May 9, 1972Owens Illinois IncSubstrate coating process
US3753757 *May 15, 1970Aug 21, 1973Union Carbide CorpTwo step porous boiling surface formation
US3877962 *Dec 18, 1972Apr 15, 1975Owens Illinois IncSubstrate coating composition and process
US3957497 *Dec 4, 1970May 18, 1976Owens-Illinois, Inc.Polystyrenes, 1a oxides, boric oxide, lead oxide
US4235644 *Aug 31, 1979Nov 25, 1980E. I. Du Pont De Nemours And CompanyThick film silver metallizations for silicon solar cells
US4257904 *Dec 30, 1974Mar 24, 1981International Business Machines Corp.Dielectric glass coating composition containing polymethylmethacrylate fugative binder
US4447550 *Jun 13, 1983May 8, 1984Corning Glass WorksOptics
US4810525 *Apr 21, 1987Mar 7, 1989Mitsubishi Denki Kabushiki KaishaLaser method of coating metal with a noble metal
US4906596 *Jul 20, 1989Mar 6, 1990E. I. Du Pont De Nemours & Co.Die attach adhesive composition
Classifications
U.S. Classification428/552, 524/560, 427/100, 427/427, 427/376.3, 228/903, 427/429, 419/69, 427/383.3, 228/122.1, 524/403, 419/21, 439/83, 501/19, 209/66, 428/434, 427/125, 29/25.35, 338/308, 75/252, 106/1.14, 427/383.5, 310/363, 428/556, 524/317
International ClassificationC03C17/06
Cooperative ClassificationY10S228/903, C03C2218/17, C03C17/06, C03C2217/251
European ClassificationC03C17/06