US3891784A - Method of preparing oxidation resistant brazed joints - Google Patents
Method of preparing oxidation resistant brazed joints Download PDFInfo
- Publication number
- US3891784A US3891784A US411965A US41196573A US3891784A US 3891784 A US3891784 A US 3891784A US 411965 A US411965 A US 411965A US 41196573 A US41196573 A US 41196573A US 3891784 A US3891784 A US 3891784A
- Authority
- US
- United States
- Prior art keywords
- copper
- aluminum
- slurry
- core
- joints
- 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.)
- Expired - Lifetime
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0012—Brazing heat exchangers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
- C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
Definitions
- the invention relates generally to brazing, to oxidation resistant structures, to copper-brazed structures which are rendered oxidation resistant and to a method of diffusion alloying copper brazed joints and fillets, hereinafter referred to simply as joints, and structures with aluminum. It is specifically concerned with providing oxidation resistant brazed joints in regenerator cores for turbine engines, although it is applicable to copper joints in similar matrix structures and to brazed copper joints generally.
- Copper-brazed joints and fillets and related structures are alloyed according to the invention with aluminum for achieving oxidation resistance.
- a more direct method of copper-brazing with oxidation resistant copper-aluminum alloys, wherein the structure to be brazed is coated with a slurry of copper-aluminum, has proven to be undesirable because of poor wetting." That is, the aluminum in the copper-aluminum alloy oxidizes and is not readily reduced by hydrogen. Consequently, the molten copper-aluminum alloy does not flow adequately to form suitable joints at the joint locations of the structure to be brazed.
- this invention starts with a copper joint, or structure, coats it with aluminum and diffusion alloys the aluminum into and with the copper, and with the structure itself in some instances, to provide an oxidation resistant copper-aluminum brazed joint or structure. Oxidation resistance is improved not only at low temperatures but at elevated temperatures as well.
- the invention uses an aluminum slurry for coating metal parts, assemblies and joints thereof with aluminum.
- the slurry consists of aluminum flake or powder suspended in a suitable vehicle.
- the slurried surface is heated in a suitable atmosphere, such as hydrogen, until the aluminum melts and diffuses into the surface.
- regenerator matrix passages in such a way as to provide a graded aluminum-copper alloy across the matrix and to promote uniform oxidation resistance of the copper and steel regenerator assembly throughout the temperature gradient encountered during operation in a turbine engine.
- Regenerator cores are usually made of ferritic stainless steel, such as 430 stainless, although other types of steel may be used.
- FIG. 1 is a plan view showing the matrix structures of a regenerator core for a turbine engine schematically in part.
- FIG. 2 is an end view of FIG. 1.
- FIG. 3 is a fragmentary enlarged plan view of a portion of the matrix illustrated in FIG. 1 showing the brazed joints.
- FIG. 4 is a schematic showing of a fixture useful in applying slurry to a core.
- FIG. 5 is a graph illustrating diffusion depth of aluminum into copper, low carbon steel, and stainless steel at various temperatures over a period of k hour.
- FIG. 6 illustrates the steps in the slurrying of copperbrazed regenerator cores into an aluminum slurry.
- FIG. 7 is a graph showing the relationship between percent aluminum distribution across the thickness of a core and the average overall percent of slurry weight gain (SWG) resulting from dipping a core into an aluminum slurry.
- SWG slurry weight gain
- FIG. 8 is a graph showing the relationship between the percent aluminum diffused into the copper joints and the percent of slurry weight gain (SWG); and also the upper limit of the percent aluminum in the alloy and the upper limits of diffusion temperature.
- FIG. 9 is a graph illustrating the relationship between the oxidation resistance of treated regenerator core samples in terms of percent of fillets oxidized and the average percent of slurry weight gain.
- FIG. 10 is a graph showing the relationship between the oxidation resistance of treated regenerator core samples in terms of oxidation weight gain and the average percent of slurry weight gain.
- regenerator cores typically consist of a rim 10, a hub 12 and a matrix portion generally indicated by 14, which is best shown in detail in FIG. 3.
- the regenerator is a relatively flat, round structure with a plurality of passageways extending axially through the matrix for the flow of gases therethrough.
- passageways in the particular design shown are formed by alternately positioned corrugated layers 16 of stainless steel stock and flat layers 18 of stainless steel stock about 3% inches wide and 0.002 inch thick.
- Other variations and designs of matrix type regenerator cores are known and this invention is applicable to them as well as to matrix structures in general.
- the matrix parts of a regenerator are assembled together and the rim and hub are attached.
- such an assembly is coated with a slurry of copper oxide and then heated in a reducing atmosphere, hydrogen being preferred, to reduce the copper oxide, forming molten copper which flows into all the various junctions between the parts, thus forming a brazed structure which is bonded with copper joints, after cool-down to room temperature.
- a slurry of copper flake may be used in place of the oxide in which case the hydrogen environment is not necessary.
- the joints are able to withstand operation at temperatures up to at least about 1,400F.
- the regenerator cores described herein which are about 15 /2 inches in diameter, 3 /2 inches thick, about 1000 grams of copper has been found to be adequate for brazing the cores without undue plugging.
- the application of the copper oxide slurry is not particularly critical insofar as its distribution over the assembly is concerned because of the tendency of molten copper to readily flow and wet the assembly when at brazing temperatures of about 1,980F. to 2,050F. Consequently, copper oxide slurries with a water vehicle may be used. The assembly is simply dipped and rinsed if excess slurry appears to be present. Hydrogen heating of a copper slurried assembly produces an assembly having copper brazed joints. Other means of providing copper joints, such as using slurries containing copper flake or powder or others may be used with this invention. The particular technique of placing the copper to form the joint, whether by slurry or any other technique, is not important to this invention.
- the copper brazed assembly is subjected to a slurrying step wherein the assembly is coated with an aluminum slurry following which it is heated to diffuse the aluminum into the copper joints thereby forming oxidation resistant copper-aluminum alloy at the joints.
- diffusion of the aluminum into the steel parts of the core will also occur simultaneously if the slurry has been applied to it. In most cases this is beneficial.
- the curve of FIG. illustrates the depth to which the diffusion of aluminum depending on temperature occurs into materials of the type described herein. A detailed procedure is described below for the preparation of regenerator cores of the type and size described above.
- Core Preparation 1 Degrease the core either by pouring cold degreasing fluid, such as trichloroethylene through the matrix or preferably by the use of a vapor degreaser using trichloroethylene vapors.
- cold degreasing fluid such as trichloroethylene
- the slurry can be stored indefinitely in glass, rubber, plastic or stainless steel containers. (Ordinary steel containers corrode rapidly and contaminate the slurry.)
- the core is preferably placed in a slurry fixture of the type shown in FIG. 4 designed to: 1. provide a reservoir for several gallons of slurry,
- a blower to the fixture.
- Attach depth indicator on rim of core This may be a piece of tape or simply a scratch mark to indicate the depth to which the core is to be dipped. (Oxidation resistant joints may only be required through part of the thickness of a core matrix depending on the temperature at which the hot face will operate and the core thickness.)
- Handles may be attached on opposite points of core rim to facilitate handling.
- the recommended and preferred weight gain is about 1.5% i 0.4% of initial weight.
- the core is outside of the limits, it may be washed out with acetone to remove all slurry, and then reslurried.
- the slurrying technique used will determine both the total amount of aluminum picked up by the core and its distribution within the individual matrix passages as shown in FIGS. 7 and 8 (SWG meaning slurry weight gain).
- SWG slurry weight gain
- the most desirable distribution of aluminum varies from zero aluminum in an area at the cold face, to high aluminum at the hot face in an axial gradient through the core which corresponds to the operating temperature gradient through it, which in turn, dictates the requirement for the oxidation resistance.
- Aluminum within each passage of the core is distributed primarily at the copper joints and fillets because of surface tension forces which operate on the aluminum slurry.
- the stainless steel matrix benefits from some aluminum diffusion. In case of 430 stainless steel which contains 16-18% chrome, the oxidation resistance of the stock is improved with the diffusion of aluminum into it.
- Heating of the slurried core at a temperature of about 1,800F. i about 50F. for a time sufficient to allow the aluminum to diffuse throughout the fillets and joints is ordinarily satisfactory. In this particular case, about 2 hours is adequate. Diffusion in a reducing atmosphere, such as hydrogen, is preferred but vacuum or inert atmosphere is acceptable.
- FIG. 5 illustrates in general that diffusion into various materials may be controlled by adjusting temperature. Time is another diffusion variable.
- FIG. 9 illustrates that 1,800F. is the optimum temperature for diffusion of a minimum of 1.0% SWG of aluminum. Additional amounts of aluminum do not appreciably add to the oxidation resistance of the coper-aluminum alloy at 1,400F.
- FIG. 10 illustrates that oxidation resistance increases with increasing amounts of aluminum.
- FIG. 8 illustrates that, if the diffusion temperature is too high, melting of the copper aluminum alloy during its formation occurs, causing loss of the fillets since the molten copper-aluminum does not wet appreciably.
- the processing temperature must be about l,800F. i about 50F.
- FIG. 8 also illustrates the relation between the percent slurry at any point in the core and the corresponding percent aluminum in copper at that point, both before and after diffusion.
- Approximately percent of Di ed wt. (cleaned) Initial wt. 100 SWG (assume matrix Cu 11,700 g on 3% inch core 15% in diameter) (10 g slurry wt. gain is about 0.085% SWG) (l centipoise difference is about g SWG difference).
- Non-uniform depth of dipping Non-uniform level of slurry in passages due to core defects or variations in time of immersion or variations in slurry.
- Oxidation resistance at about 1,400F. has been the principal quality criterion of work pieces treated by the method of this invention because that is currently regarded as the most likely maximum operating temperature in turbine engines, the preferred usage of this invention. However, this invention provides materials which are believed to exhibit improved oxidation resistance at even higher temperatures. Oxidation resistance is a corollary of the gain in weight due to oxide formation under oxidizing conditions, such as exposure to circulating room air. The weight change at I,400F. in milligrams per square centimeter, was measured and recorded periodically for samples which were exposed to such oxidizing conditions. The samples were also examined under a low power microscope to determine the mode of failure. All samples were periodically cycled from I,400F.
- oxidation resistance of the copper joints is proportional to the aluminum content thereof, a sufficient quantity of aluminum slurry should be deposited at each joint to produce on oxidation resistant alloy, i.e., up to a maximum of about l0-I5 percent aluminum, balance copper, as indicated in FIG. 8 for regenerator cores, depending on the elevated temperature to be sustained.
- the diffusion time and temperature should be sufficient to produce uniformly alloyed joints.
- Excessive aluminum, that is greater than about 15 percent in the joints of a regenerator core is detrimental because high-aluminum-copper alloys tend to be brittle at room temperature.
- Aluminum also lowers the melting point of copper and decreases its wettability, causing loss of the fillets during diffusion.
- balance copper is a composition most desirable for structures exposed to temperatures on the order of l,400F. operating temperatures, such as regenerator cores. Lower temperatures may utilize lower amounts of aluminum for oxidation resistance. Higher temperatures require higher amounts of aluminum. However, high aluminum content can provide brittle alloys and, although oxidation resistant, composition must be selected in the context of the intended use.
- This specification describes a grade of cuprous oxide brazing compound suitable for joining steel parts when used in conjunction with a reducing atmosphere brazing furnace. Brazing compound is applied to the joint area of the parts being joined. The cuprous oxide is reduced to metallic copper by the reaction of the reducing atmosphere at elevated temperatures. The metallic copper melts and forms the brazed joint between the parts being processed.
- a method of preparing oxidation resistant brazed joints comprising the steps of:
- Cuprous Oxide Particle Size The effective particle size and particle size distribution of the cuprous oxide effects the brazing compound viscosity characteristics, settling rate during storage, and fluidity of the applied brazing compound.
- the desired particle size range varies 1 from about 1-30 microns in diameter with most of the particles being in the 4-20 micron range.
- Pluronics L-64 (Wyandotte Chemical Company) 3.75 to 4.0 lbs.
- Carbowax 6000 (Carbide and Carbon Chemical Co.) 14.5 to 15.0 lbs.
- Glycol (Ethylene or Mixed Ethylene and Propylene) 11.0 to 11.5 lbs.
- Viscosity and density should be measured at 78 i 1F. approximately one hour after mixing. The viscosity should be measured with a Brookfield viscosimeter using a No. 6 spindle running at 20 rpm. a. Viscosity atmospheres.
Abstract
Description
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US411965A US3891784A (en) | 1972-12-18 | 1973-11-01 | Method of preparing oxidation resistant brazed joints |
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US31614572A | 1972-12-18 | 1972-12-18 | |
US411965A US3891784A (en) | 1972-12-18 | 1973-11-01 | Method of preparing oxidation resistant brazed joints |
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US3891784A true US3891784A (en) | 1975-06-24 |
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US411965A Expired - Lifetime US3891784A (en) | 1972-12-18 | 1973-11-01 | Method of preparing oxidation resistant brazed joints |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4139673A (en) * | 1977-02-22 | 1979-02-13 | Nihon Karoraizu Kogyo Kabushiki Kaisha | Surface-coated blast furnace tuyere made of copper or copper alloy and method of surface-coating the same |
US4141760A (en) * | 1972-11-06 | 1979-02-27 | Alloy Surfaces Company, Inc. | Stainless steel coated with aluminum |
DE3340987A1 (en) * | 1982-11-11 | 1984-12-20 | Joh. Vaillant Gmbh U. Co, 5630 Remscheid | Process for producing scale-resistant soldered chromium-steel components and component produced by the process |
DE3241706C1 (en) * | 1982-11-11 | 1985-01-10 | Joh. Vaillant Gmbh U. Co, 5630 Remscheid | Method of producing scale-resistant soldered chromium-steel components and use of the method for producing a burner |
DE3726073C1 (en) * | 1987-08-06 | 1988-07-14 | Thyssen Edelstahlwerke Ag | Process for the production of thin-walled semi-finished products and their uses |
DE3726072A1 (en) * | 1987-08-06 | 1989-02-16 | Thyssen Edelstahlwerke Ag | Soldering method |
DE3726075C1 (en) * | 1987-08-06 | 1989-03-02 | Thyssen Edelstahlwerke Ag | Method of soldering steel parts and of producing catalyst supports, heat exchangers and soot filters |
US5050790A (en) * | 1987-12-28 | 1991-09-24 | Usui Kokusai Sangyo Kabushiki Kaisha | Process for the fabrication of metal-made carrier body for exhaust gas cleaning catalyst |
DE4222026C1 (en) * | 1992-07-04 | 1993-04-15 | Thyssen Edelstahlwerke Ag, 4000 Duesseldorf, De | Semi-finished prod. mfr. used as catalyst supports - by coating starting material, e.g. ferritic stainless steel, with at least one chromium@ layer and diffusion heat treating |
US5648176A (en) * | 1994-02-08 | 1997-07-15 | Nippon Steel Corporation | Metallic honeycomb body for supporting catalyst for automobiles and process for producing the same |
US6129262A (en) * | 1997-02-24 | 2000-10-10 | Ford Global Technologies, Inc. | Fluxless brazing of unclad aluminum using selective area plating |
EP1564310A1 (en) * | 2004-01-15 | 2005-08-17 | Behr GmbH & Co. KG | Method and device for treating metal workpieces |
US20220055158A1 (en) * | 2020-08-20 | 2022-02-24 | Toyota Motor Engineering & Manufacturing North America, Inc. | Copper solder formulation |
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US3235959A (en) * | 1962-06-25 | 1966-02-22 | Alloys Res & Mfg Corp | Brazing aluminum based parts |
US3290182A (en) * | 1965-05-25 | 1966-12-06 | Olin Mathieson | Method of making aluminum bronze articles |
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US3743547A (en) * | 1969-10-27 | 1973-07-03 | R Green | Protection of metallic surfaces |
US3807030A (en) * | 1972-12-27 | 1974-04-30 | Chrysler Corp | Method of preparing oxidation resistant materials |
-
1973
- 1973-11-01 US US411965A patent/US3891784A/en not_active Expired - Lifetime
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US1091057A (en) * | 1913-03-12 | 1914-03-24 | Gen Electric | Process of treating metals. |
US2541813A (en) * | 1947-11-08 | 1951-02-13 | Gen Electric | Calorizing process |
US3183588A (en) * | 1961-03-25 | 1965-05-18 | Fond De Nogent Lafeuille & Cie | Production of alloy-clad articles |
US3235959A (en) * | 1962-06-25 | 1966-02-22 | Alloys Res & Mfg Corp | Brazing aluminum based parts |
US3395027A (en) * | 1964-03-05 | 1968-07-30 | Teleflex Inc | Coating composition and method |
US3290182A (en) * | 1965-05-25 | 1966-12-06 | Olin Mathieson | Method of making aluminum bronze articles |
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4141760A (en) * | 1972-11-06 | 1979-02-27 | Alloy Surfaces Company, Inc. | Stainless steel coated with aluminum |
US4139673A (en) * | 1977-02-22 | 1979-02-13 | Nihon Karoraizu Kogyo Kabushiki Kaisha | Surface-coated blast furnace tuyere made of copper or copper alloy and method of surface-coating the same |
DE3340987A1 (en) * | 1982-11-11 | 1984-12-20 | Joh. Vaillant Gmbh U. Co, 5630 Remscheid | Process for producing scale-resistant soldered chromium-steel components and component produced by the process |
DE3241706C1 (en) * | 1982-11-11 | 1985-01-10 | Joh. Vaillant Gmbh U. Co, 5630 Remscheid | Method of producing scale-resistant soldered chromium-steel components and use of the method for producing a burner |
DE3726075C1 (en) * | 1987-08-06 | 1989-03-02 | Thyssen Edelstahlwerke Ag | Method of soldering steel parts and of producing catalyst supports, heat exchangers and soot filters |
DE3726072A1 (en) * | 1987-08-06 | 1989-02-16 | Thyssen Edelstahlwerke Ag | Soldering method |
DE3726073C1 (en) * | 1987-08-06 | 1988-07-14 | Thyssen Edelstahlwerke Ag | Process for the production of thin-walled semi-finished products and their uses |
US5050790A (en) * | 1987-12-28 | 1991-09-24 | Usui Kokusai Sangyo Kabushiki Kaisha | Process for the fabrication of metal-made carrier body for exhaust gas cleaning catalyst |
DE4222026C1 (en) * | 1992-07-04 | 1993-04-15 | Thyssen Edelstahlwerke Ag, 4000 Duesseldorf, De | Semi-finished prod. mfr. used as catalyst supports - by coating starting material, e.g. ferritic stainless steel, with at least one chromium@ layer and diffusion heat treating |
US5648176A (en) * | 1994-02-08 | 1997-07-15 | Nippon Steel Corporation | Metallic honeycomb body for supporting catalyst for automobiles and process for producing the same |
US6129262A (en) * | 1997-02-24 | 2000-10-10 | Ford Global Technologies, Inc. | Fluxless brazing of unclad aluminum using selective area plating |
EP1564310A1 (en) * | 2004-01-15 | 2005-08-17 | Behr GmbH & Co. KG | Method and device for treating metal workpieces |
US20220055158A1 (en) * | 2020-08-20 | 2022-02-24 | Toyota Motor Engineering & Manufacturing North America, Inc. | Copper solder formulation |
US11794286B2 (en) * | 2020-08-20 | 2023-10-24 | Toyota Motor Engineering & Manufacturing North America, Inc. | Copper solder formulation |
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Owner name: CHRYSLER CORPORATION Free format text: PARTES REASSIGN, TRANSFER AND RELINQUISH THEIR ENTIRE INTEREST UNDER SAID PATENTS ALSO RELEASE THEIR SECURITY INTEREST.;ASSIGNOR:MANUFACTURERS NATIONAL BANK OF DETROIL (CORPORATE TRUSTEE) AND BLACK DONALD E., (INDIVIDUAL TRUSTEE);REEL/FRAME:004355/0154 Effective date: 19840905 |
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Owner name: HELLER FINANCIAL, INC. Free format text: AMENDMENT TO RESTATE THE ORIGINAL SECURITY AGREEMENT DATED SEPTEMBER 15, 1989.;ASSIGNOR:ICM/ KREBSOGE A GENERAL PARTNERSHIP OF DELAWARE;REEL/FRAME:005797/0303 Effective date: 19910724 |