# US 4,395,303 A · Method of manufacturing thin-walled corrosion resistant metallic objects

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- Number: US 4,395,303 A
- Document ID: US4395303A
- Status: Granted
- Kind: A
- Application number: 06/256,003
- Filed: 1981-04-22
- Granted: 1983-07-26
- Earliest claimed: 1981-04-22
- Assignees: Masco Corporation
- Inventors: Charles R. Weir
- Web page: https://patentgrep.com/patent/US4395303A

## CPC

- C23C 10/60: After-treatment
- C23F 1/04: Chemical milling
- Y10T 428/12292: Workpiece with longitudinal passageway or stopweld material [e.g., for tubular stock, etc.]
- Y10T 428/1234: Honeycomb, or with grain orientation or elongated elements in defined angular relationship in respective components [e.g., parallel, inter- secting, etc.]
- 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 (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- C23F: NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE (working metal by laser beams B23K26/00; desurfacing by applying flames B23K7/00; working of metal by electro-erosion B23H; producing decorative effects by removing surface material, e.g. by engraving, by etching, B44C1/22; electrolytic etching or polishing C25F); INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A method of manufacturing metallic objects having thin walls and comprised of corrosion resistant materials. The method has the consecutive steps of forming a workpiece in the shape of the desired end product from a metal having a low resistance to an etchant, forming within a surface of the workpiece a metallic alloy case resistant to the etchant and etching the workpiece with the etchant.

## Claims

### Claim 1

A method of making a thin-walled corrosion resistant end product from a workpiece comprised of a starting metal not resistant to an etchant and from an alloying metal which is selectively soluble in said starting metal to produce an alloy metal impervious to said etchant, the method comprising the consecutive steps of forming said workpiece into the shape of said end product, forming an alloy case of said alloy metal on a surface of said workpiece, and exposing said workpiece to said etchant to remove the portion of said workpiece which is not alloyed.

### Claim 2 (depends on 1)

The method of claim 1 wherein said workpiece is a length of wire bent into the shape of a desired tubing end product and wherein said corrosion resistant alloy case is formed on the outer cylindrical surface of the wire and is not formed on the end surfaces of said wire; whereby said end product is a thin-walled corrosion resistant tube.

### Claim 3 (depends on 2)

The method of claim 2 wherein said starting metal is copper, wherein said etchant is sulfuric acid, wherein said alloying metal is nickel and wherein said alloy metal is monel.

### Claim 4 (depends on 2)

The method of claim 2 further comprising an additional step prior to forming said case, said additional step consisting of milling a slot in the surface of said wire; whereby said tube has a fin where said surface was milled.

### Claim 5 (depends on 2)

The method of claim 2 wherein said wire has an external screw thread, whereby said tube has a spiral rib about both its outer cylindrical surface and its inner cylindrical surface.

### Claim 6 (depends on 2)

The method of claim 2 wherein said wire has knurling on its cylindrical surface whereby said tube has pyrimidal contours on its outer and inner cylindrical surfaces.

### Claim 7 (depends on 2)

The method of claim 2 wherein said wire is comprised of low carbon steel, wherein said etchant is nitric acid and wherein said alloy metal is stainless steel.

### Claim 8 (depends on 7)

The method of making a thin-walled stainless steel tube of claim 7 wherein said case is formed on said wire by the consecutive steps of plating chromium on the surface of said wire and heating said wire to a temperature above that at which diffusion of chromium into steel occurs, and below the melting temperature of said wire.

### Claim 9 (depends on 8)

The method of claim 8 wherein several of said low carbon steel wire workpieces are used, wherein each of said wires has its cylindrical surface plated with chromium and wherein each of said wires has a portion of its plated surface touching the plated surface of another of said wires during said heating step; whereby said wire workpieces fuse together during said heating step.

### Claim 10 (depends on 2)

The method of claim 2 wherein said wire is less than one foot long and less than one half of an inch thick.

### Claim 11 (depends on 2)

The method of claim 2 wherein said wire has a diameter of between thirty thousandths of an inch (0.030") and two inches (2.0").

### Claim 12 (depends on 1)

The method of claim 1 wherein said starting metal is pure iron, wherein said etchant is nitric acid, and wherein said alloying metal is chromium.

### Claim 13 (depends on 1)

The method of claim 1 wherein said starting metal is copper, wherein said etchant is sulfuric acid, wherein said alloying metal is nickel and wherein said alloy metal is monel.

### Claim 14 (depends on 1)

The method of claim 1 wherein said case is formed on said workpiece by the consecutive steps of plating an alloying metal on said surface of said workpiece and heating said workpiece to a temperature above the temperature at which said alloying metal will begin to diffuse into said starting metal to produce a corrosion resistant alloy layer but to a temperature below the melting temperature of the metal.

### Claim 15 (depends on 14)

The method of claim 14 wherein at least two of said workpieces are used, wherein each of said workpieces has a surface plated with said alloying material and wherein a portion of said plated surface of each of said workpieces is touching a portion of said plated surface of any other of said workpieces during said heating step; whereby said workpieces are welded together by said heating step.

### Claim 16

A method of making a thin-walled corrosion resistant end product, the method comprising the consecutive steps of forming a low carbon steel workpiece into the shape of said end product, forming an acid resistant alloy case on a surface of said steel workpiece, and etching said workpiece with an acid which will dissolve the steel but to which the alloy case is impervious.

### Claim 17 (depends on 16)

The method of claim 16 wherein said steel has a carbon content of less than 0.2%.

### Claim 18 (depends on 16)

The method of claim 16 wherein said acid resistant alloy is a form of stainless steel.

### Claim 19 (depends on 18)

The method of claim 18 wherein said stainless steel case is produced by the consecutive steps of plating chromium on said surface of said workpiece, and heating said workpiece to a temperature at which the chromium will diffuse into said surface.

### Claim 20 (depends on 19)

The method of claim 19 wherein said chromium is plated on said surface by electrodeposition.

### Claim 21 (depends on 16)

The method of claim 16 wherein said acid is nitric acid.

### Claim 22

A method of continuously making thin-walled corrosion resistant tubing, the method comprising the simultaneous steps of supplying a portion of a continuous line of a metallic wire comprised of a starting metal to a plating station, continuously plating said portion of said wire in said plating station with an alloying metal, continuously feeding a portion of said wire from said plating station into a furnace, continuously heating said portion of said wire in said furnace at a temperature between the temperature at which said alloying material alloys with said starting metal and the melting temperature of said wire, maintaining said wire within said furnace until said alloying material has diffused into the surface of said wire to produce an alloy metal case of a predetermined depth; continuously feeding a portion of said wire from said furnace to a cutting station, intermittingly cutting said portion of said wire at said cutting station into predetermined lengths of wire, said method further comprising the step for each of said lengths of wire of etching said lengths of wire with an etchant to which said starting metal is not resistant but to which said alloy metal is resistant.

### Claim 23 (depends on 22)

The method of claim 22 further comprising the additional steps of continuously supplying an untreated portion of said steel wire to a degreasing station, continuously cleansing said portion of said steel wire in said cleansing station in a solvent and continuously feeding a portion of said steel wire from said cleansing station to said plating station.

### Claim 24 (depends on 22)

The method of claim 22 further comprising the additional steps of continuously supplying an untreated portion of said steel wire to a pickling station, continuously cleansing the portion of said steel wire in said pickling station with a mild acid, and continuously feeding a portion of said steel wire from said cleansing station to said plating station.

### Claim 25 (depends on 22)

The method of claim 22 further comprising the additional steps of continuously supplying a portion of said wire to an extruder continuously feeding said portion of said wire through said extruder to produce a desired cross-section for said wire, and continuously feeding a portion of said wire from said extruder to said plating station.

### Claim 26 (depends on 22)

The method of claim 22 wherein said metal is low carbon steel, said alloying metal is chromium, and said alloy is stainless steel.

### Claim 27

A method of producing a corrosion resistant end product having a plurality of parallel passageways therethrough from at least three elongated workpieces comprised of a first metal having a low resistance to acid, said method comprising the consecutive steps of:
plating an alloying metal on the outer longitudinal surface of each of said workpieces;
arranging said workpieces in an array wherein the longitudinal axis of the workpieces are parallel to each other and wherein each of said workpieces is in contact along its outer longitudinal surface with the outer longitudinal surface of at least one of the other workpieces;
heating said array of workpieces in the presence of a protective atmosphere to a temperature above the temperature at which said alloying metal will diffuse into said first metal and below the melting temperature of said first metal;
maintaining said array at said temperature until said diffusion of said alloying metal into said first metal has produced a boundary layer of an alloying metal having a predetermined thickness and until said portions of said outer surfaces of said adjacent workpieces have bonded together;
maintaining said array in said protective atmosphere while cooling said array to a temperature at which the ambient atmosphere will no longer oxidize said alloying metal; and
etching the remaining unalloyed portion of said first metal from said array with an etchant that will dissolve said first metal but will not dissolve said alloy metal.

### Claim 28 (depends on 27)

The method of claim 27 wherein each of said workpieces is a wire of less than three inches in length and of less than half of an inch diameter, whereby said end product is a metallic structure having several small parallel and uniform passageways.

### Claim 29 (depends on 27)

The method of claim 27 wherein each of said workpieces is comprised of low carbon steel and wherein said alloying metal is chromium, whereby said alloy metal is stainless steel.

### Claim 30 (depends on 27)

The method of claim 27 wherein said workpieces are parallelepipeds whereby said end product is a metallic honeycomb structure.

### Claim 31 (depends on 27)

The method of claim 27 wherein each of said workpieces is comprised of copper and wherein said alloying metal is nickel, whereby said alloy metal is monel.