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US3552000A - Method of manufacturing dispersion-hardened workpieces - Google Patents

Method of manufacturing dispersion-hardened workpieces Download PDF

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Publication number
US3552000A
US3552000A US660183A US3552000DA US3552000A US 3552000 A US3552000 A US 3552000A US 660183 A US660183 A US 660183A US 3552000D A US3552000D A US 3552000DA US 3552000 A US3552000 A US 3552000A
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United States
Prior art keywords
metal
carrier
workpieces
nickel
malleable
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Expired - Lifetime
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US660183A
Inventor
Dieter Hirschfeld
Emil Hillnhagen
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Beteiligungs und Patentverwaltungs GmbH
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Beteiligungs und Patentverwaltungs GmbH
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Publication of US3552000A publication Critical patent/US3552000A/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02Combined electrolytic and electrophoretic processes with charged materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/4998Combined manufacture including applying or shaping of fluent material
    • Y10T29/49982Coating

Definitions

  • Compact, malleable and rollable metal workpieces are prepared by the electrodeposition of a metal component onto a metal carrier such as a wire or sheet, the dimensions of the carrier being small in relation to the volume of deposited metal, there being added to the deposition bath a refractory material and a wetting agent.
  • a metal carrier such as a wire or sheet
  • workpieces which are compact, malleable and rollable are produced electrolytically from dispersion-hardened materials, by depositing a metallic component, such as a pure metal or an alloy, from an electrolyte, upon a suitable carrier, such as a sheet or wire, While simultaneously introducing a refractory component; advantageously, a suitable wetting or dispersing agent is also added to the electrolyte.
  • a metallic component such as a pure metal or an alloy
  • the metallic component may be any desired metal or alloy.
  • metal which may be used to advantage in the practice of the invention include nickel, co-
  • balt, columbium, vanadium, silver, and lead examples include alloys of nickel and cobalt, containing from 10% to 50%- cobalt, or alloys of nickel and molybdenum containing from to 25% molybdenum, as well as also alloys of cobalt with nickel and tungsten, alloys of nickel with cobalt, molybdenum, tungsten and chromium, and alloys of columbium with titanium, molybdenum, tungsten and zirconium.
  • Refractory materials which may be employed in accordance with the invention include the oxides, carbides, nitrides, and borides of metals such as aluminum, thorium, cadmium, titanium and zirconium, or mixtures thereof. Examples include A1 0 ThO TiB and ZrC. The proportion of such refractory material to the metal component is from about 0.5% to about by weight.
  • metal wire As a carrier material upon which the metal component is deposited, there may be employed metal wire, sheet,
  • the carrier material is preferably identical with the metal to be deposited, or in the case of alloys, with the main component of the alloy.
  • a suitable wetting or dispersing agent in an amount ranging from about 0.01% to about 0.5% by weight of the bath.
  • suitable classes and types of wetting agents include: P18 of Langbein-Pfanhauser, AG 4 of Harshaw Chemicals Ltd., Manoxol of Hardmann & Holden Ltd., Empicol of Marchon Products Ltd.
  • wetting agents are typically sulfates of normal primary aliphatic alcohols containing from 8 to 18 carbon atoms, such as Empicol, or sodium salts of 2- ethylhexylsulfate or 2-ethylhexylsulfonate, or they are sodium salts of dioctyl sulfosuccinic acid, such as Manoxol.
  • the wetting agent is added to the electrolyte continuously during the deposition.
  • the refractory material in the form of a powder is also added to the electrolyte, whereby the refractory material remains uniformly distributed throughout the electrolyte in consequence of movement of the electrolyte.
  • Pore formation in the workpiece is best prevented by mechancal means, such as, for example, by suspending the carrier material in an electromagnetic vibrator, which is set in vibration during the deposition of the metal.
  • mechancal means such as, for example, by suspending the carrier material in an electromagnetic vibrator, which is set in vibration during the deposition of the metal.
  • Another means consists in subjecting the workpiece periodically to a blow during the deposition of the metal, for example, by means of an electromagnet.
  • the workpiece after the electrolytic deposition, is compacted by extrusion, o1 forging, or explosive molding.
  • Typical electrolyte compositions which may be employed in the practice of the invention are as follows:
  • H3BO3 per 1 H20 300 g. PbCO 60 g. HBF g. H BO per 1 H 0 (0) 0.05 mol C080,; 0.15 mol ammonium tungstate; 0.2 mol Na 'C H 0.1 mol (NH SO and 2.5 mol NH per 1 H O.
  • Example I As the electrolyte there was employed a conventional nickel deposition bath having the following composition:
  • Pore formation by gas bubbles in the workpiece was prevented by mechanical means, namely, by electromagnetically vibrating the carrier material during deposition.
  • the anode was a massive nickel anode, well known in the plating art, or alternatively, small nickel pieces contained in titanium jackets.
  • the carrier upon which deposition of the nickel took place was a formed wire of nickel, having a small cross section, so that its volume in relation to the total deposited volume would be small and would not influence the properties of the finished workpiece. Wire of 1 mm. diameter was used.
  • the nickel was deposited to a diameter of 50 mm.
  • the volume of the carrier wire is V2500 that of the finished workpiece.
  • the electrolysis was performed at a temperature of 40 C., voltage of 1-3, and current density of 0.06 a./cm.
  • the product was compressed in an extrusion press.
  • the compacted workpiece was malleable and rollable and suitable for further processing.
  • the workpieces produced in accordance with the novel method of the invention can be used in a wide variety of applications by reason of the wide range of properties which can be imparted to them according to their composition.
  • the workpiece prepared from nickel and aluminum oxide, as illustrated in Example I above exhibits a high degree of heat resistance and at the same time an enhanced resistance to wear and abrasion, so that it is particularly well suited for turbine blades, parts of combustion chambers and jet engines.
  • a workpiece made from silver with refractory components is very useful for electrical contacts.
  • the metal component is a metal selected from the group consisting of nickel, cobalt, columbium, vanadium, silver and lead, and alloys thereof.
  • the refractory material is selected from the group consisting of the oxide, carbide, nitride, and boride of aluminum, thorium, cadmium, titanium and zirconium, and mixtures thereof.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

A PROCESS FOR THE PRODUCTION OF COMPACT, MALLEABLE AND ROLLABLE METAL WORKPIECES FROM DISPERSION-HARDENED STARTING MATERIALS. COMPACT, MALLEABLE AND ROLLABLE WORKPIECES ARE PREPARED BY THE ELECTRODEPOSITION OF A METAL COMPONENT ONTO A METAL CARRIER SUCH AS A WIRE OR SHEET, THE DIMENSIONS OF THE CARRIER BEING SMALL IN RELATION TO THE VOLUME OF DEPOSITED METAL, THERE BEING ADDED TO THE DEPOSITION BATH A REFRACTORY MATERIAL AND A WETTING AGENT.

Description

tates 8 Claims ABSTRACT OF THE DISCLOSURE A process for the production of compact, malleable and rollable metal workpieces from dispersion-hardened starting materials. Compact, malleable and rollable workpieces are prepared by the electrodeposition of a metal component onto a metal carrier such as a wire or sheet, the dimensions of the carrier being small in relation to the volume of deposited metal, there being added to the deposition bath a refractory material and a wetting agent.
BACKGROUND OF THE INVENTION In known processes for the manufacture of compact, malleable and rollable metal workpieces from dispersionhardened materials in accordance with the techniques of powder metallurgy, there is the drawback that, despite subsequent heat treatment, the dispersed material frequently deposits at the grain boundaries of the former metal powder particles, whereas the main disadvantage of Working materials produced by internal oxidation or reduction lies in the frequent microscopic and macroscopic nonuniformity of subdivision of the dispersed material. This has as a consequence that the desired dispersion hardening effect is insufiiciently attained. It is an object of the invention to avoid the disadvantage of these known methods.
SUMMARY OF THE INVENTION In accordance with the present invention, workpieces which are compact, malleable and rollable are produced electrolytically from dispersion-hardened materials, by depositing a metallic component, such as a pure metal or an alloy, from an electrolyte, upon a suitable carrier, such as a sheet or wire, While simultaneously introducing a refractory component; advantageously, a suitable wetting or dispersing agent is also added to the electrolyte.
The metallic component may be any desired metal or alloy. Examples of metal which may be used to advantage in the practice of the invention include nickel, co-
balt, columbium, vanadium, silver, and lead, while examples of suitable alloys include alloys of nickel and cobalt, containing from 10% to 50%- cobalt, or alloys of nickel and molybdenum containing from to 25% molybdenum, as well as also alloys of cobalt with nickel and tungsten, alloys of nickel with cobalt, molybdenum, tungsten and chromium, and alloys of columbium with titanium, molybdenum, tungsten and zirconium.
Refractory materials which may be employed in accordance with the invention include the oxides, carbides, nitrides, and borides of metals such as aluminum, thorium, cadmium, titanium and zirconium, or mixtures thereof. Examples include A1 0 ThO TiB and ZrC. The proportion of such refractory material to the metal component is from about 0.5% to about by weight.
As a carrier material upon which the metal component is deposited, there may be employed metal wire, sheet,
or shapes, having such small dimensions, e.g., cross section and thickness, that the carrier volume is small relative to the deposited volume of the metal component, e.g., 22% by volume. The carrier material is preferably identical with the metal to be deposited, or in the case of alloys, with the main component of the alloy.
Advantageously, there may be added to the electrolyte a suitable wetting or dispersing agent, in an amount ranging from about 0.01% to about 0.5% by weight of the bath. Examples of suitable classes and types of wetting agents include: P18 of Langbein-Pfanhauser, AG 4 of Harshaw Chemicals Ltd., Manoxol of Hardmann & Holden Ltd., Empicol of Marchon Products Ltd.
These wetting agents are typically sulfates of normal primary aliphatic alcohols containing from 8 to 18 carbon atoms, such as Empicol, or sodium salts of 2- ethylhexylsulfate or 2-ethylhexylsulfonate, or they are sodium salts of dioctyl sulfosuccinic acid, such as Manoxol. Preferably the wetting agent is added to the electrolyte continuously during the deposition.
Furthermore, the refractory material in the form of a powder is also added to the electrolyte, whereby the refractory material remains uniformly distributed throughout the electrolyte in consequence of movement of the electrolyte. Pore formation in the workpiece is best prevented by mechancal means, such as, for example, by suspending the carrier material in an electromagnetic vibrator, which is set in vibration during the deposition of the metal. Another means consists in subjecting the workpiece periodically to a blow during the deposition of the metal, for example, by means of an electromagnet.
To achieve the desired properties, the workpiece, after the electrolytic deposition, is compacted by extrusion, o1 forging, or explosive molding.
Typical electrolyte compositions which may be employed in the practice of the invention are as follows:
(a) 256 g. NiSO .7H O; 45 g. NiCl .6H O; 30 g.
H3BO3 per 1 H20 (b) 300 g. PbCO 60 g. HBF g. H BO per 1 H 0 (0) 0.05 mol C080,; 0.15 mol ammonium tungstate; 0.2 mol Na 'C H 0.1 mol (NH SO and 2.5 mol NH per 1 H O.
The advantage of the novel method of the invention compared to previously known methods is especially evident in the very even distribution of the dispersed materials in the individual grains of the product.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The following example illustrates the practice of the invention, but is not to be regarded as limiting:
Example I As the electrolyte there was employed a conventional nickel deposition bath having the following composition:
256 g. NiSO .7H O; 45 g. NiCl .6H O; g. H BO per 1 H O To this bath there was continuously added as a wetting agent the compound P18 of Langbein-Pfanhauser, in an amount constituting about 0.04% by weight of the bath. As the refractory material there was introduced into the bath aluminum oxide having a particle size of less than 2 ,um, in a concentration of 80 g./l. of electrolyte, taking care that the aluminum oxide was uniformly distributed in the bath during the electrolytic deposition of the dispersionhardened alloys, e.g., rod material having a diameter of mm. Pore formation by gas bubbles in the workpiece was prevented by mechanical means, namely, by electromagnetically vibrating the carrier material during deposition. The anode was a massive nickel anode, well known in the plating art, or alternatively, small nickel pieces contained in titanium jackets. The carrier upon which deposition of the nickel took place was a formed wire of nickel, having a small cross section, so that its volume in relation to the total deposited volume would be small and would not influence the properties of the finished workpiece. Wire of 1 mm. diameter was used. The nickel was deposited to a diameter of 50 mm. Thus, the volume of the carrier wire is V2500 that of the finished workpiece. The electrolysis was performed at a temperature of 40 C., voltage of 1-3, and current density of 0.06 a./cm.
The product was compressed in an extrusion press. The compacted workpiece was malleable and rollable and suitable for further processing.
The workpieces produced in accordance with the novel method of the invention can be used in a wide variety of applications by reason of the wide range of properties which can be imparted to them according to their composition. Thus, for example, the workpiece prepared from nickel and aluminum oxide, as illustrated in Example I above, exhibits a high degree of heat resistance and at the same time an enhanced resistance to wear and abrasion, so that it is particularly well suited for turbine blades, parts of combustion chambers and jet engines. A workpiece made from silver with refractory components is very useful for electrical contacts.
It will be understood that the above description of the present invention is susceptible to various modifications, changes and adaptations, and the same are intended to be comprehended within the meaning and range of equivalents of the appended claims.
We claim:
1. Process for the manufacture of compact, malleable and rollable dispersion-hardened workpieces, comprising the steps of:
(a) introducing into an electrolytic deposition bath a carrier having a volume which is at most V3500 of the volume of the finished workpiece; and
(b) electrodepositing a metal component onto said carrier by passing a current through said deposition bath 4 in the presence of a refractory material uniformly distributed in said deposition bath during the depositing operation, until said volume of finished workpiece is attained.
2. The process of claim 1 in which a wetting agent is continuously introduced into the deposition bath during the depositing step.
3. The method of claim 1 in which the metal component is a metal selected from the group consisting of nickel, cobalt, columbium, vanadium, silver and lead, and alloys thereof.
4. The process of claim 1 in which the refractory material is selected from the group consisting of the oxide, carbide, nitride, and boride of aluminum, thorium, cadmium, titanium and zirconium, and mixtures thereof.
5. The process of claim 1 in which pore formation by gas bubbles in the workpiece is prevented by mechanical means during the step of electrodepositing.
6. The process of claim 1 in which the workpiece is further subjected to mechanical deformation for compacting the same.
7. The process of claim 1 in which the carrier is of the same metal as said component.
8. The process of claim 1 in which said component is an alloy and said carrier is of the main component of said alloy.
References Cited UNITED STATES PATENTS 2,576,922 12/1951 Camin et a1. 2,191,472 2/1940 Hopkins et a1. 29-528 3,057,048 10/1962 Hirakis. 3,066,407 12/1962 Toensing 29-528 JOHN F. CAMPBELL, Primary Examiner D. C. REILEY, Assistant Examiner US. Cl. X.R. 204l6
US660183A 1966-10-12 1967-08-14 Method of manufacturing dispersion-hardened workpieces Expired - Lifetime US3552000A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19661533441 DE1533441B1 (en) 1966-10-12 1966-10-12 Process for the production of compact, forgeable and rollable dispersion hardened metallic workpieces
DEB0089312 1966-10-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995022642A1 (en) * 1994-02-16 1995-08-24 Hans Warlimont Process for producing a hardened lead battery electrode

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1265470A (en) * 1986-07-25 1990-02-06 Falconbridge Limited Manufacture of self supporting members of copper containing phosphorus
FR2617510B1 (en) * 1987-07-01 1991-06-07 Snecma METHOD FOR THE ELECTROLYTIC CODEPOSITION OF A NICKEL-COBALT MATRIX AND CERAMIC PARTICLES AND COATING OBTAINED

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995022642A1 (en) * 1994-02-16 1995-08-24 Hans Warlimont Process for producing a hardened lead battery electrode
US5672181A (en) * 1994-02-16 1997-09-30 Hans Warlimont Method for manufacturing a hardened lead storage battery electrode
AU685581B2 (en) * 1994-02-16 1998-01-22 Hans Warlimont Process for producing a hardened lead battery electrode

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