US3765930A - Method for coating the surface of a thin wire with a layer of another metal - Google Patents

Method for coating the surface of a thin wire with a layer of another metal Download PDF

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Publication number
US3765930A
US3765930A US00160096A US3765930DA US3765930A US 3765930 A US3765930 A US 3765930A US 00160096 A US00160096 A US 00160096A US 3765930D A US3765930D A US 3765930DA US 3765930 A US3765930 A US 3765930A
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United States
Prior art keywords
wire
capillary
molten metal
walls
coated
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Expired - Lifetime
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US00160096A
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English (en)
Inventor
T Miyano
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Toshiba Corp
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Tokyo Shibaura Electric Co Ltd
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    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/38—Wires; Tubes
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/003—Apparatus
    • C23C2/0036—Crucibles
    • C23C2/00361—Crucibles characterised by structures including means for immersing or extracting the substrate through confining wall area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J19/00—Details of vacuum tubes of the types covered by group H01J21/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2893/00—Discharge tubes and lamps
    • H01J2893/0001—Electrodes and electrode systems suitable for discharge tubes or lamps
    • H01J2893/0012—Constructional arrangements
    • H01J2893/0019—Chemical composition and manufacture
    • H01J2893/0022—Manufacture

Definitions

  • the dumet wire is so far manufactured according to the following method: the surface of a wire of a ferronickel alloy is covered with a brass ribbon and the thus prepared composite piece is compactly inserted into a copper tube. The thus prepared composite article is cold-drawn in one direction and the drawn piece is then hot-drawn in the reverse direction. In this method, however, if the temperature is in excess of 900C when the composite article is preheated prior to the hot drawing, the brass part of the article may melt in places. When the hot drawing is carried out in this condition, the brass is fixed to the core wire at those places, which create greater resistance to the drawing and the smooth and uniform elongation is impaired at those places, and thus damage of the copper layer often results.
  • a wire of a ferro-nickel alloy is tightly inserted into a copper tube directly without a brass ribbon being used, and the composite article is cold-drawn until the cross sectional contraction reaches 12 to 16 percent.
  • the thus colddrawn article is then hot-drawn at a temperature of 850900C in a neutral or reducing atmosphere unitl the same contraction is reached.
  • the drawn composite wire is cooled once, and it is subjected to another cycle of cold drawing and hot drawing. Finally the wire is again subjected to the same cycle in the reverse direction. In this process there is no fear of damage of the copper layer. But this process is disadvantageous in that the steps are extremely complicated and the surface of the coated wire may be stained with lubricating oil, etc.
  • An object of this invention is to manufacture a thin wire coated with a layer of another metal, such as the dumet wire or grid wire, which is in no respect inferior to the prior art product, by a very simple process.
  • Another object of this invention is to manufacture a thin wire coated with a layer of another metal which has a finer and smoother surface.
  • FIG. 1 is a partly perspective longitudinal sectional view of an apparatus used for the present invention, wherein a small capillary device holding therein a small molten metal pool above the level of the molten metal bath, through which a thin wire is passed, is shown;
  • FIGS. 2 to 5 exemplarily show varied forms of the above-mentioned small capillary device in perspective view
  • FIG. 6 shows another embodiment of this invention, wherein the wire is vertically passed through the molten metal.
  • the strength of said capillary attraction varies depending upon the correlation between species and temperature of molten metal, material of the capillary device and dimensions thereof. It has been discovered: The height of a capillary column is the greatest, when a capillary device made of metallic molybdenum is dipped into molten gold, and said height can be as high as 50 mm when the distance of a capillary gap or the diameter of a capillary tube is 2 mm. The second greatest height is attained when tungsten is used for the device. Other metals having high melting point can be successfully used. It is needless to say that these metals must not alloy with molten metals. when in contact therewith.
  • the above-mentioned capillary phenomenon takes place when the temperature of the bath is higher than about 1 C for copper and higher than about l080C for gold.
  • the shape of the capillary device can be widely varied. Initially the inventor used a capillary device of groove type as shown in FIG. 1 as member 6. The distance between the two walls composing a capillary space is 2 mm at the greatest, and molten metal comes up in the gap so as to provide a molten metal pool 9 when the bottom of the device is put under the surface of the molten metal.
  • FIG. 2 shows a device in which the middle part of the walls are-bulged so that a larger amount of molten metal can be held therein.
  • This device is suitably used with the bottom of the device upside and the open end immersed in the bath.
  • the distance between the walls is 2 mm at the greatest and the diameter of the bulged part is 5 mm at the greatest.
  • FIG. 3 shows a device the walls of which are not in parallel but are wider apart toward the open end. This device is used with the bottom upside. The distance be tween the walls is a maximum of 2 mm at the closed off end and a maximum of 5 mm at the lower open end.
  • FIG. 4 shows a device which is substantially of the same structure as the device in FIG. 1, except that the walls and bottom are far thicker. This device is used with the bottom sideward. There is no specific meaning in that the walls are made thick, but this merely teaches that such design is possible.
  • FIG. represents a tube device.
  • a simple capillary tube the inner diameter thereof being up to 2 mm does not provide a space for the molten metal pool sufficient enough for coating, and so the middle of the capillary tube is bulged up to 5 mm in diameter.
  • holes 8 through which a thin wire to be coated runs are provided in the side walls.
  • a wire is horizontally passed through the holes of a capillary device, the one end of which is immersed in a molten metal bath, the surface of the wire is uniformly coated with the molten metal, since the wire runs through the molten metal pool.
  • the wire can be passed through the capillary gap between the walls in parallel therewith.
  • a mere pair of metal plates arranged in parallel with a distance up to 2 mm which are substantially vertically placed so that the lower ends thereof are immersed in a molten metal bath also function as a capillary device, though not shown in the drawing.
  • the device represented by FIG. 5 is limited in the space for the molten metal pool, and so processing of a thicker wire becomes difficult. If this type of device is to be used for processing of such thicker wire, the bulge of the middle portion thereof should be considerably great. However, this makes raise of the molten metal difficult because of decrease in capillary attraction. This difficulty can be overcome by connecting the upper end of the device to a vacuum system and thus maintaining the head-space of the molten metal pool in a reduced pressure, resulting in that said reduced pressure helps the drawing up of the molten metal.
  • the wire runs horizontally.
  • the wire can be passed in a substantially vertical direction, if it is convenient or desirable. This can be performed by using a little complicated apparatus as shown in FIG. 6, comprising a special capillary device 6 and a special vessel for molten metal 4.
  • the vessel 4 is furnished with a cylindrical passage 14 for the wire protruded from the bottom thereof, through which the wire runs without contacting the molten metal in the vessel.
  • the capillary device 6 is of a structure like a double-walled cap, which is provided with holes 8 at the center of the head part for the running wire, and is placed over the protruded cylindrical passage 14 of the vessel so that the holes and the passage align, and the open lower edges of the cap are immersed in the molten metal.
  • the distance between the double walls is 2 mm at the greatest. Then the space between the walls or the jacket 9 is filled with the molten metal by capillary attraction. Therefore, if a wire 10 is passed through the passage 14 and the holes 8 and 8, the wire is coated with the metal.
  • the coating metal copper and gold are most frequently used, but silver, silver solder, aluminum, etc. can be also used.
  • wires of molybdenum, tungsten, fcrro-nickel alloys, ironnickel-cobalt alloys, etc. are applicable to this invention.
  • EXAMPLE I A grid wire covered by a layer of gold was manufactured using an apparatus the outline of which is shown in FIG. 1.
  • a vessel 4 of high purity zirconia containing a molten gold bath 5 was placed in a tubular furnace 3 equipped with an electric heating element 2 imbedded in the furnace wall I.
  • a groove type capillary device 6 was placed in the molten gold bath so that the bottom thereof was immersed in the bath.
  • the capillary device was fixed at a predetermined position by a means which is not shown in the drawing.
  • the distance of the two parallel walls 7 of the capillary device was 2 mm, and the height of the walls was about 20 mm.
  • the walls were provided with a hole 8 respectively at the position suitable for passing a wire to be coated. Thus the melted gold was raised in the capillary gap to a height above the position of the holes.
  • a reducing atmosphere was establishd in the furnace 3 by passing hydrogen gas therethrough, and a molybdenum wire 20 p. in diameter was passed through the holes 8 at the speed of 12 m/min.
  • a thin grid wire coated with a p. layer of gold was obtained.
  • the conventional gold-coated grid wire is prepared by the electroplating method.
  • the grid wire prepared in accordance with this invention is quite free from inclusion of impurities such as cyanates and oxides, and has no pin holes which are incidental to the electroplating.
  • the grid wire prepared in accordance with this invention remarkably improves the characteristics of an electron tube when it is used as a control means of a secondary emission of a grid of any kind.
  • the molten metal bath has to be replenished with the metal by a suitable means as the coating operation is continued and the molten metal is consumed.
  • EXAMPLE 2 Using an apparatus similar to that of Example 1, a dumet wire was continuously manufactured. A core wire of a ferro-nickel (Fe 58 Ni 42 0.45 mm in diameter was used, and a capillary device represented by FIG. 2 was employed. The capillary gap distance thereof was 2 mm, and the inner diameter of the bulged part is 5 mm. This device was partly immersed in a melted copper bath of ll30C in the same way as shown in FIG. 1, and a core wire at a room temperature was continuously passed through the holes in the walls at the speed of 15 m/min.
  • a ferro-nickel Fe 58 Ni 42 0.45 mm in diameter was used, and a capillary device represented by FIG. 2 was employed. The capillary gap distance thereof was 2 mm, and the inner diameter of the bulged part is 5 mm.
  • This device was partly immersed in a melted copper bath of ll30C in the same way as shown in FIG. 1, and a core wire at a room
  • dumet wire had a coating p in thickness, and the surface was very homogeneous and pure, free from stain which is incidental to a product of the drawing method in which a lubricating oil is used.
  • the cross section showed that there was no offset in adhesion of the coating layer.
  • a method for coating a thin high melting refractory metal wire selected from the group consisting of molybdenum, tungsten, iron-nickel, and iron-nickelcobalt, with a coating metal selected from the group consisting of gold, copper, silver, silver solder and aluminum comprising imersing a small capillary decice into a molten bath of said coating metal, said molten bath and said capillary device being within a furnace, said capillary device providing a capillary space containing a pool of said molten coating metal and positioned above the level of said molten bath, and continuously passing said thin wire which is at room temperature at a constant speed into said furnace and through said pool of molten coating metal while maintaining a reducing atmosphere in said furnace whereby a thin smooth clean coating of said coating metal is applied on said wire.
  • the small capillary device comprises a pair of walls facing each other and a bottom connecting ends of the two walls.
  • the molten metal is contained in a vessel which has a cylindrical passage for the wire vertically protruded from the bottom of the vessel through which the wire runs without contacting the molten metal in the vessel and the capillary device is a double-walled cap put on said cylindrical passage, the open lower edges of which are immersed in the molten metal so that the molten metal fills the gap formed by the double walls by virtue of a capillary attraction, and the double walls have holes which are provided in a top position of the cap corresponding to that of the protruded cylindrical passage so that the wire runs through the passage and the holes.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
US00160096A 1970-07-10 1971-07-06 Method for coating the surface of a thin wire with a layer of another metal Expired - Lifetime US3765930A (en)

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JP45059850A JPS4941021B1 (xx) 1970-07-10 1970-07-10

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JP (1) JPS4941021B1 (xx)
DE (1) DE2134444B2 (xx)
NL (1) NL7109427A (xx)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018942A (en) * 1973-11-02 1977-04-19 Siemens Aktiengesellschaft Method for the manufacture of a superconductor with a layer of the A-15 phase of the system Nb-Al or Nb-Al-Ge
US4076510A (en) * 1976-12-23 1978-02-28 Western Electric Co., Inc. Methods and apparatus for coating a filament
CN100371111C (zh) * 2006-01-17 2008-02-27 浙江大学 利用毛细管制备微细金属丝的方法
CN108672516A (zh) * 2018-03-25 2018-10-19 江阴六环合金线有限公司 一种套铜管气烧的氧化杜镁丝的生产方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3663038D1 (en) * 1985-03-04 1989-06-01 Battelle Memorial Institute Method for selectively forming at least a coating strip of a metal or alloy on a substrate of another metal
CH668083A5 (fr) * 1986-09-10 1988-11-30 Battelle Memorial Institute Procede pour former selectivement au moins une bande de revetement d'un metal ou alliage sur un substrat d'un autre metal et support de connexion de circuit integre realise par ce procede.
DE19707089C2 (de) * 1997-02-24 2003-04-10 Alcatel Sa Verfahren und Vorrichtung zur kontinuierlichen Herstellung legierter metallischer Drähte

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1033912A (en) * 1905-07-07 1912-07-30 Belden Mfg Co Insulating device.
US1076526A (en) * 1911-08-24 1913-10-21 William E Milbank Wire coating and spooling machine.
US1454224A (en) * 1923-01-29 1923-05-08 Firm Meirowsky & Co Method and means for applying a liquid to wires, threads, and the like
US2255436A (en) * 1939-09-19 1941-09-09 Anaconda Wire & Cable Co Coating apparatus and method of operation
US2325129A (en) * 1941-11-01 1943-07-27 Du Pont Yarn finishing
US2914419A (en) * 1953-08-03 1959-11-24 Armco Steel Corp Method and apparatus for continuously coating a metal strand-like article with molten metal
US2934458A (en) * 1953-05-21 1960-04-26 Goodrich Co B F Method for coating filaments of glass
US2937108A (en) * 1955-10-21 1960-05-17 British Iron Steel Research Method of tinning steel strip
US3196830A (en) * 1959-07-06 1965-07-27 Sprague Electric Co Capillary applicator for semiconductor alloying apparatus
GB1192213A (en) * 1966-07-14 1970-05-20 Ericsson Telefon Ab L M Continuous Coating of a Long Metal Article.

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1033912A (en) * 1905-07-07 1912-07-30 Belden Mfg Co Insulating device.
US1076526A (en) * 1911-08-24 1913-10-21 William E Milbank Wire coating and spooling machine.
US1454224A (en) * 1923-01-29 1923-05-08 Firm Meirowsky & Co Method and means for applying a liquid to wires, threads, and the like
US2255436A (en) * 1939-09-19 1941-09-09 Anaconda Wire & Cable Co Coating apparatus and method of operation
US2325129A (en) * 1941-11-01 1943-07-27 Du Pont Yarn finishing
US2934458A (en) * 1953-05-21 1960-04-26 Goodrich Co B F Method for coating filaments of glass
US2914419A (en) * 1953-08-03 1959-11-24 Armco Steel Corp Method and apparatus for continuously coating a metal strand-like article with molten metal
US2937108A (en) * 1955-10-21 1960-05-17 British Iron Steel Research Method of tinning steel strip
US3196830A (en) * 1959-07-06 1965-07-27 Sprague Electric Co Capillary applicator for semiconductor alloying apparatus
GB1192213A (en) * 1966-07-14 1970-05-20 Ericsson Telefon Ab L M Continuous Coating of a Long Metal Article.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018942A (en) * 1973-11-02 1977-04-19 Siemens Aktiengesellschaft Method for the manufacture of a superconductor with a layer of the A-15 phase of the system Nb-Al or Nb-Al-Ge
US4076510A (en) * 1976-12-23 1978-02-28 Western Electric Co., Inc. Methods and apparatus for coating a filament
CN100371111C (zh) * 2006-01-17 2008-02-27 浙江大学 利用毛细管制备微细金属丝的方法
CN108672516A (zh) * 2018-03-25 2018-10-19 江阴六环合金线有限公司 一种套铜管气烧的氧化杜镁丝的生产方法

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Publication number Publication date
DE2134444A1 (de) 1972-01-20
DE2134444B2 (de) 1976-09-16
JPS4941021B1 (xx) 1974-11-06
NL7109427A (xx) 1972-01-12

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