US3799847A - Method for electrolytically producing a metal band - Google Patents

Method for electrolytically producing a metal band Download PDF

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US3799847A
US3799847A US00251737A US25173772A US3799847A US 3799847 A US3799847 A US 3799847A US 00251737 A US00251737 A US 00251737A US 25173772 A US25173772 A US 25173772A US 3799847 A US3799847 A US 3799847A
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current density
range
anode plates
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A Bobrov
E Bobrova
I Bobrova
V Trofimov
V Bobrov
A Migina
T Perelygina
A Buzhinskaya
L Sergeev
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/04Wires; Strips; Foils

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  • the current density is maintained within a range from 4,000 to 50,000 a./sq. rn. for a period from 1 second to 200 seconds, the electrolytic solution being positively agitated during all said stages except the last one.
  • the apparatus comprises at least three anode plates arranged about the periphery of the cathode drum and raidially spaced therefrom within the bath containing the electrolytic solution, the anode plates being connected to the individual power supply sources.
  • the two anode plates which are the last ones in the direction of the progress of the metal band, have the ratio of the respective surface areas thereof within a range from 1511 to 5:1.
  • the interelectrode space pertaining to the last one of these anode plates, is separated by a partition from the rest of the internal space of the bath.
  • the invention relates to methods of production of metal bands and to apparatus for accomplishment of such methods, which are used in non-ferrous metallurgy, in the electronics industry and in electrical engineering for the manufacture of thin metal bands.
  • the metal band produced by the above known method and apparatus has a smooth side contacting the cathode and the opposite side which is mat, the surface of this opposite side being unsufiiciently developed.
  • the invention resides in a method of producing a metal band by depositing the metal electrolytically from an electrolytic solution on the surface of a cathode with the current density being above 1,000 amperes per square metre and with said electrolytic solution being positively agitated, in which method, in accordance with the invention, said process of electrolytic deposition is performed with a single cathode, with the current density being successively varied in a plurality of stages, said current density being maintained during the first ones of said plurality of stages within a range from 1,000 amperes per square metre to 5,000 amperes per square meter, said current density being maintained during the stage preceding the final one of said stages Within a range from 5,000 to 10,000 amperes per square metre for a period from 1 second to 300 seconds, said current density being maintained during said final stage within a range from 4,000 to 50,000 amperes per square metre for a period from 1 second to 200 seconds, said electrolytic solution being positively agitated during all said stages except said final one
  • an apparatus comprising a bath containing the electrolytic solution, said bath incorporating barbotage means for agitating said electrolytic solution, and a cathode drum mounted interiorly of said bath, at least three anode plates being mounted interiorly of said bath about the periphery of said cathode drum, in which apparatus, in accordance with the present invention, said anode plates are electrically connected to their respective individual power supply sources, the two of said anode plates, which are the last ones in the direct of the progress of said metal band, having the ratio of the respective surface areas thereof within a range from 15:1 to 5:1 the inter-electrode space within said band, pertaining to said anode plate which is the last one in the direction of the progress of said metal band, being separated from the rest of the internal space of said bath by a partition means.
  • FIG. 1 is a cross-sectional schematic view of an apparatus embodying the invention
  • FIG. 2 is a sectional view taken along line IIII of FIG. 1.
  • the apparatus comprises a metal housing 1 (FIG 1) consisting of two all-welded titanium semi-cylinders, the housing also acting as an electrolytic bath. Positioned interiorly of this bath is a cathode drum 2. Positioned about the periphery of the cathode drum 2 and radially spaced therefrom are anode plates 3, 4, 5 and 6. The anode plate 3, which is the first one in the direction of the progress of the band 7, is secured on the first one of the two semi-cylinders making up the housing 1, while the anode plates 4, and 6 are secured in succession on the other one of the two semi-cylinders.
  • the anode plates 3 and 4 are connected to a common source of power supply, and the anode plates 5 and 6 are connected, respectively, to their individual-diflierent sources of power supply, whereby the two last-mentioned anodes are mounted on the housing 1 with the insulating members 8 and 9, respectively, interposed therebetween.
  • the apparatus is provided with barbotage means 10 for agitating the electrolyte in the bath with the help of air streams.
  • Manifolds 11 are disposed in the bottom portion of the housing 1 for introduction of the electrolyte into the housing, while overflow pockets 12 are provided in the upper portion of the housing 1, through which the electrolyte leaves the bath.
  • the air and the anode gases are withdrawn from the internal space of the housing 1 through exhaust ventilation pipes 13.
  • the cathode drum 2 is journalled for rotation in bearings 14 (FIG. 2) and is imparted rotation by an appropriate drive mechanism (not shown in the appended drawings). To prevent deposition of copper on the end faces of the cathode drum 2, these end faces are protected with rings 15 made from an acid-resistant dielectric material. The rings are secured in spring-biased end covers 16. Annular diaphragms 17 are interposed between the end covers 16 and the respective ends of the housing 1.
  • the left-hand and the right-hand semi-cylinders of the housing 1 can be easily swung aside from the cathode drum 2, the semicylinders in this case being pivoted about a pivot axis 18 with the help of the respective actuators 19.
  • the herein disclosed apparatus is supplied with electric power from three different current sources, the respective negative poles of the three sources being jointly connected electrically to the cathode drum 2 through brush contacts 20, whereas the positive poles of the three current sources are individually connected with the re spective ones of the anode plates.
  • the first current supply source supplies current to the anodes 3 and 4
  • the second current supply source supplies current to the anode plate 5
  • the third current supply source supplies current to the anode plate 6.
  • each successive anode plate has the surface area which is smaller than that of the preceding anode plate.
  • the anode plates 3 and 4 are intended for formation of the metal band, as such; the anode plate 5 is intended to ensure sufiicient roughness of the surface of this metal band, while the anode plate 6the last in the successionis intended to ensure formation of an adhesion layer with a highly developed surface on the rough side of the band.
  • the surface areas of the respective anode plates is determined by the time needed for each one of the abovementioned processes. For example, when a micron thick metal band is produced, the ratio of the surface areas of the two anode plates 5 and 6, which are the last ones in the direction of the progress of the band, equals (15 to 5):l.
  • the inter-electrode space pertaining to the anode plate 6 which is the last one in the direction of the progress of the metal band 7 is separated from the rest of the internal space of the bath by an elastic partition 21 slidingly engaging the periphery of the cathode drum 2, the partition being made from a resilient dielectric materia
  • the herein disclosed apparatus operates, as follows.
  • the electrolyte is introduced into the bath through the inlet manifold 11. Air is supplied through the barbotage means10 to agitate the electrolyte, and the power supply to the anode plates 3, 4 and 5 is switched on, with the cathode drum 2 kept immovable. Anappropriate time is given under these conditions for a layer of met l t be deposited on the cathode drum 2. Then the drive imparting rotation to the cathode drum 2 is engaged. As the cathode drum 2 thus set into rotation, the metal deposit in the form of a band advancing from the electrolyte is separated from the surface of the cathode drum 2 and is threaded over a guiding roller 22. Thereafter the power supply to the anode plate 6 is switched on, to apply an adhesion layer on the metal cathode deposit being formed.
  • the metal deposit is primarily formed on the cathode drum 2 adjacent to the anode plates 3 and 4, the current density being from 1,000 a./sq. m. to 5,000 a./sq. m.; then, as the cathode drum with the metal deposit thereon passes adjacent to the anode plate 5, the respective current density in this area is maintained within a range from 5,000 a./sq. m. to 10,000 a./sq. m. (i.e. the density here approaches the critical value), and thus within a period from 1 second to 300 seconds the exposed surface of the metal deposit acquires the necessary roughness.
  • the metal deposit enters the zone adjacent to the anode plate 6, separated from the rest of the internal space of the bath by the partition 21.
  • the current density is maintained within a range from 4,000 a./sq. m. to 50,000 a./sq. m. (i.e. above the critical value), and thus Within a period from 1 second to 200 seconds there is deposited an adhesion layer which is an electrolytic deposit with a highly developed surface.
  • This final stage of the processing of the surface of the metal deposit takes place in the zone where the electrolyte is relatively calm, i.e. where the electrolyte is practically not agitated.
  • the electrolyte is continuously recirculated.
  • the interelectrode space pertaining to the anode plate 6 communicates with the general volume of the electrolyte through the overflow outlet pocket 12 and also through the gaps (not shown) left between the ends of the partition 21 and the respective ones of the two end covers 16.
  • the above described method can be employed for production of a metal band within a wide range of thicknesses, for example, from 10 microns to 110 microns.
  • the required thickness of the metal band being produced is obtained by selecting the appropriate speed of the rotation of the cathode drum 2.
  • EXAMPLE 35 micron thick metal band is produced, as follows. Copper band is deposited onto the titanium cathode drum from sulfuric acidbased electrolyte containing 250 to 275 grams per litre of blue vitriol (sulfuric copper) and 70 to grams per litre of free sulfuric acid, at a temperature of 35 C., and air agitation, the current density being 2,500 a./sq. m. (the anode may be either a soluble one, or a non-soluble one).
  • the duration of the first stage i.e. of the deposition stage, is 6 minutes 27 seconds.
  • the second stage is commenced.
  • the above conditions of the electrolysis are maintained the same, but the current density is increased to 5,000 a./sq. m., i.e. to the value approach in the critical one.
  • the third stage of the process the electrolyte is no longer agitated, and the current density is increased to a value above the critical one, i.e. to 7,500 a./sq. m.
  • the duration of the third stage is 1.5 seconds.
  • Materials incorporating the copper band thus obtained have displayed stability of the strength of the adhesion of the band to the dielectric layer, both over the delivery period and after having been tested for galvanic stability, thermal stability and resistance to moisture, unlike oxidized band which is apt to have the strength of the adhesion considerably afiected by such tests (see Table 1 said final stage the current density is maintained within a hereinbelow). range from 4,000 amperes per square metre to 50,000
  • Atter Delivered After exposure After in the Alter exposure to 95% exposure state galvanic to 180 C. humidity to 265 C. manuiecstability during for 48 for Sample of band-incorporating material, NED-type tm'e test 100 hours hours seconds Band obtained by the herein disclosed method, 35 micron thick 1,640 1, 600 1,475 1, 620 1, 925 Oxidized hand 1,650 1,100 100-200 Permissible value, not below 1, 500 700 800 1,000
  • Method of producing a metal band having one side thereof rough and provided on its rough side with an ad- 3,674,656 7/1972 Yates hesion layer having a highly developed surface compris- 3,293,109 12/1966 Luce et 204-52 ing the step of depositing electrolytically the metal from FO GN PATENTS an electrolytic solution onto the surface of a single cath- 18,870 5/1961 Japan 204 12 ode, with the current density being successively varied in a plurality of stages: during the first ones of said stages the current density is maintained within a range from JOHN MACK Pnmary Exammer 1,000 to 5,000 amperes per square metre, during the stage T.

Abstract

THE METHOD RESIDES IN DEPOSITING THE METAL ELECTROLYTICALLY ON THE SURFACE OF A CATHODE FROM AN ELECTROLYTIC SOLUTION, WITH THE CURRENT DENSITY BEING SUCCESSIVELY VARIED IN A PLURALITY OF STAGES: DURING THE FIRST ONES OF THESE STAGES THE CURRENT DENSITY IS MAINTAINED WITHIN A RANGE FROM 1,000 TO 5,000 A./SQ. M., DURING THE LAST STAGE BUT ONE THE CURRENT DENSITY IS MAINTAINED WITHIN A RANGE FROM 5,000 TO 10,000 A./SQ. M. FOR A PERIOD FROM 1 SECOND TO 300 SECONDS, DURING THE LAST STAGE THE CURRENT DENSITY IS MAINTAINED WITHIN A RANGE FROM 4,000 TO 50,000 A./SQ. M. FOR A PERIOD FROM 1 SECOND TO 200 SECONDS, THE ELECTROLYTIC SOLUTION BEING POSITIVELY AGITATED DURING ALL SAID STAGES EXCEPT THE LAST ONE. THE APPARATUS COMPRISES AT LEAST THREE ANODE PLATES ARRANGED ABOUT THE PERIPHERY OF THE CATHODE DRUM AND RAIDIALLY SPACED THEREFROM WITHIN THE BATH CONTAINING THE ELECTROLYTIC SOLUTION, THE ANODE PLATES BEING CONNECTED TO THE INDIVIDUAL POWER SUPPLY SOURCES. THE TWO ANODE PLATES, WHICH ARE THE LAST ONES IN THE DIRECTION OF THE PROGRESS OF THE METAL BAND, HAVE THE RATIO OF THE RESPECTIVE SURFACE AREAS THEREOF WITHIN A RANGE FROM 15:1 TO 5:1. THE INTERELECTRODE SPACE, PERTAINING TO THE LAST ONE OF THESE ANODE PLATES, IS SEPARATED BY A PARTITION FROM THE REST OF THE INTERNAL SPACE OF THE BATH.

Description

Maw}! 26, 1974 A. VLADIMIROVNA ETA!- $1 METHOD FOR EQE'JTROLYTICALLY PRODUCING A METAL BAND Filed May 9, 1972 United States Patent 3,799,847 METHOD FOR ELECTROLYTICALLY PRODUCING A METAL BAND AntoninaVladimirovna Buzhinskaya, Murmansky proezd 6, kv. 54; Leonid Alexandrovich Sergeev, prospekt Miro 34, kv. 2; Vladimir Ivanovich Trofimov, Neglinnaya ulitsa 17, kv. 29; Vyacheslav Borisovich Bobrov, Yaroslavskaya ulitsa 1/9, kv. 30; Anna Iliuichna Migina, B. Spasskaya ulitsa 36/2, kv. 5; and Tatyana Fedorovna Perelygina, Vorgtnikovsky perevlok 11, kv. 31, all of Moscow, U.S.S.R.; and Anatoly Borisovich Bobrov, deceased, late of Moscow, U.S.S.R.; by Evodika Nikolaevna Bobrova, ulitsa Arbat 51, kv. 117; and Irina Maximovna Bobrova, Konkovo-Derevlevo 1, mikroraion, korpus 4, kv. 118, both of Moscow, U.S.S.R., administrators Filed May 9, 1972, Ser. No. 251,737 Int. Cl. C23b 7/02, .7/04; B01k 3/02 U.S. Cl. 204-13 1 Claim ABSTRACT OF THE DISCLOSURE The method resides in depositing the metal electrolytically on the surface of a cathode from an electrolytic solution, with the current density being successively varied in a plurality of stages: during the first ones of these stages the current density is maintained within a range from 1,000 to 5,000 a./sq. m., during the last stage but one the current density is maintained within a range from 5,000 to 10,000 a./sq. rn. for a period from 1 second to 300 seconds, during the last stage the current density is maintained within a range from 4,000 to 50,000 a./sq. rn. for a period from 1 second to 200 seconds, the electrolytic solution being positively agitated during all said stages except the last one.
The apparatus comprises at least three anode plates arranged about the periphery of the cathode drum and raidially spaced therefrom within the bath containing the electrolytic solution, the anode plates being connected to the individual power supply sources. The two anode plates, which are the last ones in the direction of the progress of the metal band, have the ratio of the respective surface areas thereof within a range from 1511 to 5:1. The interelectrode space, pertaining to the last one of these anode plates, is separated by a partition from the rest of the internal space of the bath.
The invention relates to methods of production of metal bands and to apparatus for accomplishment of such methods, which are used in non-ferrous metallurgy, in the electronics industry and in electrical engineering for the manufacture of thin metal bands.
Widely known in the art is a method of producing a metal band by depositing the metal electrolytically from an elecrtolytic solution on the surface of the cathode, with the current density above 1,000 amperes per square metre, with the electrolytic solution being positively agitated, and an apparatus employing this method, comprising a bath containing the electrolytic solution, incorporating barbotage means for agitating this solution, this bath having mounted interiorly thereof a cathode drum and a plurality of anode plates mounted about the periphery of said drum.
The metal band produced by the above known method and apparatus has a smooth side contacting the cathode and the opposite side which is mat, the surface of this opposite side being unsufiiciently developed.
Such band cannot be used for the manufacture of dielectric articles Without additional treatment in a specially designed apparatus, since the strength of its adhesion to the dielectric layer proves to be insuflicient.
A disadvantage of the known methods and apparatus 3,799,847 Patented Mar. 26, 1974 ice for production of metal bands of the kind referred to is also the necessity of additionally re-winding the band, which results in repeated breakages of the band, whereby the yield of quality product is brought down.
It is an object of the present invention to provide a method of producing a metal band and an apparatus for accomplishment of this method, which should be capable of producing the metal band and of having one side of this band treated on a single cathode.
With this object in view, the invention resides in a method of producing a metal band by depositing the metal electrolytically from an electrolytic solution on the surface of a cathode with the current density being above 1,000 amperes per square metre and with said electrolytic solution being positively agitated, in which method, in accordance with the invention, said process of electrolytic deposition is performed with a single cathode, with the current density being successively varied in a plurality of stages, said current density being maintained during the first ones of said plurality of stages within a range from 1,000 amperes per square metre to 5,000 amperes per square meter, said current density being maintained during the stage preceding the final one of said stages Within a range from 5,000 to 10,000 amperes per square metre for a period from 1 second to 300 seconds, said current density being maintained during said final stage within a range from 4,000 to 50,000 amperes per square metre for a period from 1 second to 200 seconds, said electrolytic solution being positively agitated during all said stages except said final one. In this way it has become possible to produce a metal band having one side thereof smooth and the other side thereof rough with a highly developed surface, providing for sufiicient strength of adhesion to a dielectric layer.
For accomplishment of this method, there has been provided an apparatus comprising a bath containing the electrolytic solution, said bath incorporating barbotage means for agitating said electrolytic solution, and a cathode drum mounted interiorly of said bath, at least three anode plates being mounted interiorly of said bath about the periphery of said cathode drum, in which apparatus, in accordance with the present invention, said anode plates are electrically connected to their respective individual power supply sources, the two of said anode plates, which are the last ones in the direct of the progress of said metal band, having the ratio of the respective surface areas thereof within a range from 15:1 to 5:1 the inter-electrode space within said band, pertaining to said anode plate which is the last one in the direction of the progress of said metal band, being separated from the rest of the internal space of said bath by a partition means.
Thus it has become possible to obtain a required metal band and to have one of the sides thereof treated to a desired effect within a single apparatus on a single cathode.
Given below is a detailed description of an embodiment of the invention, with reference being had to the accompanying drawings, wherein:
FIG. 1 is a cross-sectional schematic view of an apparatus embodying the invention;
FIG. 2 is a sectional view taken along line IIII of FIG. 1.
Referring now in particular to the appended drawings, the apparatus comprises a metal housing 1 (FIG 1) consisting of two all-welded titanium semi-cylinders, the housing also acting as an electrolytic bath. Positioned interiorly of this bath is a cathode drum 2. Positioned about the periphery of the cathode drum 2 and radially spaced therefrom are anode plates 3, 4, 5 and 6. The anode plate 3, which is the first one in the direction of the progress of the band 7, is secured on the first one of the two semi-cylinders making up the housing 1, while the anode plates 4, and 6 are secured in succession on the other one of the two semi-cylinders. The anode plates 3 and 4 are connected to a common source of power supply, and the anode plates 5 and 6 are connected, respectively, to their individual-diflierent sources of power supply, whereby the two last-mentioned anodes are mounted on the housing 1 with the insulating members 8 and 9, respectively, interposed therebetween. The apparatus is provided with barbotage means 10 for agitating the electrolyte in the bath with the help of air streams. Manifolds 11 are disposed in the bottom portion of the housing 1 for introduction of the electrolyte into the housing, while overflow pockets 12 are provided in the upper portion of the housing 1, through which the electrolyte leaves the bath. The air and the anode gases are withdrawn from the internal space of the housing 1 through exhaust ventilation pipes 13. The cathode drum 2 is journalled for rotation in bearings 14 (FIG. 2) and is imparted rotation by an appropriate drive mechanism (not shown in the appended drawings). To prevent deposition of copper on the end faces of the cathode drum 2, these end faces are protected with rings 15 made from an acid-resistant dielectric material. The rings are secured in spring-biased end covers 16. Annular diaphragms 17 are interposed between the end covers 16 and the respective ends of the housing 1.
To facilitate mounting, dismantling, inspection and routine maintenance of the apparatus, the left-hand and the right-hand semi-cylinders of the housing 1 can be easily swung aside from the cathode drum 2, the semicylinders in this case being pivoted about a pivot axis 18 with the help of the respective actuators 19.
The herein disclosed apparatus is supplied with electric power from three different current sources, the respective negative poles of the three sources being jointly connected electrically to the cathode drum 2 through brush contacts 20, whereas the positive poles of the three current sources are individually connected with the re spective ones of the anode plates. As it has been mentioned hereinabove, the first current supply source supplies current to the anodes 3 and 4, the second current supply source supplies current to the anode plate 5, and the third current supply source supplies current to the anode plate 6. In the direction of the progress of the band 7 each successive anode plate has the surface area which is smaller than that of the preceding anode plate. This feature of the herein disclosed apparatus is explained, as follows: the anode plates 3 and 4 are intended for formation of the metal band, as such; the anode plate 5 is intended to ensure sufiicient roughness of the surface of this metal band, while the anode plate 6the last in the successionis intended to ensure formation of an adhesion layer with a highly developed surface on the rough side of the band. The surface areas of the respective anode plates is determined by the time needed for each one of the abovementioned processes. For example, when a micron thick metal band is produced, the ratio of the surface areas of the two anode plates 5 and 6, which are the last ones in the direction of the progress of the band, equals (15 to 5):l.
The inter-electrode space pertaining to the anode plate 6 which is the last one in the direction of the progress of the metal band 7 is separated from the rest of the internal space of the bath by an elastic partition 21 slidingly engaging the periphery of the cathode drum 2, the partition being made from a resilient dielectric materia The herein disclosed apparatus operates, as follows.
The electrolyte is introduced into the bath through the inlet manifold 11. Air is supplied through the barbotage means10 to agitate the electrolyte, and the power supply to the anode plates 3, 4 and 5 is switched on, with the cathode drum 2 kept immovable. Anappropriate time is given under these conditions for a layer of met l t be deposited on the cathode drum 2. Then the drive imparting rotation to the cathode drum 2 is engaged. As the cathode drum 2 thus set into rotation, the metal deposit in the form of a band advancing from the electrolyte is separated from the surface of the cathode drum 2 and is threaded over a guiding roller 22. Thereafter the power supply to the anode plate 6 is switched on, to apply an adhesion layer on the metal cathode deposit being formed.
The metal deposit is primarily formed on the cathode drum 2 adjacent to the anode plates 3 and 4, the current density being from 1,000 a./sq. m. to 5,000 a./sq. m.; then, as the cathode drum with the metal deposit thereon passes adjacent to the anode plate 5, the respective current density in this area is maintained within a range from 5,000 a./sq. m. to 10,000 a./sq. m. (i.e. the density here approaches the critical value), and thus within a period from 1 second to 300 seconds the exposed surface of the metal deposit acquires the necessary roughness. As the cathode drum 2 rotates further on, the metal deposit enters the zone adjacent to the anode plate 6, separated from the rest of the internal space of the bath by the partition 21. Here, in the space between the anode plate 6 and the cathode drum 2, the current density is maintained within a range from 4,000 a./sq. m. to 50,000 a./sq. m. (i.e. above the critical value), and thus Within a period from 1 second to 200 seconds there is deposited an adhesion layer which is an electrolytic deposit with a highly developed surface. This final stage of the processing of the surface of the metal deposit takes place in the zone where the electrolyte is relatively calm, i.e. where the electrolyte is practically not agitated.
In operation of the herein disclosed apparatus the electrolyte is continuously recirculated. The interelectrode space pertaining to the anode plate 6 communicates with the general volume of the electrolyte through the overflow outlet pocket 12 and also through the gaps (not shown) left between the ends of the partition 21 and the respective ones of the two end covers 16.
The above described method can be employed for production of a metal band within a wide range of thicknesses, for example, from 10 microns to 110 microns. The required thickness of the metal band being produced is obtained by selecting the appropriate speed of the rotation of the cathode drum 2.
EXAMPLE 35 micron thick metal band is produced, as follows. Copper band is deposited onto the titanium cathode drum from sulfuric acidbased electrolyte containing 250 to 275 grams per litre of blue vitriol (sulfuric copper) and 70 to grams per litre of free sulfuric acid, at a temperature of 35 C., and air agitation, the current density being 2,500 a./sq. m. (the anode may be either a soluble one, or a non-soluble one).
The duration of the first stage, i.e. of the deposition stage, is 6 minutes 27 seconds. Then the second stage is commenced. During this stage the above conditions of the electrolysis are maintained the same, but the current density is increased to 5,000 a./sq. m., i.e. to the value approach in the critical one. During the third stage of the process the electrolyte is no longer agitated, and the current density is increased to a value above the critical one, i.e. to 7,500 a./sq. m. The duration of the third stage is 1.5 seconds.
When the above described process is completed, the band is removed from the cathode, washed and dried. The foil thus obtained is ready for manufacture of materials incorporating copper foil.
Materials incorporating the copper band thus obtained have displayed stability of the strength of the adhesion of the band to the dielectric layer, both over the delivery period and after having been tested for galvanic stability, thermal stability and resistance to moisture, unlike oxidized band which is apt to have the strength of the adhesion considerably afiected by such tests (see Table 1 said final stage the current density is maintained within a hereinbelow). range from 4,000 amperes per square metre to 50,000
TABLE 1 Adhesion strength, grams/em.
Atter Delivered After exposure After in the Alter exposure to 95% exposure state galvanic to 180 C. humidity to 265 C. manuiecstability during for 48 for Sample of band-incorporating material, NED-type tm'e test 100 hours hours seconds Band obtained by the herein disclosed method, 35 micron thick 1,640 1, 600 1,475 1, 620 1, 925 Oxidized hand 1,650 1,100 100-200 Permissible value, not below 1, 500 700 800 1,000
The herein disclosed method of producing metal band amperes per square metre; said electrolytic solution being and the apparatus employing this method make it possible positively agitated during all said stages except said final to obtain metal band of which one side can be continuone. ously processed within a single apparatus. References Cited What UNITED STATES PATENTS 1. Method of producing a metal band having one side thereof rough and provided on its rough side with an ad- 3,674,656 7/1972 Yates hesion layer having a highly developed surface, compris- 3,293,109 12/1966 Luce et 204-52 ing the step of depositing electrolytically the metal from FO GN PATENTS an electrolytic solution onto the surface of a single cath- 18,870 5/1961 Japan 204 12 ode, with the current density being successively varied in a plurality of stages: during the first ones of said stages the current density is maintained within a range from JOHN MACK Pnmary Exammer 1,000 to 5,000 amperes per square metre, during the stage T. TUFARIELLO, Assistant Examiner preceding the final stage the current density is maintained within a range from 5,000 to 10,000 amperes per square US. Cl. X.R. metre for a period from 1 second to 300 seconds; during 204-208, 231
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Cited By (12)

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US4053370A (en) * 1975-09-18 1977-10-11 Koito Manufacturing Company Limited Process for the fabrication of printed circuits
US4129492A (en) * 1975-12-23 1978-12-12 Imperial Metal Industries (Kynoch) Limited Electrolytic cell
DE3307748A1 (en) * 1982-03-05 1983-09-15 Olin Corp., 62024 East Alton, Ill. METHOD FOR TREATING A METAL FILM IN ORDER TO IMPROVE YOUR ADHESION
US4490218A (en) * 1983-11-07 1984-12-25 Olin Corporation Process and apparatus for producing surface treated metal foil
US4515671A (en) * 1983-01-24 1985-05-07 Olin Corporation Electrochemical treatment of copper for improving its bond strength
US4549940A (en) * 1984-04-23 1985-10-29 Karwan Steven J Method for surface treating copper foil
US4692221A (en) * 1986-12-22 1987-09-08 Olin Corporation In-situ dendritic treatment of electrodeposited foil
US5009750A (en) * 1988-11-15 1991-04-23 Maschinenfabrik Andritz Actiengesellschaft Process and apparatus for the manufacture of a metal foil
EP0491163A1 (en) * 1990-12-19 1992-06-24 Nikko Gould Foil Co., Ltd. Method and apparatus for producing electrolytic copper foil
US5326455A (en) * 1990-12-19 1994-07-05 Nikko Gould Foil Co., Ltd. Method of producing electrolytic copper foil and apparatus for producing same
CN102797026A (en) * 2012-08-16 2012-11-28 成都崇安科技有限公司 Inclined taper-shaped hexagonal roller electroplating device
CN103556188A (en) * 2013-10-31 2014-02-05 常州华日升反光材料股份有限公司 Electroforming equipment

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053370A (en) * 1975-09-18 1977-10-11 Koito Manufacturing Company Limited Process for the fabrication of printed circuits
US4129492A (en) * 1975-12-23 1978-12-12 Imperial Metal Industries (Kynoch) Limited Electrolytic cell
DE3307748A1 (en) * 1982-03-05 1983-09-15 Olin Corp., 62024 East Alton, Ill. METHOD FOR TREATING A METAL FILM IN ORDER TO IMPROVE YOUR ADHESION
US4468293A (en) * 1982-03-05 1984-08-28 Olin Corporation Electrochemical treatment of copper for improving its bond strength
US4515671A (en) * 1983-01-24 1985-05-07 Olin Corporation Electrochemical treatment of copper for improving its bond strength
US4490218A (en) * 1983-11-07 1984-12-25 Olin Corporation Process and apparatus for producing surface treated metal foil
US4549940A (en) * 1984-04-23 1985-10-29 Karwan Steven J Method for surface treating copper foil
US4692221A (en) * 1986-12-22 1987-09-08 Olin Corporation In-situ dendritic treatment of electrodeposited foil
US5009750A (en) * 1988-11-15 1991-04-23 Maschinenfabrik Andritz Actiengesellschaft Process and apparatus for the manufacture of a metal foil
US5100522A (en) * 1988-11-15 1992-03-31 Maschinonfabrik Andritz Actiengesellschaft Process and apparatus for the manufacture of a metal foil
EP0491163A1 (en) * 1990-12-19 1992-06-24 Nikko Gould Foil Co., Ltd. Method and apparatus for producing electrolytic copper foil
US5326455A (en) * 1990-12-19 1994-07-05 Nikko Gould Foil Co., Ltd. Method of producing electrolytic copper foil and apparatus for producing same
CN102797026A (en) * 2012-08-16 2012-11-28 成都崇安科技有限公司 Inclined taper-shaped hexagonal roller electroplating device
CN103556188A (en) * 2013-10-31 2014-02-05 常州华日升反光材料股份有限公司 Electroforming equipment
CN103556188B (en) * 2013-10-31 2016-08-31 常州华日升反光材料股份有限公司 A kind of electroforming apparatus

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