US2651610A - Method of electroplating zinc - Google Patents

Method of electroplating zinc Download PDF

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US2651610A
US2651610A US174242A US17424250A US2651610A US 2651610 A US2651610 A US 2651610A US 174242 A US174242 A US 174242A US 17424250 A US17424250 A US 17424250A US 2651610 A US2651610 A US 2651610A
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current
zinc
plating
alternating
volts
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US174242A
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Allan E Chester
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Brent Chemicals Corp
Poor and Co
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Poor and Co
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Assigned to BRENT CHEMICALS CORPORATION, A CORP. OF DE. reassignment BRENT CHEMICALS CORPORATION, A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: STAUFFER CHEMICAL COMPANY
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18Electroplating using modulated, pulsed or reversing current
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/22Electroplating: Baths therefor from solutions of zinc

Definitions

  • This invention relates to a new and improved method of electroplating, and more particularly to a method of electrodepositing metals from a plating bath in a new and improved manner adapted to produce substantially uniform distribution on articles or objects of configurations such that the ordinary type of electroplating causes uneven distribution of the electrodeposited metal.
  • One of the objects of the present invention is to provide a new and improved method for overcoming the difficulty mentioned above and for electrodepositing metals from plating baths in a uniform manner.
  • Another object of the invention is to provide a new and improved method for electrodepositing metals on flat sheets or other flat-objects in a manner such that substantial uniformity of distribution is obtained.
  • a still further object is the provision of a new and improved method for controlling the distribution of a metal from a plating bath.
  • FIG. 1 illustrates diagrammatically one form of apparatus suitable for the practice of the invention
  • Fig. 2 illustrates graphically one of the limits of the wave form of the plating current
  • Fig. 3 illustrates another limit of thewave form of the plating current in accordance with the preferred practice of the invention.
  • the invention involves a new and improved method of controlling the distribution of zinc deposited on an electrically conducting surface from a plating bath by superimposing alternating current on direct current within certain predetermined limits.
  • the invention is especially applicable to electroplating operations in which the work or article is so shaped that the electrodeposited metal builds up in some areas more than others.
  • the plating current for the purpose of this invention may be described as an asymmetric alternating current in which the negative peak value of the wave form varies from zero (as illustrated in Fig. 2) to -2/3 of the positive peak value (as illustrated in Fig. 3).
  • the apparatus illustrated comprises a suitable receptacle I containing the plating bath, provided with one or more electrodes, generally indicated at 2, and a work piece or conducting surface to be plated, generally indicated at 3.
  • the electrode 2 forms the anode and the work piece 3 the cathode.
  • the anode 2 is connected by suitable conductors to the secondary -4 of a power transformer having a core 5 and a primary 6.
  • the primary 6 is connected to a regulating auto-transformer, generally illustrated at 1, which in turn is connected to a suitable source of electrical energy, such as a 220 or 440 volt alternating current.
  • Direct current is supplied by means of a low voltage current generator, generally shown at 8, one side of which passes to the work piece 3 through a rheostat 9, and the other side of which is connected to the secondary 4 in the manner shown.
  • y(Y1) falls below the X-axis and is a different value from the positive peak value (Y in Fig. 2, Z in Fig. 3) represents the maximum negative value (Z1) which may be employed for the purpose of this invention.
  • Any wave form similar to Fig. 2 in which the negative peak value is positive or above the X-axis may be described as pulsating direct current.
  • the apparatus described and the hook-up of the component parts is believed to represent a new and improved system for the electrodeposition of metals by the superimposition of an alternating current on a direct current, irrespective of whether the ratios of alternating current to direct current are within the limits preferred for uniform distribution.
  • this type of apparatus may be employed in plating articles of any configuration with other ratios of alternating current to direct current where the distribution of the electrodeposited metal is not an important factor.
  • This type of apparatus is suitable, therefore, for electroplating operations by the superimposition Aof alternating current on direct current in such a manner as to form a pulsating direct current.
  • this invention is especially adapted for forming coatings of Zinc on steel or cast iron objects in which the thickness of the coating is within the range of .000005 inch to .00005 inch.
  • Steel or cast iron objects, when plated with zinc in accordance with the invention to the thickness described, are especially suitable for the addition of coatings of vitreous enamels, as described and claimed in my copending application Serial No. 555,953 filed September 27, 1944, now Patent No. 2,615,836.
  • the thickness and uniformity of the plate is an important factor because it has been found that if the electrodeposited plate is insumcient, the desired bonding action will not occur. The same is true if the thickness of the coating is too great.
  • this invention makes possible new and improved results in the art of enameling, as well as new and improved results in controlling the distribution of metals by electrodeposition.
  • Example A typical zinc plating bath which may be employed has the following composition:
  • the bath may be puriiied by electrolyzing it as described in Transactions of Electrochemical Society, vol. 80, (1941) pages 391 and 392.
  • the ratios of alternating to direct current may be varied in order to obtain the optimum wave form in the manner previously described.
  • the ratios of alternating to direct current which are preferably employed in accordance with the invention in order to obtain the desired Wave form, are about 2-4 volts (root mean square) A. C.: 2.5 volts D. C., preferably at current densities from 2 to 15 amperes per square foot. Alternating currents of different frequencies may be used, but it is preferable to employ either a 25 cycle or a 60 cycle current.
  • the plating time will vary depending upon the amount of metal which it is desired to deposit. Thus, for thicknesses of the type previously mentioned for vitreous enamel work, a plating time from 8 seconds to 11/2 minutes is sufficient.
  • the alternating and direct current voltages may be larger or smaller, provided that the ratio produces a predetermined wave form of the type previously described.
  • the direct current is 0.5 volt
  • the alternating current would be correspondingly reduced in accordance with the foregoing ratio.
  • the direct current is 10 volts, the alternating current is increased in the foregoing ratio.
  • the plating current will be governed by the surface area of the article being plated, the size of the bath, power facilities and other factors 4 which will be recognized by those skilled in the art.
  • zinc plating bat is intended to include plating baths of the type described in the example Where other metals or salts thereof are present in minor proportion as well as those in which such metals or salts are absent.
  • the invention provides a new and improved method for controlling the deposition of zinc on electrically conducting surfaces. It is especially useful in applying even, uniform coatings to articles having a configuration in which, by ordinary direct current plating methods, the deposited metal tends to build up in some areas more than others. Thus, it is especially important for electroplating fiat surfaces when a thin plate of substantially uniform thickness is desired.
  • a method of controlling the electrodeposition of zinc from an acid zinc sulphate plating bath onto an electrically conducting object of a type in which the zinc would normally be deposited in greater concentrations in some areas than in others by a direct plating current comprising electrodepositing the zinc by subjecting said object in an acid plating bath to a plating current having an asymmetric alternating wave form comprising an alternating current superimposed on a direct current in the ratio of 2-4 volts R. M. S. to 2.5 volts D. C., regardless of the speciiic current values, at current densities from about 2 to about 15 amperes per square foot.
  • a method of controlling the electrodeposition of zinc from an acid zinc sulfate plating bath onto a work piece of a type in which the zinc is normally deposited in greater concentrations in some areas of the work than in others by direct current plating comprising electrodepositing zinc on said work piece from an acid bath by a superimposed alternating-direct plating current comprising an alternating current to direct current ratio from about 2 to about 4 volts R. M. S. alternating current having a frequency within the limits from about 25 cycles to about 60 cycles to about 2.5 volts D. C., regardless of the specific current values, at current densities from about 2 to about 15 amperes per square foot for a'period of time within the range from 8 seconds to about 11/2 ⁇ minutes.

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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)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Description

1 Sept 8, 1953 A. E. cHEsTER` 2,651,610
METHOD OF ELECTROPLATING ZINC 'Filed July 17, 1950 220- 440KHC [lavan/iva Hura- 7AM/umana 3 ow 1647465 mwf ufasrar acide-Mmm HH 1 raaf o Q.. ...T/Mt.
Patented Sept. 8, 1953 METHOD F ELECTROPLATING ZINC Allan E. Chester, Highland Park, Ill., assigner to Poor & Company, Chicago, Ill., a corporation of Delaware Application July 17, 1950, Serial No. 174,242
2 Claims. 1
This invention relates to a new and improved method of electroplating, and more particularly to a method of electrodepositing metals from a plating bath in a new and improved manner adapted to produce substantially uniform distribution on articles or objects of configurations such that the ordinary type of electroplating causes uneven distribution of the electrodeposited metal.
It is well known that flat objects, when electroplated in the usual way in an electroplating bat tend to build up a higher concentration of metal near the edges than in the middle. This is true to some extent in objects of other configurations and various devices have been proposed in order to overcome this diiiiculty.
One of the objects of the present invention is to provide a new and improved method for overcoming the difficulty mentioned above and for electrodepositing metals from plating baths in a uniform manner.
Another object of the invention is to provide a new and improved method for electrodepositing metals on flat sheets or other flat-objects in a manner such that substantial uniformity of distribution is obtained.
A still further object is the provision of a new and improved method for controlling the distribution of a metal from a plating bath.
Other features and advantages of the invention Will appear hereinafter by reference to the following description thereof, in conjunction with v the accompanying drawings in which:
Fig. 1 illustrates diagrammatically one form of apparatus suitable for the practice of the invention;
Fig. 2 illustrates graphically one of the limits of the wave form of the plating current; and
Fig. 3 illustrates another limit of thewave form of the plating current in accordance with the preferred practice of the invention.
Generally stated, the invention involves a new and improved method of controlling the distribution of zinc deposited on an electrically conducting surface from a plating bath by superimposing alternating current on direct current within certain predetermined limits. The invention is especially applicable to electroplating operations in which the work or article is so shaped that the electrodeposited metal builds up in some areas more than others. The plating current for the purpose of this invention may be described as an asymmetric alternating current in which the negative peak value of the wave form varies from zero (as illustrated in Fig. 2) to -2/3 of the positive peak value (as illustrated in Fig. 3).
Referring to Fig. 1, the apparatus illustrated comprises a suitable receptacle I containing the plating bath, provided with one or more electrodes, generally indicated at 2, and a work piece or conducting surface to be plated, generally indicated at 3. As will be understood, the electrode 2 forms the anode and the work piece 3 the cathode.
The anode 2 is connected by suitable conductors to the secondary -4 of a power transformer having a core 5 and a primary 6. The primary 6 is connected to a regulating auto-transformer, generally illustrated at 1, which in turn is connected to a suitable source of electrical energy, such as a 220 or 440 volt alternating current. Direct current is supplied by means of a low voltage current generator, generally shown at 8, one side of which passes to the work piece 3 through a rheostat 9, and the other side of which is connected to the secondary 4 in the manner shown.
In Figs. 2 and 3 the Wave form of the current is graphically illustrated in a conventional manner,-
the horizontal axis (X--X) representing time and the vertical axis amplitude. The peak values are calculated from the equation E=1.414\/E2A. C. (R. M. S.) +E2 D. C.
y(Y1) falls below the X-axis and is a different value from the positive peak value (Y in Fig. 2, Z in Fig. 3) represents the maximum negative value (Z1) which may be employed for the purpose of this invention. Any wave form similar to Fig. 2 in which the negative peak value is positive or above the X-axis may be described as pulsating direct current.
In a broader sense, the apparatus described and the hook-up of the component parts is believed to represent a new and improved system for the electrodeposition of metals by the superimposition of an alternating current on a direct current, irrespective of whether the ratios of alternating current to direct current are within the limits preferred for uniform distribution. Thus, this type of apparatus may be employed in plating articles of any configuration with other ratios of alternating current to direct current where the distribution of the electrodeposited metal is not an important factor. This type of apparatus is suitable, therefore, for electroplating operations by the superimposition Aof alternating current on direct current in such a manner as to form a pulsating direct current.
'I'he method of controlling distribution of the electrodeposited metal as described herein is especially suited for the formation of very thin, substantially uniform films or coatings of a metal on an electrically conductive surface. For example, it has been found that this invention is especially adapted for forming coatings of Zinc on steel or cast iron objects in which the thickness of the coating is within the range of .000005 inch to .00005 inch. Steel or cast iron objects, when plated with zinc in accordance with the invention to the thickness described, are especially suitable for the addition of coatings of vitreous enamels, as described and claimed in my copending application Serial No. 555,953 filed September 27, 1944, now Patent No. 2,615,836. The thickness and uniformity of the plate is an important factor because it has been found that if the electrodeposited plate is insumcient, the desired bonding action will not occur. The same is true if the thickness of the coating is too great. Thus, this invention makes possible new and improved results in the art of enameling, as well as new and improved results in controlling the distribution of metals by electrodeposition.
The invention will be further illustrated but is not limited by the following example:
Example A typical zinc plating bath which may be employed has the following composition:
Ounces per gallon ZnSOrJYI-IZO 48 NH4Cl 4 NaCzHsOaSHbO (sodium acetate) 2 l-IzSOrx 0.4
- The bath may be puriiied by electrolyzing it as described in Transactions of Electrochemical Society, vol. 80, (1941) pages 391 and 392. The ratios of alternating to direct current may be varied in order to obtain the optimum wave form in the manner previously described.
It will be understood that the invention is susceptible vto some variation and modication in the manner of its practicalv application.
The ratios of alternating to direct current which are preferably employed in accordance with the invention in order to obtain the desired Wave form, are about 2-4 volts (root mean square) A. C.: 2.5 volts D. C., preferably at current densities from 2 to 15 amperes per square foot. Alternating currents of different frequencies may be used, but it is preferable to employ either a 25 cycle or a 60 cycle current. The plating time will vary depending upon the amount of metal which it is desired to deposit. Thus, for thicknesses of the type previously mentioned for vitreous enamel work, a plating time from 8 seconds to 11/2 minutes is sufficient. It will be understood that higher current densities may be used, and that the alternating and direct current voltages may be larger or smaller, provided that the ratio produces a predetermined wave form of the type previously described. Thus, if the direct current is 0.5 volt, the alternating current would be correspondingly reduced in accordance with the foregoing ratio. If the direct current is 10 volts, the alternating current is increased in the foregoing ratio.
The plating current will be governed by the surface area of the article being plated, the size of the bath, power facilities and other factors 4 which will be recognized by those skilled in the art.
The expression zinc plating bat is intended to include plating baths of the type described in the example Where other metals or salts thereof are present in minor proportion as well as those in which such metals or salts are absent.
The invention provides a new and improved method for controlling the deposition of zinc on electrically conducting surfaces. It is especially useful in applying even, uniform coatings to articles having a configuration in which, by ordinary direct current plating methods, the deposited metal tends to build up in some areas more than others. Thus, it is especially important for electroplating fiat surfaces when a thin plate of substantially uniform thickness is desired.
This application is a continuation-in-part of my copending application Serial N o. 555,954, filed September 27, 1944, now U. S. Patent No. 2,515,192.
The invention is hereby claimed as follows:
1. In a method of controlling the electrodeposition of zinc from an acid zinc sulphate plating bath onto an electrically conducting object of a type in which the zinc would normally be deposited in greater concentrations in some areas than in others by a direct plating current; the step which comprises electrodepositing the zinc by subjecting said object in an acid plating bath to a plating current having an asymmetric alternating wave form comprising an alternating current superimposed on a direct current in the ratio of 2-4 volts R. M. S. to 2.5 volts D. C., regardless of the speciiic current values, at current densities from about 2 to about 15 amperes per square foot.
2. In a method of controlling the electrodeposition of zinc from an acid zinc sulfate plating bath onto a work piece of a type in which the zinc is normally deposited in greater concentrations in some areas of the work than in others by direct current plating; the step which comprises electrodepositing zinc on said work piece from an acid bath by a superimposed alternating-direct plating current comprising an alternating current to direct current ratio from about 2 to about 4 volts R. M. S. alternating current having a frequency within the limits from about 25 cycles to about 60 cycles to about 2.5 volts D. C., regardless of the specific current values, at current densities from about 2 to about 15 amperes per square foot for a'period of time within the range from 8 seconds to about 11/2` minutes.
ALLAN E. CHESTER.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,918,605 Jones July 18, 1933 2,063,760 Schulen Dec. 8, 1936 2,443,599 Chester June 22, 1948 2,515,192 Chester July 18, 1950 OTHER REFERENCES vol. 18

Claims (1)

1. IN A METHOD OF CONTROLLING THE ELECTRODEPOSITION OF ZINC FROM AN ACID ZINC SULPHATE PLATING BATH ONTO AN ELECTRICALLY CONDUCTING OBJECT OF A TYPE IN WHICH THE ZINC WOULD NORMALLY BE DEPOSITED IN GREATER CONCENTRATIONS IN SOME AREAS THAN IN OTHERS BY A DIRECT PLATING CURRENT; THE STEP WHICH COMPRISES ELECTRODEPOSITING THE ZINC BY SUBJECTING SAID OBJECT IN AN ACID PLATING BATH TO A PLATING CURRENT HAVING AN ASYMMETRIC ALTERNATING WAVE FROM COMPRISING AN ALTERNATING CURRENT SUPERIMPOSED ON A DIRECT CURRENT IN THE RATIO OF 2-4 VOLTS R. M. S. TO 2.5 VOLTS D. C., REGARDLESS OF THE SPECIFIC CURRENT VALUES, AT CURRENT DENSITIES FROM ABOUT 3 TO ABOUT 15 AMPERES PER SQUARE FOOT.
US174242A 1950-07-17 1950-07-17 Method of electroplating zinc Expired - Lifetime US2651610A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905603A (en) * 1957-09-04 1959-09-22 American Zinc Inst Zinc plating

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1918605A (en) * 1928-01-09 1933-07-18 Parker Rust Proof Co Chromium plating
US2063760A (en) * 1931-09-10 1936-12-08 Schulein Joseph Bath for and process of electrodeposition of metal
US2443599A (en) * 1942-05-04 1948-06-22 Poor & Co Electroplating method employing pulsating current of adjustable wave form
US2515192A (en) * 1944-09-27 1950-07-18 Poor & Co Method of electroplating

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1918605A (en) * 1928-01-09 1933-07-18 Parker Rust Proof Co Chromium plating
US2063760A (en) * 1931-09-10 1936-12-08 Schulein Joseph Bath for and process of electrodeposition of metal
US2443599A (en) * 1942-05-04 1948-06-22 Poor & Co Electroplating method employing pulsating current of adjustable wave form
US2515192A (en) * 1944-09-27 1950-07-18 Poor & Co Method of electroplating

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905603A (en) * 1957-09-04 1959-09-22 American Zinc Inst Zinc plating

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