CA1161782A - Nickel-coated electrode of sheared low carbon steel - Google Patents
Nickel-coated electrode of sheared low carbon steelInfo
- Publication number
- CA1161782A CA1161782A CA000328133A CA328133A CA1161782A CA 1161782 A CA1161782 A CA 1161782A CA 000328133 A CA000328133 A CA 000328133A CA 328133 A CA328133 A CA 328133A CA 1161782 A CA1161782 A CA 1161782A
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- Prior art keywords
- nickel
- iron
- activator
- anode material
- sulfur
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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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)
Abstract
ABSTRACT OF THE DISCLOSURE
Relates to a material consisting of a nickel-iron sandwich having specific interrelation of components and adapted for use as a consumable anode material in nickel-iron alloy plating baths. The ratio of exposed areas of nickel and from is related to the amount of activator in the nickel.
Relates to a material consisting of a nickel-iron sandwich having specific interrelation of components and adapted for use as a consumable anode material in nickel-iron alloy plating baths. The ratio of exposed areas of nickel and from is related to the amount of activator in the nickel.
Description
~ 161782 The present invention relates to electroplating materials and more particularly to consl~mable anode matcrial for electrodeposition of nickel-iron alloys.
Background of the Invention:
Alloy nickel-iron electrodeposition is carried out commercially both for decorative purposes and for specific utilitarian purposes related to the production of electronic magnetizable components. Baths and processing conditions for such plating are well known. Consumable anode materials which have been used in commercial operations are of two tvpes (a) alloY anode ma-terials and (b) separate iron and nickel anode materials used separately either as slabs or as small pieces in separate nickel and iron baskets. The terms nickel and iron baskets refer, of course, to baskets made of titanium metal which are adapted in one instance to contain pieces of nickel, for example, rounds, squares or pellets and in the other instance to contain pieces of iron and which, when connected to the positive side of an essentially uni-directional circuit become anodes. The two types of anodes used have some disadvantage. The principal disadvantages of the separate iron and nickel anodes are (a) the necessity for maintaining separate inventories of iron and nickel, ~b) the need in some instances for separate anode controls, (c) the danger of placing the wrong material in a basket and (d) the possible effect of the imbalance to the electroplating system if one anode loses current. Alloy anodes have the disadvantage that they must be specially melted and cast and thus are more costly than the basic metals.
Objects of the Invention:
It is an object of the present invention to provide '~
1 ~617~2 an anode product which avoicls these disadvantages.
Another object of the present invention is to provide nickel-iron alloy electrodeposition process employing the novel material of the present invention.
Other ob~ects and advantages will become apparent from the following description.
De$c~ o~ of the Invention:
Generally speaking, the present invention contemplates an electroplating anode material comprising sheared pieces of low carbon steel sheet coated on both sides with nickel. The ratio of the exposed area o~ nickel to the exposed area of steel in the sheared pieces is about 3 to about 80 and the nickel contains from 0% to 0.2% of sulPur as an activator or from 0% to 5% of an activator other than sulfur. The activator content of the nickel is related to the ratio of exposed areas of nickel to steel such that when the activator content of the nickel is zero or near zero, the ratio of the exposed areas is at the high end of the aforestated range and when the activator content of the nickel is near 0.2% if the activator is sulfur or is near 5~ if the activator is a material other than sulfur the ratio of the exposed areas is at the low end of the aforestated range. The exposed area of nickel relative to the exposed area of iron largely determines dissolution characteristics of the anode material of this invention.
Ratios of exposed area of nickel to e~posed area of iron ranging ~rom about 3 to about 80 represent practical limits.
The nickel in the anode material can contain up to about 5%
activator, e.g., from 0% to about 0.2% sulfur. When the sulfur content of the nickel is at the low end of the range, the . ï --2--~ 1~17~
ratio of exposed area of nickel to iron is kept at the high end of the aforestated range. Conversely, when the sulfur content of the nickel in the sandwich is high the ratio of exposed areas is kept low.
While the anode material of the present invention has been described in terms of a nickel-iron-nickel sandwich in which the nickel has been electrodeposlted upon the iron, those skilled in the art will appreciate -that the nickel can be coated on the iron in other ways as well. For example, sheet of nickel can be hot rolled onto iron or nickel could be deposited on iron in the form of a powder and sintered and compacted onto the iron surface. With methods of production other than electrolytic those skilled in the art will appreciate that materials other than sulfur can be used to activate the nickel for electrodeposition purposes. Examples of such other activating materials include silicon, oxygen and carbon. Those skilled in the art will appreciate that use of activating materials in nickel for electrodissolution purposes is well known having been described in one or more of U.S. patents Nos. 1,552,609; 1,552,610; 1,751,630; 1,941,256; 1,941,257;
Background of the Invention:
Alloy nickel-iron electrodeposition is carried out commercially both for decorative purposes and for specific utilitarian purposes related to the production of electronic magnetizable components. Baths and processing conditions for such plating are well known. Consumable anode materials which have been used in commercial operations are of two tvpes (a) alloY anode ma-terials and (b) separate iron and nickel anode materials used separately either as slabs or as small pieces in separate nickel and iron baskets. The terms nickel and iron baskets refer, of course, to baskets made of titanium metal which are adapted in one instance to contain pieces of nickel, for example, rounds, squares or pellets and in the other instance to contain pieces of iron and which, when connected to the positive side of an essentially uni-directional circuit become anodes. The two types of anodes used have some disadvantage. The principal disadvantages of the separate iron and nickel anodes are (a) the necessity for maintaining separate inventories of iron and nickel, ~b) the need in some instances for separate anode controls, (c) the danger of placing the wrong material in a basket and (d) the possible effect of the imbalance to the electroplating system if one anode loses current. Alloy anodes have the disadvantage that they must be specially melted and cast and thus are more costly than the basic metals.
Objects of the Invention:
It is an object of the present invention to provide '~
1 ~617~2 an anode product which avoicls these disadvantages.
Another object of the present invention is to provide nickel-iron alloy electrodeposition process employing the novel material of the present invention.
Other ob~ects and advantages will become apparent from the following description.
De$c~ o~ of the Invention:
Generally speaking, the present invention contemplates an electroplating anode material comprising sheared pieces of low carbon steel sheet coated on both sides with nickel. The ratio of the exposed area o~ nickel to the exposed area of steel in the sheared pieces is about 3 to about 80 and the nickel contains from 0% to 0.2% of sulPur as an activator or from 0% to 5% of an activator other than sulfur. The activator content of the nickel is related to the ratio of exposed areas of nickel to steel such that when the activator content of the nickel is zero or near zero, the ratio of the exposed areas is at the high end of the aforestated range and when the activator content of the nickel is near 0.2% if the activator is sulfur or is near 5~ if the activator is a material other than sulfur the ratio of the exposed areas is at the low end of the aforestated range. The exposed area of nickel relative to the exposed area of iron largely determines dissolution characteristics of the anode material of this invention.
Ratios of exposed area of nickel to e~posed area of iron ranging ~rom about 3 to about 80 represent practical limits.
The nickel in the anode material can contain up to about 5%
activator, e.g., from 0% to about 0.2% sulfur. When the sulfur content of the nickel is at the low end of the range, the . ï --2--~ 1~17~
ratio of exposed area of nickel to iron is kept at the high end of the aforestated range. Conversely, when the sulfur content of the nickel in the sandwich is high the ratio of exposed areas is kept low.
While the anode material of the present invention has been described in terms of a nickel-iron-nickel sandwich in which the nickel has been electrodeposlted upon the iron, those skilled in the art will appreciate -that the nickel can be coated on the iron in other ways as well. For example, sheet of nickel can be hot rolled onto iron or nickel could be deposited on iron in the form of a powder and sintered and compacted onto the iron surface. With methods of production other than electrolytic those skilled in the art will appreciate that materials other than sulfur can be used to activate the nickel for electrodeposition purposes. Examples of such other activating materials include silicon, oxygen and carbon. Those skilled in the art will appreciate that use of activating materials in nickel for electrodissolution purposes is well known having been described in one or more of U.S. patents Nos. 1,552,609; 1,552,610; 1,751,630; 1,941,256; 1,941,257;
2,117,284; 2,304,059; 2,392,708; 2,453,757; 2,623,848;
3,437,571 and 3,449,224. I~t is known from these sources and others that the relative activity of nickel under electrocorroding conditions can be controlled by the amounts and type of activator. Consequently, when a particular activator system is used in the nickel portion of the anode materials of the present invention it is clearly within the skill of the art to adjust the activator content relative to the ratio of exposed areaof nickel to exposed ,,;, area of iron in the same manner as disclosed hereinbefore with respect to sulfur as an activator.
While the term steel has been equated hereinbefore with the term iron, it will be appreciated that what is desired for the iron portion of the composite electrode of the present invention is a relatively pure lron material.
Some materials classified as steels which contain larye amounts of elements other than iron, for example, stainless steels are not contemplated as being useful in the anode ]o material of the present invention. Likewise, high alloyed carbon steels containing elements such as molybdenum, chro-mium, tungsten and the like should not be used because of the possibility that these elements will be carried into the electroplating bath and cause contamination therein. Steel suitable for use along with sheet iron in manufacturing the anode of the present invention include but are not limited to the following grades 1010, 1020 and low carbon grade steels.
A highly advantageous method of making the anode material of the present invention is to employ a piece of sheet iron or steel of appropriate dimension for example, 1 meter square and about 0.08 centimeter thick as mandrel on which sulfur-containin~ nickel is electrodeposited in a typical nickel electrowinning or electrorefining operation. It is con-venient to deposit approximately 0.32 centimeters of nickel containing about 200 to 300 parts per million (ppm) of sulfur on both sides of the iron mandrel. Following completion of electrodeposition of the sulfur-bearing nickel, the mandrel is removed from the electrolytic cell washed, dried, and sheared into the appropriately sized pieces. By this means it is very convenient to provide squares or rectangular pieces of anode 11 ~61782 material. Alternatively, the iron mandrel bearing the electro-nickel deposit can be blanked to form round or oval pieces and the scrap sheared to produce irregular pieces of anode material. Those skilled in the art will appreciate that the term shearing is intended to include all forms of cutting including sawing and the like. Those skilled in ~he art in the electrorefining art will also appreciate -that the cathode mandrel can be selectively masked to provide lines of weak-ness where the mandrel can be sheared with less effort than required with an unmasked mandrel. In general, however, such masking is not necessary and is somewhat troublesome in that it dictates the size of the ultimate product at a time when the desirable size may not be readily determinable.
It is important to note with respect to the use of iron mandrels in electrowinning and electrorefining that the mandrel must be treated so as to maximize adhesion of electro-deposited nickel thereto. Ic the adhesive forces between nickel and the iron are not strong there is a chance that upon shearing the nickel and iron will delaminate which delamination is detrimental to the production of anode mate-rials of the present invention.
In accordance with the present invention the nickel-iron anode material as described hereinbefore is employed in a typical, co~mercial nickel-iron a~ueous sulfate electrolyte containing about 30 to about 120 grams per liter (gpl) of nickel ab~ut l to about lO gpl of iron about lO to about 75 gpl of chloride ion, about 30 gpl to about saturation with boric acid, a bath stabilizer to prevent precipitation of iron hydrate (iron hydroxide1 a stress reducer with the balance being water. The pH of the electrolyte was maintained 1 ~L 6 1 h~ ~ 2 at about 2.3 to about 4.2. In the aforedescribed bath, the bath stabilizer can comprise either a reducing agent such as ascorbic acid or an isomer of ascorbic aeid to maintain iron in the ferrous state or it can comprise a complexing agent, for example, sodium gluconate or sodium oxalate which will complex ferric ions in solution. A typieal stress redueer used along with the bath stabilizer in commereial baths is sodium saccharin. This hath is :normally operated at tempera-tures o~ about 50 to 75C. Of course, ~rom time to time, adjustments o~ bath composition may be necessary. The anode material of the present invention is normally employed in the ~oregoing bath at an anode current density o~ about 1.0 to about 7.5 amperes per square deeimeter (A/dm2). It is well known to those skilled in the art that other -types of niekel-iron baths can be employed with other eleetroplating eonditions usual to those baths. For example, iron-nickel plating baths are diselosed in the following U.S. patents:
U.S. Pat.
No. In~entor Date 3,716,464 Ko~ak 2/13/73 3,795,591 Clauss et al3/ 5/74 3,806,429 Clauss et al4/23/74 3,812,566 Clauss 5/28/74 3,922,209 Passal 11/25/75 3,969,198 Law et al 7/13/76 3,974,044 Tr~mmel 8/10/76
While the term steel has been equated hereinbefore with the term iron, it will be appreciated that what is desired for the iron portion of the composite electrode of the present invention is a relatively pure lron material.
Some materials classified as steels which contain larye amounts of elements other than iron, for example, stainless steels are not contemplated as being useful in the anode ]o material of the present invention. Likewise, high alloyed carbon steels containing elements such as molybdenum, chro-mium, tungsten and the like should not be used because of the possibility that these elements will be carried into the electroplating bath and cause contamination therein. Steel suitable for use along with sheet iron in manufacturing the anode of the present invention include but are not limited to the following grades 1010, 1020 and low carbon grade steels.
A highly advantageous method of making the anode material of the present invention is to employ a piece of sheet iron or steel of appropriate dimension for example, 1 meter square and about 0.08 centimeter thick as mandrel on which sulfur-containin~ nickel is electrodeposited in a typical nickel electrowinning or electrorefining operation. It is con-venient to deposit approximately 0.32 centimeters of nickel containing about 200 to 300 parts per million (ppm) of sulfur on both sides of the iron mandrel. Following completion of electrodeposition of the sulfur-bearing nickel, the mandrel is removed from the electrolytic cell washed, dried, and sheared into the appropriately sized pieces. By this means it is very convenient to provide squares or rectangular pieces of anode 11 ~61782 material. Alternatively, the iron mandrel bearing the electro-nickel deposit can be blanked to form round or oval pieces and the scrap sheared to produce irregular pieces of anode material. Those skilled in the art will appreciate that the term shearing is intended to include all forms of cutting including sawing and the like. Those skilled in ~he art in the electrorefining art will also appreciate -that the cathode mandrel can be selectively masked to provide lines of weak-ness where the mandrel can be sheared with less effort than required with an unmasked mandrel. In general, however, such masking is not necessary and is somewhat troublesome in that it dictates the size of the ultimate product at a time when the desirable size may not be readily determinable.
It is important to note with respect to the use of iron mandrels in electrowinning and electrorefining that the mandrel must be treated so as to maximize adhesion of electro-deposited nickel thereto. Ic the adhesive forces between nickel and the iron are not strong there is a chance that upon shearing the nickel and iron will delaminate which delamination is detrimental to the production of anode mate-rials of the present invention.
In accordance with the present invention the nickel-iron anode material as described hereinbefore is employed in a typical, co~mercial nickel-iron a~ueous sulfate electrolyte containing about 30 to about 120 grams per liter (gpl) of nickel ab~ut l to about lO gpl of iron about lO to about 75 gpl of chloride ion, about 30 gpl to about saturation with boric acid, a bath stabilizer to prevent precipitation of iron hydrate (iron hydroxide1 a stress reducer with the balance being water. The pH of the electrolyte was maintained 1 ~L 6 1 h~ ~ 2 at about 2.3 to about 4.2. In the aforedescribed bath, the bath stabilizer can comprise either a reducing agent such as ascorbic acid or an isomer of ascorbic aeid to maintain iron in the ferrous state or it can comprise a complexing agent, for example, sodium gluconate or sodium oxalate which will complex ferric ions in solution. A typieal stress redueer used along with the bath stabilizer in commereial baths is sodium saccharin. This hath is :normally operated at tempera-tures o~ about 50 to 75C. Of course, ~rom time to time, adjustments o~ bath composition may be necessary. The anode material of the present invention is normally employed in the ~oregoing bath at an anode current density o~ about 1.0 to about 7.5 amperes per square deeimeter (A/dm2). It is well known to those skilled in the art that other -types of niekel-iron baths can be employed with other eleetroplating eonditions usual to those baths. For example, iron-nickel plating baths are diselosed in the following U.S. patents:
U.S. Pat.
No. In~entor Date 3,716,464 Ko~ak 2/13/73 3,795,591 Clauss et al3/ 5/74 3,806,429 Clauss et al4/23/74 3,812,566 Clauss 5/28/74 3,922,209 Passal 11/25/75 3,969,198 Law et al 7/13/76 3,974,044 Tr~mmel 8/10/76
4,002,543 Clauss et allJ11/77 4,014,759 McMullen et al3/29/77 4,036,709 Harbulak 7/19/77 4,Q46,647 Harbulak 9~ 6/77 4,053,373 McMullen et al10/11/77 ~ t' 1 lB1782 In order to give those skilled in the art a greater appreciation of the advantages of the invention, the following examples are given.
EXAMPLE Ia Anode material in accordance with the present inven-tion was made by the electrodeposition of 0.119 centimeter thickness of nickel containing about 200 to 300 ppm sulfur on both sides of a 0.079 centimeter thick iron sheet. The slleet was then sheared into square pieces 2.54 centimeter on edge to form anode material of the present invention having a ratio of surface area of nickel to exposed area of iron of about 19. The anode of this example contained about 75 nickel, 25% iron.
-6a-EXAMP:LE Ib Anode material was made in the same way as Exaple Ia except that type 1010 steel sheet 0.094 cm thick was used instead of iron sheet and the nickel was electrodeposited to a thickness of 0.131 cm to produce a ratio of surface area of nickel to exposed area of iron o:E about 16.3~ The anode of this example also contained about 75~ nickel, 25% iron.
EXAMPLE IC
Anode material was made in the same way as in Example Ia except that the nickel was essentially free of an activator, containing only 5 to 10 ppm sulfur.
EXAMPLE Id Anode material was made in a manner similar to Example Ib except that the nickel was electrodeposited to a thickness of 0.093 cm to produce anode material containing about 65%
nickel, 35~ iron. The ratio of exposed nickel to iron surface area of the anode material of this example is about 15.5.
EXAMPLE Ie Anode material was made in the same way as Example Ib except the sheet was sheared into square pieces 1.27 cm on edge to form anode material having a ratio of surface area of nickel to exposed area of iron of about 11Ø
EXAMPLE I I
The anode materials of Examples Ia and Ib were electrodissolved separately in a titanium basket in a plating bath having the following nominal composition at the start of dissolution:
NiSo4 6H20 300 g/liter NiCl 6H20 60 g/liter H3BO3 30 g/liter -I 16~7~
Sodit~ Gluconate 20 g/liter Sodium Saccharin 0.2 g/li.ter The bath was operated at a temperature of 60~C and pH was maintained at about 3.2. The superficial anode current density was 2.7 A/dm and the cathode current density was 2~7 A/dm . Over a period of 32 and 44 days the anode materials of Examples Ia and Ib, respectively, dissolved and after an initial equilibration period, established the equilibrium composition of.the electrolyte with respect to ionic nickel/
iron ratio and maintained this composition substantially constant. The cathodic deposits produced were of commercial quality.
EXAMPLE IIIa The anode material of Example Ia was electrodissolved in a titanium basket in a proprietary decorative nickel-iron alloy plating bath having the following nominal composition at the start of dissolution as recommended by the proprietor:
NiS04 6H20 105 gpl NiC12 6H2 60 gpl H3B03 45 gpl Total Iron 2 gpl Proprietary Additives--as recommended by proprietor The bath was operated at a temperature of 60C and pH was maintained in the range 2.8 to 3.5. Brightener addi-tions were made as recommended during plating. The superficial anode current density was 3.6 A/dm and the cathode current density was 5.4 A/dm . Over a period of 42 days the anode material of Example Ia dissolved and after an initial equili-bration period, established and maintained the equilibrium 1 1817~
composition of the electrolyte as in Example II. The cathodic deposit was bright and level and of decorative quality.
EXAMPLE IIIb The anode material of Example Id was electrodissolved in a titanium basket in a proprietary decorative nickel-iron alloy plating bath different from the proprietary bath Example IIIa. This bath had the following nominal composition at the start of dissolution as recommended by the proprietor:
NiS04 6~20 85 gpl 10 2 2 135 gpl H3B03 45 gpl Proprietary Additives--as recommended by proprietor The bath was operated at a temperature of 57C and pH was maintained in the range 3.5 to 4Ø Brightener addi-tions were made as recommended during plating. Anode and cathode current densities were the same as in Example IIIa.
Over a period of 30 days the anode material of Example Ib dissolved and after an initial equilibration period, estab-lished and maintained the equilibrium composition of theelectrolyte as in Example II. The cathodic deposit was brlght and level and of decorative quality.
_XAMPLE IIIc The anode material of Example Ie was electrodissolved as in Example IIIb in a third proprietary decorative nickel-iron alloy plating bath different fro~ those of Examples IIIa and IIIb. This bath had the following nominal composition at the start of the dissolution as recommended by the proprietor:
NiS04 2 120 gpl NiC12 6H20 90 gpl t 16~"78~
H3BO3 43 ~pl Proprietor ~dditives--as recommended by proprietor The bath was operated at a temperature of 57C and - pH was maintained in the range 3.4 to 4.2. Brightener addi-tions were made as recommended during plating. Anode and cathode current densities were the same as in Example IIlb.
Over a period of 31 days the anode material of Example Ie dissolved and after an initial equilibration period established and maintained the equilibrium composition of the electrolyte as in Example II. The cathodic deposit was bright and level and of decorative quality.
EXAMPLE IV
The anode material of Example Ic was electrodissolved in a titanium basket in the plating bath of Example II and under the same operating conditions as Example II. Over a period of 39 days the anode material of Example Ic dissolved and after an initial equilibration period established the equilibrium composition of the electrolyte with respect to ionic nickel/iron ratio and maintained this composition sub-stantially constant. The cathodic deposit was of commercial quality.
The equilibrium composition of this electrolyte was, however, not maintained as constant using the anode of Example Ic as was the equilibrium composition of the electro~
lyte in Example II which used the anodes of Example Ia or Ib.
Abrupt changes in iron content relative to nickel about the equilibrium composition occurred as the anode material of Example Ic dissolved and settled in the anode basket and as fresh anode material was added to the basket. This behavior I ~ 61 7~'~2 indicates an excessive rate of iron dissolution relative to nickel dissolution in the anode material of Example Ic. The fluctuations of iron content of the electrolyte relative to nickel content in this example were not so great as to render the anode material of Example Ic inoperative because the high ratio of exposed nickel to iron surface area permitted the anode material of Example Ic to function adequately in this example despite the fact that the nickel contained essentially no activator.
Examples Ia, b, d, e, II, and LIa, b, c demonstrate a preferred aspect of the anode of the present invention when the nickel portion of the anode contains sulfur as an acti-vator. Examples Ic and IV show the action of anode of the present invention when the nickel is essentially sulfur-free~
These examples taken together demonstrate the importance of correlating the ratio of exposed nickel to iron surface area to the amount of activator in the nickel.
Although the present invention has been described in conjunction with preferred embodiments, it is to be understood that modifica~ions and variations may be resorted to without departing from the spirit and scope of the invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the invention and appended claims.
. ~
EXAMPLE Ia Anode material in accordance with the present inven-tion was made by the electrodeposition of 0.119 centimeter thickness of nickel containing about 200 to 300 ppm sulfur on both sides of a 0.079 centimeter thick iron sheet. The slleet was then sheared into square pieces 2.54 centimeter on edge to form anode material of the present invention having a ratio of surface area of nickel to exposed area of iron of about 19. The anode of this example contained about 75 nickel, 25% iron.
-6a-EXAMP:LE Ib Anode material was made in the same way as Exaple Ia except that type 1010 steel sheet 0.094 cm thick was used instead of iron sheet and the nickel was electrodeposited to a thickness of 0.131 cm to produce a ratio of surface area of nickel to exposed area of iron o:E about 16.3~ The anode of this example also contained about 75~ nickel, 25% iron.
EXAMPLE IC
Anode material was made in the same way as in Example Ia except that the nickel was essentially free of an activator, containing only 5 to 10 ppm sulfur.
EXAMPLE Id Anode material was made in a manner similar to Example Ib except that the nickel was electrodeposited to a thickness of 0.093 cm to produce anode material containing about 65%
nickel, 35~ iron. The ratio of exposed nickel to iron surface area of the anode material of this example is about 15.5.
EXAMPLE Ie Anode material was made in the same way as Example Ib except the sheet was sheared into square pieces 1.27 cm on edge to form anode material having a ratio of surface area of nickel to exposed area of iron of about 11Ø
EXAMPLE I I
The anode materials of Examples Ia and Ib were electrodissolved separately in a titanium basket in a plating bath having the following nominal composition at the start of dissolution:
NiSo4 6H20 300 g/liter NiCl 6H20 60 g/liter H3BO3 30 g/liter -I 16~7~
Sodit~ Gluconate 20 g/liter Sodium Saccharin 0.2 g/li.ter The bath was operated at a temperature of 60~C and pH was maintained at about 3.2. The superficial anode current density was 2.7 A/dm and the cathode current density was 2~7 A/dm . Over a period of 32 and 44 days the anode materials of Examples Ia and Ib, respectively, dissolved and after an initial equilibration period, established the equilibrium composition of.the electrolyte with respect to ionic nickel/
iron ratio and maintained this composition substantially constant. The cathodic deposits produced were of commercial quality.
EXAMPLE IIIa The anode material of Example Ia was electrodissolved in a titanium basket in a proprietary decorative nickel-iron alloy plating bath having the following nominal composition at the start of dissolution as recommended by the proprietor:
NiS04 6H20 105 gpl NiC12 6H2 60 gpl H3B03 45 gpl Total Iron 2 gpl Proprietary Additives--as recommended by proprietor The bath was operated at a temperature of 60C and pH was maintained in the range 2.8 to 3.5. Brightener addi-tions were made as recommended during plating. The superficial anode current density was 3.6 A/dm and the cathode current density was 5.4 A/dm . Over a period of 42 days the anode material of Example Ia dissolved and after an initial equili-bration period, established and maintained the equilibrium 1 1817~
composition of the electrolyte as in Example II. The cathodic deposit was bright and level and of decorative quality.
EXAMPLE IIIb The anode material of Example Id was electrodissolved in a titanium basket in a proprietary decorative nickel-iron alloy plating bath different from the proprietary bath Example IIIa. This bath had the following nominal composition at the start of dissolution as recommended by the proprietor:
NiS04 6~20 85 gpl 10 2 2 135 gpl H3B03 45 gpl Proprietary Additives--as recommended by proprietor The bath was operated at a temperature of 57C and pH was maintained in the range 3.5 to 4Ø Brightener addi-tions were made as recommended during plating. Anode and cathode current densities were the same as in Example IIIa.
Over a period of 30 days the anode material of Example Ib dissolved and after an initial equilibration period, estab-lished and maintained the equilibrium composition of theelectrolyte as in Example II. The cathodic deposit was brlght and level and of decorative quality.
_XAMPLE IIIc The anode material of Example Ie was electrodissolved as in Example IIIb in a third proprietary decorative nickel-iron alloy plating bath different fro~ those of Examples IIIa and IIIb. This bath had the following nominal composition at the start of the dissolution as recommended by the proprietor:
NiS04 2 120 gpl NiC12 6H20 90 gpl t 16~"78~
H3BO3 43 ~pl Proprietor ~dditives--as recommended by proprietor The bath was operated at a temperature of 57C and - pH was maintained in the range 3.4 to 4.2. Brightener addi-tions were made as recommended during plating. Anode and cathode current densities were the same as in Example IIlb.
Over a period of 31 days the anode material of Example Ie dissolved and after an initial equilibration period established and maintained the equilibrium composition of the electrolyte as in Example II. The cathodic deposit was bright and level and of decorative quality.
EXAMPLE IV
The anode material of Example Ic was electrodissolved in a titanium basket in the plating bath of Example II and under the same operating conditions as Example II. Over a period of 39 days the anode material of Example Ic dissolved and after an initial equilibration period established the equilibrium composition of the electrolyte with respect to ionic nickel/iron ratio and maintained this composition sub-stantially constant. The cathodic deposit was of commercial quality.
The equilibrium composition of this electrolyte was, however, not maintained as constant using the anode of Example Ic as was the equilibrium composition of the electro~
lyte in Example II which used the anodes of Example Ia or Ib.
Abrupt changes in iron content relative to nickel about the equilibrium composition occurred as the anode material of Example Ic dissolved and settled in the anode basket and as fresh anode material was added to the basket. This behavior I ~ 61 7~'~2 indicates an excessive rate of iron dissolution relative to nickel dissolution in the anode material of Example Ic. The fluctuations of iron content of the electrolyte relative to nickel content in this example were not so great as to render the anode material of Example Ic inoperative because the high ratio of exposed nickel to iron surface area permitted the anode material of Example Ic to function adequately in this example despite the fact that the nickel contained essentially no activator.
Examples Ia, b, d, e, II, and LIa, b, c demonstrate a preferred aspect of the anode of the present invention when the nickel portion of the anode contains sulfur as an acti-vator. Examples Ic and IV show the action of anode of the present invention when the nickel is essentially sulfur-free~
These examples taken together demonstrate the importance of correlating the ratio of exposed nickel to iron surface area to the amount of activator in the nickel.
Although the present invention has been described in conjunction with preferred embodiments, it is to be understood that modifica~ions and variations may be resorted to without departing from the spirit and scope of the invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the invention and appended claims.
. ~
Claims (4)
1. An electroplating anode material comprising a sheared piece of low carbon steel sheet coated on both sides with nickel, the ratio of the exposed area of nickel to the exposed area of steel in said sheared pieces being about 3 to about 80, the nickel containing from 0% to 0.2% of sulfur as an activator or from 0% to 5% of an activator other than sulfur, and the activator content of the nickel being related to the ratio of exposed areas of nickel to steel such that when the activator content of the nickel is zero or near zero, the ratio of the exposed areas is at the high end of the aforestated range and when the activator content of the nickel is near 0.2% if the activator is sulfur or is near 5% if the activator is a material other than sulfur the ratio of the exposed areas is at the low end of the afore-stated range.
2. An electroplating anode material as in claim 1 wherein the activator is sulfur.
3. An electroplating anode material as in claim 1 wherein the nickel on the steel sheet is a nickel electrodeposit.
4. An electroplating anode material as in claim 3 wherein the nickel electrodeposit contains co-deposited sulfur.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US92038378A | 1978-06-29 | 1978-06-29 | |
| US920,383 | 1978-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1161782A true CA1161782A (en) | 1984-02-07 |
Family
ID=25443641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000328133A Expired CA1161782A (en) | 1978-06-29 | 1979-05-23 | Nickel-coated electrode of sheared low carbon steel |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0006759A1 (en) |
| CA (1) | CA1161782A (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2208537A (en) * | 1937-09-17 | 1940-07-16 | Firestone Tire & Rubber Co | Art of vehicle suspension |
| GB520211A (en) * | 1938-11-22 | 1940-04-17 | Deutsch & Brenner Ltd | Improvements in or relating to anodes for electro-plating or depositing |
| GB539882A (en) * | 1939-09-16 | 1941-09-26 | Mond Nickel Co Ltd | Improvements relating to apparatus for electroplating |
| BE470874A (en) * | 1940-12-21 | |||
| DE1259666B (en) * | 1963-11-29 | 1968-01-25 | Ibm | Process for the galvanic deposition of a non-magnetostrictive nickel-iron alloy coating |
-
1979
- 1979-05-23 CA CA000328133A patent/CA1161782A/en not_active Expired
- 1979-06-28 EP EP79301254A patent/EP0006759A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0006759A1 (en) | 1980-01-09 |
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