US3671409A - Electrodeposition of nickel - Google Patents
Electrodeposition of nickel Download PDFInfo
- Publication number
- US3671409A US3671409A US34638A US3671409DA US3671409A US 3671409 A US3671409 A US 3671409A US 34638 A US34638 A US 34638A US 3671409D A US3671409D A US 3671409DA US 3671409 A US3671409 A US 3671409A
- Authority
- US
- United States
- Prior art keywords
- nickel
- bath
- bromide
- ions
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/08—Other arrangements or adaptations of exhaust conduits
- F01N13/087—Other arrangements or adaptations of exhaust conduits having valves upstream of silencing apparatus for by-passing at least part of exhaust directly to atmosphere
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Definitions
- the bath can include other electrodepositable metals besides nickel, so References Cited that the electrodeposition of hard nickel alloys can also be ac- UNXTED STATES PATENTS complished.
- nickel plating 3,271 ,274 9/1966 Guilio et al. ..204/43 baths are given 3,454.3 76 7/1969 Luce et al ..204/49 3,489,660 l/l970 Semienko et a].
- This invention relates to the electrodeposition of nickel and nickel-containing alloys and is particularly. concerned with providing an improved method of forming electrodeposits of nickel or of nickel alloys.
- Nickel electroplating commonly uses, as the electrolytic bath. a solution of a nickel salt, e.g. nickel sulphate or sulphamate or nickel chloride, other components being included to produce a harder deposit or to reduce stress or to improve the performance of the electrolytic process.
- a harder deposit normally involves the inclusion in the plating bath of a source of one or more metal ions in addition to nickel ions, so that more than one metal is plated out and the deposit is a nickel-based alloy.
- the reduction of stress and other improvements in the electrolytic process often involve the inclusion in the bath of components which do not plate out with the nickel, so that the deposit is nickel rather than a nickel alloy. Since essentially the same conditions apply to electroplating with nickel and to electroplating with nickel alloys, references to nickel plating herein are intended to refer generally to both nickel and nickel alloy deposits unless otherwise indicated.
- bromide is usually introduced as nickel bromide, as in the Harstan nickel sulphamate process.
- the amount of bromide used up till now has been relatively small, e. g. up to one-third of the amount of nickel present by weight.
- the present invention is based upon the use, in an acid nickel electrolyte including a source of nickel ions, an amount of bromide ions in excess of the amount stoichiometrically equivalent to the amount of nickel ions calculated as nickel bromide.
- a nickel plating bath comprises an aqueous solution containing at least one water-soluble nickel salt as a source of nickel ions and at least one water-soluble bromide as a source of bromide ions, the amount of the bromide preferably being to times and most preferably l0 times the amount of nickel by weight. Stated otherwise, the amount of bromide ions present is greater than if the nickel ions are derived from nickel bromide as the sole source of nickel ions in the bath.
- the invention also provides a method of forming a nickel or nickel alloy electrodeposit, which may be an electroform, which comprises electrolyzing a plating bath of the composition just defined. 7
- the benefits of the present invention are obtained with any bromide which has the essential requirements of being watersoluble and of not containing any ions which might adversely affect the performance of the bath.
- the invention can be carried out both with sodium bromide and with potassium bromide.
- the other alkali metal bromides and ammonium bromide can be used. It is surprising that bromides are effective in the way now discovered, for it has been found that sodium and potassium iodides have no comparable effect to that of the corresponding bromides.
- the electrodeposit or electroform formed with a plating bath according to this invention can either be nickel or a nickel-based alloy.
- the requisite source of nickel ions can, if
- nickel bromide which also contributes to the source of bromide ions also needed, though in this case additional bromide ions must be provided.
- Any other water-soluble nickel compound can also provide the source of nickel ions, though for most practical baths it is constituted by nickel chloride.
- the source of bromide ions is preferably provided by sodium bromide, which is the water-soluble bromide most readily available.
- the other alkali metal bromides which are regarded as comprising those of potassium, ammonium, lithium, rubidium and caesium for the purposes of this invention are also eminently suitable, though the latter three are somewhat costly. More than one bromide can be provided in the same bath if desired.
- the acidity of the plating bath is important and in practice the pH of the bath should not normally be above 5.0 and, for most purposes, not above 4.0.
- a preferred range of pH is 1.8-4.0, the most suitable pl-l usually being about 3.5; higher pHs up to 4.5 are suitable if the bath is formulated so as to produce an alloy deposit.
- Electrodepositable metal ions which can be included are, for example, one or more of cobalt, iron, zinc, manganese, uranium, molybdenum and vanadium.
- the invention can be used for the electrodeposition of low-stress or even substantially stress-free nickel/cobalt, nickel/iron and other alloys.
- Another advantageous feature of the invention consists in the optional inclusion in a nickel or nickel alloy bath of the invention of a small amount of sulphite ion, e.g. provided in the form of sodium sulphite.
- a suitable quantity is constituted by up to 0.6 g/l of sodium sulphite; larger concentrations are possible, but it is usually unnecessary to use them.
- the main benefit afforded is stress reduction in the resultant deposits; low stress, coupled with high throwing power and heat-resistance, are characteristic benefits of the invention; with the inclusion of sodium sulphite, the stress can be further reduced and it is possible to obtain deposits with virtually no stress or even with compressive stress.
- Organic stress reducers i.e. compounds which are known to have a reducing effect upon the stress in a deposit, may be incorporated in baths of the invention inorder to augment the tendency of the bathos to produce low-stress deposits or to ensure that stress is maintained sufficiently low.
- Suitable additives for this include saccharin, sodium naphthalene trisulphonate, sodium meta-benzene disulphonate and other conventional stress reducers.
- the acid electrolyte of the invention serves to produce an evenly distributed nickel or alloy deposit over a wide current density range, without excessive over-growths; stated otherwise, the electrolyte has high throwing power.
- Throwing power may be defined as the characteristic of a solution which determines the evenness with which a metal may be deposited from it.
- There are several methods of determining the throwing power of a solution such as those based upon the Haring cell or the Field apparatus.
- the test used to determine the throwing power of the present invention is that which was used for the solution described in specification No. 765,958, namely: weighing the deposit per unit area at the extreme inside center of a angular test piece consisting of two square faces 2 X 2 inches at right angles to each other, stopped off at the back, dividing this weight by the weight per unit area deposited on the extreme outside corners and multiplying the result by 100.
- the deposits obtained by electrolyzing a bath according to the invention without conventional stress reducers are heatresistant, for instance they are capable of being brazed.
- Heatresistant deposits have hitherto only been obtained from solutions which have a low inherent stress, such as nickel sulphamate baths. Such solutions usually have a low throwing power and consequently produce deposits which have very uneven distribution with nodular over-growths.
- the invention for the first time provides a bath capable of forming a nickel or nickel alloy deposit at high throwing power, the deposit being both heat-resistant and free from excessive stress.
- a nickel deposit produced with a bath according to this invention typically has a Rockwell C hardness in the range of 20-30 Rc. Harder deposits can be obtained by modifying the bath composition and the conditions of operating and hardnesses of 50 Re or even higher can be achieved.
- One effect of the inclusion of other electrodepositable ions besides nickel ions in the bath is to produce a nickel alloy deposit which is often characterized by greater hardness.
- cobalt, manganese, molybdenum and vanadium and mixtures thereof in particular, when incorporated in the high bromide bath of the invention, preferably as the respective chlorides, give hard alloy deposits. For example, 5 g/l of cobalt gives hardnesses up to 480 DPN and 0.1-0.5 g/l of manganese gives hardnesses up to 350 DPN.
- the deposits have a very low stress, which can often be obtained without the use of organic stress reducers, and can be produced at relatively high current densities, e.g. up to 100 A.S.F.
- the plating bath of the invention can be used without agitation or with agitation, such as air agitation, stirring or rod movement.
- the solutions of this invention provide a combination of good hardness, ductility and low stress characteristic of nickel deposited without the use of organic stress reducers.
- Typical plating bath compositions of the invention are as follows:
- Ni l-60 H BO 32 (25-40) Breg provided as NaBr or KBr) 100-600 pH 3.0-4.0 Operating temperature l850 C.
- EXAMPLE 1 A bath was made up as an aqueous solution of the following composition:
- the bath had a pH of 3,5 and was operated at 40 C. at a current density of up to 40 ASP. in still conditions and up to 80 ASP. with air or other agitation.
- step (3) is cong/l tinued until an electroformed article is obtained which has a minimum thickness of about 0.1 inch.
- Nickel sulphate I79 4- A method as claimed in claim 1, wherein the bath also Boric acid 32 contains at least one source of metal ions selected from the Sodium bromide 400 group of metals consisting of cobalt, iron, zinc, manganese,
- an electroforming bath of acidic pH and devoid of ammonium ions which comprises an aqueous solution containing a nickel ion source and at least one water-soluble bromide as a source of bromide ions in which the weight of bromide in the aq the weight of nickel, 2. immersing a substrate in 5.
- the bath contains a source of sulphite ions.
- step (3) is car ried out in a static bath at a current density below about 50 A.S.F.
- An electrolytic bath for the production of electroformed nickel articles comprising an acidic aqueous solution, devoid of ammonium ions, and comprising a source of nickel ions and at least one water-soluble bromide as a source of bromide ions, the weight of bromide being 5 to 20 times the weight of nickel.
- ueous solution is 5 to 20 times the electroforming bath for
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2328569 | 1969-05-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3671409A true US3671409A (en) | 1972-06-20 |
Family
ID=10193186
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US34638A Expired - Lifetime US3671409A (en) | 1969-05-07 | 1970-05-04 | Electrodeposition of nickel |
Country Status (10)
Country | Link |
---|---|
US (1) | US3671409A (de) |
CH (1) | CH534743A (de) |
DE (1) | DE2020840C3 (de) |
ES (1) | ES379357A1 (de) |
FR (2) | FR2042462B1 (de) |
GB (1) | GB1289511A (de) |
IL (1) | IL34459A0 (de) |
NL (1) | NL7006301A (de) |
SE (1) | SE353352B (de) |
ZA (1) | ZA703053B (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4743346A (en) * | 1986-07-01 | 1988-05-10 | E. I. Du Pont De Nemours And Company | Electroplating bath and process for maintaining plated alloy composition stable |
US4846941A (en) * | 1986-07-01 | 1989-07-11 | E. I. Du Pont De Nemours And Company | Electroplating bath and process for maintaining plated alloy composition stable |
US4849303A (en) * | 1986-07-01 | 1989-07-18 | E. I. Du Pont De Nemours And Company | Alloy coatings for electrical contacts |
US5672262A (en) * | 1993-08-18 | 1997-09-30 | The United States Of America, As Represented By The Secretary Of Commerce | Methods and electrolyte compositions for electrodepositing metal-carbon alloys |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1524748A (en) * | 1976-05-28 | 1978-09-13 | Inco Europ Ltd | Production of hard heat-resistant nickel-base electrodeposits |
US4699696A (en) * | 1986-04-15 | 1987-10-13 | Omi International Corporation | Zinc-nickel alloy electrolyte and process |
DK172937B1 (da) * | 1995-06-21 | 1999-10-11 | Peter Torben Tang | Galvanisk fremgangsmåde til dannelse af belægninger af nikkel, kobalt, nikkellegeringer eller kobaltlegeringer |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB902499A (en) * | 1960-03-02 | 1962-08-01 | Albright & Wilson Mfg Ltd | Electodeposition of bright nickel deposits from a pyrophosphate bath |
US3244603A (en) * | 1962-06-08 | 1966-04-05 | Gen Electric | Electrodeposition of a nickel-manganese alloy |
US3271274A (en) * | 1962-10-31 | 1966-09-06 | Sperry Rand Corp | Electrodeposition of a ternary alloy of nickel, iron and molybdenum |
GB1059915A (en) * | 1966-11-25 | 1967-02-22 | John Preston And Company Chemi | Improvements relating to bright nickel electroplating |
US3454376A (en) * | 1966-06-06 | 1969-07-08 | Clevite Corp | Metal composite and method of making same |
US3489660A (en) * | 1966-01-03 | 1970-01-13 | Honeywell Inc | Electroplating bath and method |
-
0
- FR FR16632A patent/FR16632E/fr not_active Expired
-
1969
- 1969-05-07 GB GB2328569A patent/GB1289511A/en not_active Expired
-
1970
- 1970-04-29 NL NL7006301A patent/NL7006301A/xx unknown
- 1970-04-29 DE DE2020840A patent/DE2020840C3/de not_active Expired
- 1970-04-30 CH CH650770A patent/CH534743A/de not_active IP Right Cessation
- 1970-05-04 SE SE06086/70A patent/SE353352B/xx unknown
- 1970-05-04 US US34638A patent/US3671409A/en not_active Expired - Lifetime
- 1970-05-04 IL IL34459A patent/IL34459A0/xx unknown
- 1970-05-05 ZA ZA703053A patent/ZA703053B/xx unknown
- 1970-05-06 FR FR7016632A patent/FR2042462B1/fr not_active Expired
- 1970-05-06 ES ES379357A patent/ES379357A1/es not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB902499A (en) * | 1960-03-02 | 1962-08-01 | Albright & Wilson Mfg Ltd | Electodeposition of bright nickel deposits from a pyrophosphate bath |
US3244603A (en) * | 1962-06-08 | 1966-04-05 | Gen Electric | Electrodeposition of a nickel-manganese alloy |
US3271274A (en) * | 1962-10-31 | 1966-09-06 | Sperry Rand Corp | Electrodeposition of a ternary alloy of nickel, iron and molybdenum |
US3489660A (en) * | 1966-01-03 | 1970-01-13 | Honeywell Inc | Electroplating bath and method |
US3454376A (en) * | 1966-06-06 | 1969-07-08 | Clevite Corp | Metal composite and method of making same |
GB1059915A (en) * | 1966-11-25 | 1967-02-22 | John Preston And Company Chemi | Improvements relating to bright nickel electroplating |
Non-Patent Citations (1)
Title |
---|
Endicott et al., Plating, Vol. 43, No. 1, p. 47 Jan. 1966 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4743346A (en) * | 1986-07-01 | 1988-05-10 | E. I. Du Pont De Nemours And Company | Electroplating bath and process for maintaining plated alloy composition stable |
US4846941A (en) * | 1986-07-01 | 1989-07-11 | E. I. Du Pont De Nemours And Company | Electroplating bath and process for maintaining plated alloy composition stable |
US4849303A (en) * | 1986-07-01 | 1989-07-18 | E. I. Du Pont De Nemours And Company | Alloy coatings for electrical contacts |
US5672262A (en) * | 1993-08-18 | 1997-09-30 | The United States Of America, As Represented By The Secretary Of Commerce | Methods and electrolyte compositions for electrodepositing metal-carbon alloys |
Also Published As
Publication number | Publication date |
---|---|
DE2020840B2 (de) | 1973-07-12 |
FR2042462B1 (de) | 1973-11-16 |
DE2020840C3 (de) | 1974-02-14 |
ES379357A1 (es) | 1972-10-16 |
NL7006301A (de) | 1970-11-10 |
GB1289511A (de) | 1972-09-20 |
DE2020840A1 (de) | 1971-02-04 |
SE353352B (de) | 1973-01-29 |
CH534743A (de) | 1973-03-15 |
FR2042462A1 (de) | 1971-02-12 |
IL34459A0 (en) | 1970-07-19 |
ZA703053B (en) | 1971-01-27 |
FR16632E (fr) | 1913-03-18 |
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