US3506547A - Nickel-iron electrolytes containing hydrolyzing metal ions and process of electro-depositing ferromagnetic films - Google Patents

Nickel-iron electrolytes containing hydrolyzing metal ions and process of electro-depositing ferromagnetic films Download PDF

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US3506547A
US3506547A US668561A US3506547DA US3506547A US 3506547 A US3506547 A US 3506547A US 668561 A US668561 A US 668561A US 3506547D A US3506547D A US 3506547DA US 3506547 A US3506547 A US 3506547A
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bath
ions
nickel
iron
concentration
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US668561A
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Alphonse Ambrosia
Harald Dahms
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International Business Machines Corp
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International Business Machines Corp
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/24—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates from liquids
    • H01F41/26—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates from liquids using electric currents, e.g. electroplating

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  • the method is one for electroplating magnetic films of nickel iron alloys using conventional plating baths in which there is added metallic ions having hydrolysis constants in a pH range of from pH 2 to pH 7.
  • the method involves the preparing of an electrolytic bath comprising a nickel salt, an iron salt, an electrolyte and metal ions selected from the group consisting of aluminum, magnesium, and a rare earth metal.
  • the substrate to be plated is immersed in the above bath and subjected to an electrolytic action.
  • the plated film has uniform proportions of nickel and iron throughout the film thickness. Additionally, the plating bath is stable over a wide range of temperatures.
  • This invention relates to a method of electroplating magnetic films and to an improved electroplating bath therefor.
  • this initial iron-rich deposit becomes a severe problem. This is especially so in terms of the magnetostriction of the deposited film, since zero magnetostriction is achieved with alloys including approximately 80% nickel and iron. When the alloy varies by any considerable degree from these proportions, it does not exhibit zero magneto striction. Additionally, the prior art Ni-Fe plating baths are unstable especially when used at high temperatures. For example, such baths can be used only for about 1 to 2 hours, after which they become opaque due to the hydrolysis and oxidation of ferrous ions.
  • the current is thereafter reduced in time, and the shape of the current pulse is controlled so that the initial current of high magnitude is sufficient to cause more nickel to be deposited at that time and, thereafter, a sufiicient amount of nickel as the current is decreased, so that the proportions of nickel and iron remain essentially constant throughout the thickness of the film.
  • Patent No. 1,960,029 to Alexander G. Russell discloses an electrodeposition method in which the ratio of the metals to be deposited in the alloy is maintained constant in solution by providing separate anodes of nickel and iron and adjusting the anode areas in the solution so that the current flows through the anode in the proper amount to replace the metal removed from the solution at the cathode.
  • this method employs a conventional plating bath to which has been added metal ions exhibiting hydrolysis i.e., metal ions which form precipitable hydroxides, in the pH range of from pH 2 to pH 7 and having a deposition potential more negative than Fe and Ni, so that no electrodeposition of the additive occurs. Additionally, the prepared bath may be used for periods far in excess of the prior art plating bath without appreciable decomposition thereof.
  • FIG. 1 is a plot of nickel and iron deposition versus the concentration of a rare earth metal ion.
  • FIG. 2 is a plot of the ferric iron concentration variation with time for a conventional plating bath and for the plating bath of this invention.
  • FIG. 3 is a plot of the percentage of iron deposited versus current density.
  • FIG. 4 is a plot of the composition gradient versus time for the bath composition of this invention.
  • the plating bath preferably contains simple salts of iron, nickel, and a metal selected from the group consisting of aluminum, magnesium, lanthanum, cerium, praseodymium, erbium, europium, gadolinium, hafnium, lutetium, neodymium, scandium, samarium, thulium, yttrium, ytterbium, holmium, terbium, and other rare earth metal ions hydrolyzing in a pH range of from pH 2 and pH 7.
  • a metal selected from the group consisting of aluminum, magnesium, lanthanum, cerium, praseodymium, erbium, europium, gadolinium, hafnium, lutetium, neodymium, scandium, samarium, thulium, yttrium, ytterbium, holmium, terbium, and other rare earth metal ions hydrolyzing in a pH range of from pH 2 and
  • Iron is initially added as a ferrous salt, such as ferrous chloride (FeCl AH O), ferrous sulphate, or as other simple salts of iron.
  • the ferrous salt is present in amounts sufficient to produce -Fe++ ions in concentrations of from to 0.5 mole per liter.
  • Nickel is preferably added to the plating bath as nickel chloride (NiCl .6H O).
  • the nickel salt used is present in sufficient amounts to produce Ni++ ions in concentrations of from 0.1 to 0.5 mole per liter.
  • nickel species may appear as free nickel ions, nickel amine complexes, nickel chelates, nickel addition agent complexes, and nickel complex with other added metal salts.
  • Nickel may be added in the form of other salts, as an illustrative example, nickel sulphate, provided precipitation does not occur.
  • the form in which nickel exists in a given system depends upon many factors, such as nickel concentration, pH, ammonium ion concentration, chelate agent concentration, iron concentration, addition agent concentration, complexing agent concentration, temperature, and concentration of other metals.
  • Aluminum, magnesium, and the above rare earth elements have an appreciable effect on the plating bath; and it is preferably added to the bath in the form of a simple salt.
  • the choice of salts is dependent upon the ability of the given salt to dissolve in the plating bath, and that the metallic ion hydrolyzes before nickel and ferrous ions.
  • the nitrates, chlorides, sulphates, etc. are salts that are found to be satisfactory.
  • the rare earth metals are generally acquired as their sesquioxides, which are converted into one of the above mentioned salts.
  • the chloride salt of the rare earth metal is prepared by dissolving the sesquioxide in hot concentrated HCl, which is subsequently evaporated. The residue are crystals of the rare earth metal chloride.
  • the above salts are added to the bath in amounts of from 7 l0- to 1X10 mole per liter.
  • the pH of the bath is limited to a range of 1.5 to 7.
  • other additives, such as boric acid and saccharin may also be added to the bath.
  • Example I Several plating baths were prepared having the following composition: 0.2 mole of NiSO 0.2 mole of FeSo 10 gms. of H BO /liter and 2 10- mole of H 80 in one liter of water. Thulium chloride was added to each of the severally prepared baths in amounts sufficient to provide Tinions in the range of 1 10- to 1 10' A current having a current density of ma./
  • Example II The experiments of Example I were repeated except that Sc+++ ions were used in place of the Tm+++ ions in the same concentrations indicated. A curve of the results obtained was plotted, which closely approximated that shown in FIG. 1.
  • Example III The experiments of Example I were repeated except that Lu+++ ions were used in place of the T m+++ ions in the same concentrations indicated. A curve of the results obtained was plotted. The curve showed similar results to the curve shown in FIG. 1.
  • FIG. 2 Shown in FIG. 2 is the effect of the presence or absence of the Al ion on the rate of hydrolysis and oxidation of the Fe++ ions in baths 1 and 2.
  • the curve represented by the triangular points (bath 1) shows that the hydrolysis and oxidation of ferrous ions in the presence of aluminum ions proceeds at a much lower rate when compared to the representative curve of the conventional bath 2 (circular points). This effect is not simply due to the lowering of the pH, since equivalent additions of sulfuric acid to bath 1 do not produce a similar effect.
  • EXAMPLE V A substrate was immersed in a plating bath consisting of 0.4 mole of nickel sulphate, 0.2 mole of ferrous sulphate, 10 grams of H BO 10 mole of H SO 2X10- mole of Al(NO and one gram of Na-saccharine per liter. The plating bath was heated to a temperature of about 95 C. Nitrogen was continuously bubbled into the solution. A current having a varying current density from 15 to 35 milliamperes/centimeters was applied. The resulting films had a bright appearance. It was found that the plating bath remained completely free of any iron oxide deposits for 3 /2 hours.
  • the composition of the plated filn1 varies from 15% to 31% Fe.
  • This range of Fe composition can be plated from a conventional bath, only it the bath contains an Fe concentration as low as 1X10 mole.
  • This experiment demonstrates that with the addition of Al the iron content of the bath can be maintained at a much higher level and that the iron concentration of the bath does not have to be controlled as closely as in the case of plating from a conventional bath.
  • FIG. 4 shows that the iron composition gradients, which are commonly found in conventional constant current plating, do not occur in high temperature plating with the presence of aluminum, "magnesium, or a rare earth metal ion, i.e., the iron composition deposited from the baths of this invention remains relatively constant throughout the plating operation.
  • Example VI The experiment of Example V was repeated except that 0.2 mole of MgSo .7H O was substituted for the Results similar to those of Example V were obtained.
  • Salts of cerium, erbium, europium, gadolinium, hafnium, lanthanum, neodymium, samarium, terbium, yttrium, holmium, praseodymium, dysprosium and ytter bium can be added in similar baths given in Examples I to V1 in amounts such that that metal ion was present in a concentration range of from 1 l0- to 1 10 mole per liter. Since all metal ion additions had similar effects on plate composition and bath stability, it is thought that the hydrolysis of the added metal ions is mainly responsible for the effects observed.
  • An aqueous electrolytic bath for use in the process of deposition of a ferromagnetic coating on an electrical- 1y conductive substrate, said bath having a pH in the range of from 1.3 to 7 and including as essential constituents ferrous ions in a concentration in the range of 1X10 to 5 10- mole/1., Ni++ ions in a concentration in the range of 1X10 to 5 10- mole/l.
  • metallic ions having negative deposition potentials such that said metallic ions do not codeposit from said bath with said Ni++ and said Fe++ ions, said metallic ions being selected from the group consisting of Al, Ce, Er, Eu, Gd, Hf, La, Lu, Nd, Sc, Sm, Tm, Tb, Y, Yb, Dy, Pr and Ho, and being present in the range of about 1 10- to 1X 10- mole per liter.
  • a process for depositing a ferromagnetic thin film comprising the steps of:

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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US668561A 1967-09-18 1967-09-18 Nickel-iron electrolytes containing hydrolyzing metal ions and process of electro-depositing ferromagnetic films Expired - Lifetime US3506547A (en)

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DE (1) DE1796184A1 (enrdf_load_stackoverflow)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101388A (en) * 1977-03-30 1978-07-18 M & T Chemicals Inc. Prevention of anode bag clogging in nickel iron plating
US4231847A (en) * 1978-06-21 1980-11-04 Trw Inc. Electrodeposition of nickel-iron alloys having a low temperature coefficient and articles made therefrom

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1837355A (en) * 1926-09-08 1931-12-22 Bell Telephone Labor Inc Electrodeposition of alloys
US1960029A (en) * 1931-11-19 1934-05-22 Bell Telephone Labor Inc Electrodeposition of alloys
US3047475A (en) * 1958-09-25 1962-07-31 Burroughs Corp Method for producing magnetic materials
US3138785A (en) * 1959-05-21 1964-06-23 Ibm Deposited magnetic memory array
US3255033A (en) * 1961-12-28 1966-06-07 Ibm Electroless plating of a substrate with nickel-iron alloys and the coated substrate
US3271274A (en) * 1962-10-31 1966-09-06 Sperry Rand Corp Electrodeposition of a ternary alloy of nickel, iron and molybdenum

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1837355A (en) * 1926-09-08 1931-12-22 Bell Telephone Labor Inc Electrodeposition of alloys
US1960029A (en) * 1931-11-19 1934-05-22 Bell Telephone Labor Inc Electrodeposition of alloys
US3047475A (en) * 1958-09-25 1962-07-31 Burroughs Corp Method for producing magnetic materials
US3138785A (en) * 1959-05-21 1964-06-23 Ibm Deposited magnetic memory array
US3255033A (en) * 1961-12-28 1966-06-07 Ibm Electroless plating of a substrate with nickel-iron alloys and the coated substrate
US3271274A (en) * 1962-10-31 1966-09-06 Sperry Rand Corp Electrodeposition of a ternary alloy of nickel, iron and molybdenum

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101388A (en) * 1977-03-30 1978-07-18 M & T Chemicals Inc. Prevention of anode bag clogging in nickel iron plating
US4231847A (en) * 1978-06-21 1980-11-04 Trw Inc. Electrodeposition of nickel-iron alloys having a low temperature coefficient and articles made therefrom

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FR1582679A (enrdf_load_stackoverflow) 1969-10-03
GB1227220A (enrdf_load_stackoverflow) 1971-04-07
DE1796184A1 (de) 1972-03-30

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